CN110467583A - A kind of production method of 3- isothiazolinone stability aqueous solution - Google Patents
A kind of production method of 3- isothiazolinone stability aqueous solution Download PDFInfo
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Abstract
The present invention provides a kind of synthetic method of fungicide 3- isothiazolinone stability aqueous solution, this method specifically includes following content: in the same reaction tower reactor realize using methyl acrylate, sulphur powder and hydrogen sulfide as starting material, respectively by vulcanization, amide, chloro cyclization, cancellation, neutralization and etc. synthesizing fungicide 3- isothiazolinone aqueous solution method.This method realizes the circular response of gas-liquid material by using reaction kettle and reaction tower gas-liquid reaction apparatus, and the efficient circulation for improving each material especially gas material utilizes, and effectively improves product yield；Respectively by corresponding reaction raw materials as absorbing liquid, absorbing liquid can be recycled for reaction raw materials the corresponding tail gas of each order reaction.The method of the present invention does not need to carry out the purification of intermediate product, separation, realizes that the continuity of each step of product feeds intake, simple to operation, is conducive to realize industrialized production；Synthesis process is without waste liquid generation, safety and environmental protection.
Description
Technical field
The invention belongs to organic chemical synthesis fields, and in particular to a kind of production of 3- isothiazolinone stability aqueous solution
Method, more particularly to it is a kind of using methyl acrylate as raw material, through addition, amidation and chlorination loop production 3- isothiazolinone water
The method of solution.
Background technique
3- isothiazolinone is mainly by 2-methyl-4-isothiazolin-3-one and 5- chloro-2-methyl -4- isothiazoline -3-
Ketone composition is a kind of less toxic, efficient non-oxidative bactericide of spectrum, because with killing livestock, high-efficient, degradability is good, operation peace
Entirely, the features such as compatibility is good, use cost is low and be widely used in steel, oil field, oil refining, power generation, papermaking, coating and industry
The fields such as cleaning need isothiazolinone solution form is made in many practical applications, especially with water or ethyl alcohol etc.
Polar organic matter matter is as solvent.
About the synthetic method of isothiazolinone, domestic and foreign literature has a large amount of reports.Chinese patent CN102786455B
One kind is disclosed using alcohol or acetone as solvent, sodium alkoxide is catalyst, makes 3,3`- dimethyl propionate of dithio and alkylamine that acyl occur
The preparation side of aminating reaction preparation 3- isothiazolinone disinfecting agent intermediate N, N`- dialkyl -3,3`- dithio dipropyl acidamide
Method.Patent CN102786491B disclose it is a kind of in the presence of solvent, with N, N`- dimethyl -3,3`- dithio dipropyl acidamide or
N- methyl -3- mercaptopropionyl amine is raw material, reacts under alkaline metal iodide catalysis with chlorine and prepares fungicide 2- methyl -
The preparation method of -3 ketone of 4- isothiazoline.United States Patent (USP) US5466818 describe it is a kind of using N- methyl -3- mercaptopropionyl amine,
Chlorine is raw material, synthesizes 5-Chloro-2-methyl-4-isothiazolin-3-one and 2- methyl -4- isothiazole by solvent of ethyl acetate
The method of the mixture of quinoline -3- ketone.Chinese patent CN104961705B discloses one kind using methyl acrylate as starting material, leads to
Cross different phase each lead into hydrogen sulfide gas, methylamine gas and chlorine mode one pot process bis- chloro-2-methyls of 4,5- it is different
The technique of thiazolinone.In such existing process, there is complicated for operation, separation costs are high, waste water yield is big, environment
The problems such as pollution and low yield.
Summary of the invention
In order to solve the problems, such as that prior art exists, the present invention provide it is a kind of it is convenient using tower reactor formula operation,
No waste water generates, the production method of the 3- isothiazolinone of safety and environmental protection.
