CN110467583B - Production method of 3-isothiazolinone stable aqueous solution - Google Patents
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Abstract
The invention provides a method for synthesizing a bactericide 3-isothiazolinone stable aqueous solution, which comprises the following steps: the method for synthesizing the bactericide 3-isothiazolinone aqueous solution by taking methyl acrylate, sulfur powder and hydrogen sulfide as starting raw materials through steps of sulfuration, amide, chloro-cyclization, elimination, neutralization and the like in the same reaction tower kettle. The method realizes the cyclic reaction of gas-liquid materials by using the reaction kettle and the gas-liquid reaction device of the reaction tower, improves the high-efficiency cyclic utilization of the materials, particularly the gas materials, and effectively improves the product yield; the corresponding tail gas of each stage of reaction is respectively used as absorption liquid by the corresponding reaction raw material, and the absorption liquid can be circularly used for the reaction raw material. The method does not need to purify and separate intermediate products, realizes continuous feeding of each step of the product, is simple and easy to operate, and is beneficial to realizing industrial production; no waste liquid is generated in the synthesis process, and the method is safe and environment-friendly.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a production method of a 3-isothiazolinone stable aqueous solution, in particular to a method for producing a 3-isothiazolinone aqueous solution by taking methyl acrylate as a raw material through addition, amidation and chlorination ring closure.
Background
The 3-isothiazolinone mainly comprises 2-methyl-4-isothiazolinone-3-ketone and 5-chlorine-2-methyl-4-isothiazolinone-3-ketone, is a non-oxidation type bactericide with low toxicity and high spectrum efficiency, is widely applied to the fields of steel, oil fields, oil refining, power generation, paper making, coatings, industrial cleaning and the like due to the characteristics of high biocidal efficiency, good degradability, safe operation, good compatibility, low use cost and the like, and in many practical applications, the isothiazolinone needs to be prepared into a solution form, and particularly, polar organic substances such as water or ethanol are used as a solvent.
A large number of reports are made on the synthesis method of isothiazolinone in domestic and foreign literatures. Chinese patent CN102786455B discloses a preparation method for preparing 3-isothiazolinone bactericide intermediate N, N ' -dialkyl-3,3 ' -dithiodipropionamide by amidation reaction of 3,3' -dithiodipropionic acid methyl ester and hydrocarbyl amine with alcohol or acetone as solvent and sodium alkoxide as catalyst. Patent CN102786491B discloses a method for preparing bactericide 2-methyl-4-isothiazolin-3-one by taking N, N '-dimethyl-3,3' -dithiodipropionamide or N-methyl-3-mercaptopropionamide as raw materials and reacting with chlorine under the catalysis of alkali metal iodide in the presence of a solvent. The US patent No. 5466818 describes a method for synthesizing a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one by using N-methyl-3-mercaptopropionamide and chlorine as raw materials and ethyl acetate as a solvent. Chinese patent CN104961705B discloses a one-pot synthesis process of 4,5-dichloro-2-methylisothiazolinone by using methyl acrylate as a starting material and respectively introducing hydrogen sulfide gas, methylamine gas and chlorine gas at different stages. The prior process methods all have the problems of complex operation, high separation cost, large wastewater yield, environmental pollution, low yield and the like.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for producing 3-isothiazolinone, which is convenient to operate by using a tower kettle type reaction, free of waste water generation, safe and environment-friendly.