A kind of production method of fungicide 3- isothiazolinone is realized especially by following technical solution:
(1) synthesis of 3,3'- dimethyl propionate of dithio: the methyl acrylate measured, sulphur powder and catalyst are sequentially added
In reaction kettle, 20 ~ 30 DEG C of reaction temperature are controlled, gas-liquid mixed material in kettle is passed through into material when being slowly introducing hydrogen sulfide gas
Circulating pump is squeezed into reaction packed tower and is reacted, and the reacted tower bottom circulation of reaction mass is drenched into reaction kettle, according to this circular response 3
Exist into kettle without solid matter within ~ 5 hours, 3,3'- dimethyl propionate of dithio crude product is made, the sulphur that wherein reaction process generates
Change hydrogen tail gas and enters level-one device for absorbing tail gas through filler column overhead；
(2) synthesis of N, N'- dimethyl -3,3'- dithiodipropionic acid dipropyl acidamide: a certain amount of organic solvent is added above-mentioned
In reaction product obtained by step (1), control reactor temperature is 20 ~ 30 DEG C, while being at the uniform velocity passed through methylamine gas, by following
Gas-liquid mixed material is squeezed into the reaction of packed tower mixing by ring pump, and reaction mass, into reaction kettle, recycles according to this through tower bottom circulation leaching
After reaction 10 ~ 15 hours, keeping temperature of reaction system is 50 ± 2 DEG C, removes what reaction generated under -0.05 ~ -0.06MPa under reduced pressure
Methanol obtains faint yellow N, N'- dimethyl -3,3'- dithiodipropionic acid dipropyl acidamide solution, the methylamine that wherein reaction process generates
Tail-gas enters second level device for absorbing tail gas through filler column overhead；
(3) synthesis of 3- isothiazolinone aqueous solution: control reactor temperature is 0 ~ 5 DEG C, in above-mentioned steps (2) products therefrom
It is passed through a certain amount of chlorine in system, while being passed through chlorine, gas-liquid mixed material is squeezed by packed tower by circulating pump and is carried out
External mixing reaction, reaction mass is through tower bottom circulation leaching into reaction kettle, and according to this after circular response 2 hours, stopping is passed through chlorine,
After reaction dissolvent is recycled in heating vacuum distillation, a certain amount of deionized water dilution is added in insulation reaction 1.5 ~ 3 hours at room temperature,
It is added after magnesia neutralizes up to stability 2-methyl-4-isothiazolin-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one
Mixed aqueous solution, the chlorine tail gas that wherein reaction process generates enter three-level device for absorbing tail gas through filler column overhead.
Methyl acrylate described in above-mentioned steps (1), sulphur powder and be passed through hydrogen sulfide the mass ratio of the material be 2:(1.0 ~
1.5): (1.0 ~ 1.8)；Wherein, preferably, nMethyl acrylate: ns: nH2S=2:(1.0 ~ 1.2): (1.0 ~ 1.3).
The mass percent that catalyst amount described in above-mentioned steps (1) accounts for methyl acrylate inventory is 1 ~ 10%；Its
In, preferably, the mass percent that catalyst amount accounts for methyl acrylate inventory is 2 ~ 4%.
Catalyst described in above-mentioned steps (1) can choose as the aqueous solution of ammonium sulfide, vulcanized sodium, methylamine or ammonia etc.；
Wherein, preferably, catalyst choice is the ammonium sulfide or methylamine water solution that mass percent concentration is 20 ~ 30%.
3,3'- dimethyl propionate of dithio crude product described in above-mentioned steps (1) is through its constituent of makings chromatography are as follows:
3,3'- dimethyl propionate of dithio content 75 ~ 82%；More thio-2 acid methyl ester contents 13 ~ 17%；Single thio-methyl propionate content
3~5%。
Organic solvent described in above-mentioned steps (2) can choose as any one of dichloroethanes or ethyl acetate.
The mass ratio of methyl acrylate is (1.0 ~ 2.0) in organic solvent described in above-mentioned steps (2) and step (1):
1；Wherein, preferably, the two mass ratio is (1.2 ~ 1.5): 1.
The molar ratio that methyl acrylate in methylamine gas and step (1) is passed through described in above-mentioned steps (2) is (1.0 ~ 1.5):
1；Wherein, preferably, the molar ratio of the two is (1.05 ~ 1.15): 1.
The molar ratio that methyl acrylate in chlorine and step (1) is passed through described in above-mentioned steps (3) is (2.0 ~ 4.0): 1；
Wherein, preferably, the molar ratio of the two is (2.7 ~ 3.2): 1.
3- isothiazolinone aqueous solution active quantities described in above-mentioned steps (3) can be 0.5 ~ 15%.
In 3- isothiazolinone aqueous solution described in above-mentioned steps (3) effective component 2-methyl-4-isothiazolin-3-one and
The mass ratio of 5-Chloro-2-methyl-4-isothiazolin-3-one is 1:(0.8 ~ 3.5).
Absorbing liquid is methyl acrylate, sulphur powder and catalyst mixing in device for absorbing tail gas described in above-mentioned steps (1)
System, the absorbing liquid can be recycled for step (1) reaction raw materials.
Absorbing liquid is step (1) reaction product solution, the absorbing liquid in device for absorbing tail gas described in above-mentioned steps (2)
It can recycle for step (2) reaction raw materials.
Absorbing liquid is step (2) reaction product solution, the absorbing liquid in device for absorbing tail gas described in above-mentioned steps (3)
It can recycle for step (3) reaction raw materials.
Gas described in above-mentioned steps (1), (2) and (3), which enters kettle mode and is all made of under liquid, to be at the uniform velocity passed through.
Beneficial effect of the invention:
(1) method reacted by using tower reactor formula extracorporal circulatory system, make to react gas that each stage is constantly passed through with from reaction tower
Liquid material under continuous circulation leaching forms reverse mixing, reacts more abundant；Each elementary reaction tail gas absorption liquid is respectively simultaneously
Previous step reaction raw materials utilize conducive to the efficient circulation for realizing each material especially gas material, effectively improve product yield；
(2) this method does not need to carry out the purification of intermediate product, separation, realizes that the continuity of each step of product feeds intake, simple easy
Operation is conducive to realize industrialized production；
(3) production method of the present invention is without waste liquid generation, safety and environmental protection.
Detailed description of the invention
Fig. 1 is synthetic method schematic diagram of the present invention.
Specific embodiment
For convenience of further description meaning of the present invention, below with reference to embodiment to content according to the present invention into
Row is illustrated, but is not defined to its content.
Embodiment 1
The first for being 27% by methyl acrylate 694g, sulphur powder 128g and mass percent that the mass percentage measured is 99%
Amine aqueous solution 27.76g is sequentially added in reaction kettle, is controlled 25 ± 2 DEG C of reaction temperature, is slowly introducing hydrogen sulfide gas 150g, together
When gas-liquid mixture in kettle squeezed into reaction packed tower by Matter Transfer pump, then reacted tower bottom circulation leaching to reaction kettle
In, it circuits sequentially when reaction is shared into kettle without solid matter 3.5 hours, 3,3'- dimethyl propionate of dithio crude product, warp is made
Gas chromatographic detection analyzes 3,3'- dimethyl propionate of dithio crude product constituent are as follows: 3,3'- dimethyl propionate of dithio content
81.32%；More thio-2 acid methyl ester contents 14.21%；Single thio-methyl propionate content 3.39%, wherein reaction process generates
Hydrogen sulfide tail gas enters level-one device for absorbing tail gas through filler column overhead；
835g dichloroethane solvent is added into aforesaid reaction vessel, control reactor temperature is 28 ± 2 DEG C, is at the uniform velocity passed through methylamine
Gas amounts to 261g, meanwhile, gas-liquid mixed material is squeezed by packed tower by circulating pump, reaction mass is through tower bottom circulation leaching to reaction
In kettle, after 12 hours materials of circular response are all recycled in reaction kettle according to this, increase temperature of reaction system to 50 ± 2 DEG C ,-
It removes the methanol that reaction generates under 0.05 ~ -0.06MPa under reduced pressure, obtains faint yellow N, N'- dimethyl -3,3'- dithiodipropionic acid two
Propionyl amine aqueous solution, the methylamine tail-gas that wherein reaction process generates enter second level device for absorbing tail gas through filler column overhead；
Controlling reactor temperature is 0 ~ 5 DEG C, and control chlorine flow velocity is that 1.0 L/min are continuously passed through chlorine 2 into above-mentioned product
Hour, while gas-liquid mixed material is squeezed by packed tower by circulating pump and carries out external mixing reaction, reaction mass is followed through tower bottom
Ring is drenched into reaction kettle.Chlorine, which is passed through, to be finished, when material is all recycled in reaction kettle, system insulation reaction under room temperature
After 2.5 hours, raising system temperature is established outside -0.05MPa negative pressure simultaneously to 65 DEG C steams the total 795.78g of recycling reaction dissolvent,
Through detecting, 2-methyl-4-isothiazolin-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one liquid chromatogram in reaction product
Content is respectively 53.71% and 44.74%；
A certain amount of deionized water is added in above-mentioned product and magnesia neutralizes, and can obtain the 3- that mass percentage content is 0.5 ~ 15%
The aqueous solution of isothiazolinone；Tail gas absorption liquid at different levels are circularly used for the order reaction raw material；Outer steaming solvent dichloroethanes can be with
It recycles.