A production method of bactericide 3-isothiazolinone is realized by the following technical scheme:
(1) Synthesis of 3,3' -Dithiodipropionic acid methyl ester: adding metered methyl acrylate, sulfur powder and a catalyst into a reaction kettle in sequence, controlling the reaction temperature to be 20-30 ℃, pumping a gas-liquid mixed material in the kettle into a reaction packed tower through a material circulating pump while slowly introducing hydrogen sulfide gas to react, circularly spraying the reaction material into the reaction kettle through the bottom of the reaction kettle, circularly reacting for 3~5 hours until no solid matter exists in the kettle, and preparing a 3,3' -dithiodipropionic acid methyl ester crude product, wherein hydrogen sulfide tail gas generated in the reaction process enters a primary tail gas absorption device through the top of the packed tower;
(2) Synthesis of N, N '-dimethyl-3,3' -dithiodipropionic acid dipropionamide: adding a certain amount of organic solvent into the reaction product obtained in the step (1), controlling the temperature in a reaction kettle to be 20-30 ℃, introducing methylamine gas at a constant speed, simultaneously pumping a gas-liquid mixed material into a packed tower for mixing reaction through a circulating pump, circularly spraying the reaction material into the reaction kettle through the bottom of the tower, keeping the temperature of a reaction system at 50 +/-2 ℃ after carrying out circular reaction for 10-15 hours, and evaporating methanol generated in the reaction under reduced pressure at-0.05-0.06 MPa to obtain a faint yellow N, N '-dimethyl-3,3' -dithiodipropionamide solution, wherein methylamine gas tail gas generated in the reaction process enters a secondary tail gas absorption device through the top of the packed tower;
(3) Synthesis of 3-isothiazolinone aqueous solution: controlling the temperature in the reaction kettle to be 0~5 ℃, introducing a certain amount of chlorine into a product system obtained in the step (2), introducing the chlorine, simultaneously introducing a gas-liquid mixed material into a packed tower through a circulating pump to perform in-vitro mixing reaction, circularly spraying the reaction material into the reaction kettle through the bottom of the tower, after performing cyclic reaction for 2 hours, stopping introducing the chlorine, performing heat preservation reaction for 1.5 to 3 hours at room temperature, heating, performing reduced pressure distillation to recover a reaction solvent, adding a certain amount of deionized water for dilution, adding magnesium oxide for neutralization to obtain a stable 2-methyl-4-isothiazoline-3-one and 5-chloro-2-methyl-4-isothiazoline-3-one mixed aqueous solution, wherein chlorine tail gas generated in the reaction process enters a three-stage tail gas absorption device through the top of the packed tower.
The mass ratio of the methyl acrylate, the sulfur powder and the substances introduced with the hydrogen sulfide in the step (1) is 2: (1.0 to 1.5): (1.0 to 1.8); wherein, preferably, n Acrylic acid methyl ester ：n s ：n H2S =2:（1.0~1.2）：（1.0~1.3）。
The mass percentage of the catalyst in the step (1) in the feeding amount of the methyl acrylate is 1 to 10 percent; wherein, preferably, the mass percentage of the catalyst used in the feeding amount of the methyl acrylate is 2~4%.
The catalyst in the step (1) can be selected from aqueous solutions of ammonium sulfide, sodium sulfide, methylamine or ammonia gas and the like; wherein, the catalyst is preferably selected from ammonium sulfide or methylamine water solution with the mass percentage concentration of 20 to 30 percent.
The 3,3' -dithiodipropionic acid methyl ester crude product in the step (1) is analyzed by gas chromatography and comprises the following components: 3,3' -dithiodipropionic acid methyl ester content 75-82%; the content of the methyl polythiodipropionate is 13 to 17 percent; methyl monothiopropionate content 3~5%.
The organic solvent in the step (2) may be any one of dichloroethane and ethyl acetate.
The mass ratio of the organic solvent in the step (2) to the methyl acrylate in the step (1) is (1.0 to 2.0): 1; wherein, the mass ratio of the two is preferably (1.2 to 1.5): 1.
the molar ratio of the introduced methylamine gas in the step (2) to the methyl acrylate in the step (1) is (1.0 to 1.5): 1; among them, the molar ratio of the two is preferably (1.05 to 1.15): 1.
the molar ratio of the introduced chlorine gas in the step (3) to the methyl acrylate in the step (1) is (2.0 to 4.0): 1; wherein, the molar ratio of the two is preferably (2.7 to 3.2): 1.
the active content of the 3-isothiazolinone aqueous solution in the step (3) can be 0.5 to 15 percent.
In the step (3), the mass ratio of the effective components 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one in the 3-isothiazolinone aqueous solution is 1: (0.8 to 3.5).