Embodiment 2
It is 27% by methyl acrylate 694g, sulphur powder 163.2g and mass percent that the mass percentage measured is 99%
Methylamine water solution 20.82g is sequentially added in reaction kettle, is controlled 28 ± 2 DEG C of reaction temperature, is slowly introducing hydrogen sulfide gas 164g,
Gas-liquid mixture in kettle is squeezed into reaction packed tower by Matter Transfer pump simultaneously, then reacted tower bottom circulation leaching to reaction kettle
In, it circuits sequentially when reaction is shared into kettle without solid matter 4 hours, 3,3'- dimethyl propionate of dithio crude product is made, through gas
Phase chromatography tests and analyzes 3,3'- dimethyl propionate of dithio crude product constituent are as follows: 3,3'- dimethyl propionate of dithio content
76.09%；More thio-2 acid methyl ester contents 16.38%；Single thio-methyl propionate content 4.58%, wherein reaction process generates
Hydrogen sulfide tail gas enters level-one device for absorbing tail gas through filler column overhead；
835g ethyl acetate solvent is added into aforesaid reaction vessel, control reactor temperature is 25 ± 2 DEG C, is at the uniform velocity passed through methylamine
Gas amounts to 275g, meanwhile, gas-liquid mixed material is squeezed by packed tower by circulating pump, reaction mass is through tower bottom circulation leaching to reaction
In kettle, after 10 hours materials of circular response are all recycled in reaction kettle according to this, increase temperature of reaction system to 50 ± 2 DEG C ,-
It removes the methanol that reaction generates under 0.05 ~ -0.06MPa under reduced pressure, obtains faint yellow N, N'- dimethyl -3,3'- dithiodipropionic acid two
Propionyl amine aqueous solution, the methylamine tail-gas that wherein reaction process generates enter second level device for absorbing tail gas through filler column overhead；
Controlling reactor temperature is 0 ~ 5 DEG C, and control chlorine flow velocity is that 1.5 L/min are continuously passed through chlorine into above-mentioned product
1.5 hours, while gas-liquid mixed material is squeezed by packed tower by circulating pump and carries out external mixing reaction, reaction mass is through tower bottom
Circulation leaching is into reaction kettle.Chlorine, which is passed through, to be finished, and when material is all recycled in reaction kettle, system is kept the temperature instead under room temperature
After answering 2.5 hours, raising system temperature is established steaming recycling reaction dissolvent outside -0.05MPa negative pressure to 55 DEG C simultaneously and is amounted to
804.27g, through detecting, 2-methyl-4-isothiazolin-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one in reaction product
Liquid chromatogram content is respectively 45.86% and 52.91%；
A certain amount of deionized water is added in above-mentioned product and magnesia neutralizes, and can obtain the 3- that mass percentage content is 0.5 ~ 15%
The aqueous solution of isothiazolinone；Tail gas absorption liquid at different levels are circularly used for the order reaction raw material；Outer steaming solvent dichloroethanes can be with
It recycles.
Embodiment 3
It is 27% by methyl acrylate 694g, sulphur powder 163.2g and mass percent that the mass percentage measured is 99%
Methylamine water solution 13.88g is sequentially added in reaction kettle, is controlled 25 ± 2 DEG C of reaction temperature, is slowly introducing hydrogen sulfide gas 136g,
Gas-liquid mixture in kettle is squeezed into reaction packed tower by Matter Transfer pump simultaneously, then reacted tower bottom circulation leaching to reaction kettle
In, it circuits sequentially when reaction is shared into kettle without solid matter 5 hours, 3,3'- dimethyl propionate of dithio crude product is made, through gas
Phase chromatography tests and analyzes 3,3'- dimethyl propionate of dithio crude product constituent are as follows: 3,3'- dimethyl propionate of dithio content
75.31%；More thio-2 acid methyl ester contents 15.28%；Single thio-methyl propionate content 3.07%, wherein reaction process generates
Hydrogen sulfide tail gas enters level-one device for absorbing tail gas through filler column overhead；
835g dichloroethane solvent is added into aforesaid reaction vessel, control reactor temperature is 28 ± 2 DEG C, is at the uniform velocity passed through methylamine
Gas amounts to 286g, meanwhile, gas-liquid mixed material is squeezed by packed tower by circulating pump, reaction mass is through tower bottom circulation leaching to reaction
In kettle, after 12 hours materials of circular response are all recycled in reaction kettle according to this, increase temperature of reaction system to 50 ± 2 DEG C ,-
It removes the methanol that reaction generates under 0.05 ~ -0.06MPa under reduced pressure, obtains faint yellow N, N'- dimethyl -3,3'- dithiodipropionic acid two
Propionyl amine aqueous solution, the methylamine tail-gas that wherein reaction process generates enter second level device for absorbing tail gas through filler column overhead；
Controlling reactor temperature is 0 ~ 5 DEG C, and control chlorine flow velocity is that chlorine 2 is continuously passed through into above-mentioned product is small by 1.2L/min
When, while gas-liquid mixed material is squeezed by packed tower by circulating pump and carries out external mixing reaction, reaction mass is recycled through tower bottom
Leaching is into reaction kettle.Chlorine, which is passed through, to be finished, when material is all recycled in reaction kettle, system insulation reaction 3 under room temperature
After hour, raising system temperature is established outside -0.05MPa negative pressure simultaneously to 65 DEG C steams the total 796.42g of recycling reaction dissolvent, through examining
It surveys, 2-methyl-4-isothiazolin-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one liquid chromatogram content in reaction product
Respectively 33.15% and 64.28%；
A certain amount of deionized water is added in above-mentioned product and magnesia neutralizes, and can obtain the 3- that mass percentage content is 0.5 ~ 15%
The aqueous solution of isothiazolinone；Tail gas absorption liquid at different levels are circularly used for the order reaction raw material；Outer steaming solvent dichloroethanes can be with
It recycles.
Claims (10)
1. a kind of production method of 3- isothiazolinone stability aqueous solution, which is characterized in that specifically comprise the following steps:
The synthesis of (1) 3,3'- dimethyl propionate of dithio: methyl acrylate, sulphur powder and catalyst are sequentially added in reaction kettle,
20 ~ 30 DEG C of reaction temperature of control is squeezed into mixed material in kettle instead by Matter Transfer pump when being slowly introducing hydrogen sulfide gas
Answer tower to be reacted, reaction mass reacted tower bottom circulation leaching into reaction kettle, according to this circular response 3 ~ 5 hours into kettle without solid
Body substance exists, and 3,3'- dimethyl propionate of dithio crude product is made, the reacted tower of hydrogen sulfide tail gas that wherein reaction process generates
Tower top enters level-one device for absorbing tail gas；
(2) above-mentioned steps (1) synthesis of N, N'- dimethyl -3,3'- dithiodipropionic acid dipropyl acidamide: is added in organic solvent
In gained reaction product, control reactor temperature is 20 ~ 30 DEG C, while being at the uniform velocity passed through methylamine gas, will by circulating pump
Gas-liquid mixed material squeeze into packed tower mixing reaction, reaction mass through tower bottom circulation leaching into reaction kettle, according to this circular response 10 ~
After 15 hours, keeping temperature of reaction system is 50 ± 2 DEG C, the methanol that vacuum distillation is generated except dereaction under -0.05 ~ -0.06MPa
And partial solvent, faint yellow N is obtained, N'- dimethyl -3,3'- dithiodipropionic acid dipropyl acidamide solution, wherein reaction process is excessive
The reacted column overhead of methylamine gas escapes into second level device for absorbing tail gas, and distillate separates Ke Xunhuanliyong through rectifying；
(3) synthesis of 3- isothiazolinone aqueous solution: control reactor temperature is 0 ~ 5 DEG C, in above-mentioned steps (2) products therefrom
It is passed through a certain amount of chlorine in system, while being passed through chlorine, gas-liquid mixed material is squeezed by reaction tower by circulating pump and is carried out
External mixing reaction, reaction mass is through tower bottom circulation leaching into reaction kettle, and according to this after circular response 2 hours, stopping is passed through chlorine,
After reaction dissolvent is recycled in heating vacuum distillation, deionized water dilution is added, and oxygen is added in insulation reaction 1.5 ~ 3 hours at room temperature
Change after magnesium neutralizes up to stability 2-methyl-4-isothiazolin-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one mixing water
Solution, the chlorine tail gas that wherein reaction process generates enter three-level device for absorbing tail gas through filler column overhead.
2. a kind of method according to claim 1, which is characterized in that the step (1), (2), each material third in (3)
E pioic acid methyl ester, sulphur powder, hydrogen sulfide, methylamine gas and chlorine the mass ratio of the material that feeds intake be nMethyl acrylate: nSulphur powder: nHydrogen sulfide: nMethylamine: nChlorine=2:
1.0 ~ 1.5:1.0 ~ 1.8:2.0 ~ 2.5:2.0 ~ 4.0.
3. a kind of method according to claim 1, which is characterized in that in the step (1) catalyst can choose for
The aqueous solution of ammonium sulfide, vulcanized sodium, methylamine or ammonia etc..
4. according to claim 1 with method described in 3, which is characterized in that the catalyst amount accounts for methyl acrylate and feeds intake
The mass percent of amount is 1 ~ 10%.
5. a kind of method according to claim 1, which is characterized in that organic solvent dichloroethanes in the step (2)
Or the mass ratio of methyl acrylate is 1.0 ~ 2.0:1 in any and step (1) of ethyl acetate.
6. a kind of method according to claim 1, which is characterized in that 3- isothiazolinone is water-soluble in the step (3)
Liquid active quantities can be 0.5 ~ 20%, and wherein effective component 2-methyl-4-isothiazolin-3-one and 5- chloro-2-methyl -4- are different
The mass ratio of thiazoline -3- ketone is 1:0.8 ~ 3.5.
7. a kind of method according to claim 1, which is characterized in that tail gas absorption liquid is propylene in the step (1)
Sour methyl esters, sulphur powder and catalyst mixed system, the absorbing liquid are circularly used for the reaction raw materials of step (1).
8. a kind of method according to claim 1, which is characterized in that tail gas absorption liquid is step in the step (2)
(1) reaction product, the absorbing liquid are circularly used for step (2) reaction raw materials.
9. a kind of method according to claim 1, which is characterized in that tail gas absorption liquid is step in the step (3)
(2) reaction product, the absorbing liquid are circularly used for step (3) reaction raw materials.
10. a kind of method according to claim 1, which is characterized in that gas enters in the step (1), (2) and (3)
Kettle mode is all made of under liquid and is at the uniform velocity passed through.
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| CN113698326A (en) * | 2021-08-06 | 2021-11-26 | 唐山金硕化工有限公司 | Method and device for pipeline type continuous production of thiopropionate series compounds |
| CN113698326B (en) * | 2021-08-06 | 2024-04-09 | 唐山金硕化工有限公司 | Method and device for continuously producing thiopropionate series compounds through pipeline |
| CN115838346A (en) * | 2022-10-08 | 2023-03-24 | 大连百傲化学股份有限公司 | Method for synthesizing N, N '-dialkyl-3, 3' -dithiodipropionamide by one-pot method |
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