The absorption liquid in the tail gas absorption device in the step (1) is a mixed system of methyl acrylate, sulfur powder and a catalyst, and the absorption liquid can be recycled for the reaction raw materials in the step (1).
The absorption liquid in the tail gas absorption device in the step (2) is the reaction product solution in the step (1), and the absorption liquid can be recycled for the reaction raw material in the step (2).
The absorption liquid in the tail gas absorption device in the step (3) is the reaction product solution in the step (2), and the absorption liquid can be recycled for the reaction raw material in the step (3).
And (3) introducing the gas into the kettle in the steps (1), (2) and (3) at a constant speed under liquid.
The invention has the beneficial effects that:
(1) By adopting a tower kettle type extracorporeal circulation reaction method, the gas continuously introduced in each stage of the reaction and the liquid material continuously and circularly sprayed from the reaction tower are reversely mixed, so that the reaction is more sufficient; meanwhile, the reaction tail gas absorption liquid in each stage is the reaction raw material in the previous step, so that the efficient recycling of materials, particularly gas materials, is facilitated, and the product yield is effectively improved;
(2) The method does not need to purify and separate intermediate products, realizes continuous feeding of each step of the product, is simple and easy to operate, and is beneficial to realizing industrial production;
(3) The production method of the invention has no waste liquid, and is safe and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of the synthesis method of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
For the purpose of further explaining the meaning of the present invention, the following examples are given for the purpose of illustration and are not intended to limit the scope of the present invention.
Example 1
Adding 694g of 99 mass percent methyl acrylate, 128g of sulfur powder and 27.76g of 27 mass percent methylamine aqueous solution into a reaction kettle in sequence, controlling the reaction temperature to be 25 +/-2 ℃, slowly introducing 150g of hydrogen sulfide gas, pumping the gas-liquid mixture in the kettle into a reaction packed tower through a material circulating pump, then circularly spraying the gas-liquid mixture into the reaction kettle through the bottom of the reaction kettle, circularly reacting in sequence until no solid matter is shared in the kettle for 3.5 hours to prepare 3,3 '-methyl dithiodipropionate crude product, and analyzing the composition of the 3,3' -methyl dithiodipropionate crude product through gas chromatography detection: 3,3' -Dithiodipropionic acid methyl ester content 81.32%; the content of methyl polythiodipropionate is 14.21 percent; the content of methyl monothiopropionate is 3.39%, wherein hydrogen sulfide tail gas generated in the reaction process enters a first-stage tail gas absorption device through the top of a packed tower;
835g of dichloroethane solvent is added into the reaction kettle, the temperature in the reaction kettle is controlled to be 28 +/-2 ℃, the total amount of methylamine gas is 261g at a constant speed, meanwhile, a gas-liquid mixed material is pumped into a packed tower through a circulating pump, the reaction material is sprayed into the reaction kettle through the circulation of the tower bottom, after the material is completely circulated into the reaction kettle after the circulation reaction is carried out for 12 hours, the temperature of a reaction system is raised to 50 +/-2 ℃, methanol generated by the reaction is evaporated under reduced pressure of-0.05 to-0.06 MPa, a light yellow N, N '-dimethyl-3,3' -dithiodipropionic acid dipropionamide solution is obtained, wherein methylamine gas tail gas generated in the reaction process enters a secondary tail gas absorption device through the tower top of the packed tower;
controlling the temperature in the reaction kettle to be 0~5 ℃, controlling the flow rate of chlorine gas to be 1.0L/min, continuously introducing the chlorine gas into the product for 2 hours, simultaneously pumping the gas-liquid mixed material into a packed tower through a circulating pump to perform in-vitro mixing reaction, and circularly spraying the reaction material into the reaction kettle through the tower bottom. After chlorine is introduced, when materials are completely circulated into the reaction kettle, after the materials are subjected to heat preservation reaction for 2.5 hours under the condition of room temperature, the temperature of the system is raised to 65 ℃, and simultaneously-0.05 MPa negative pressure external evaporation is established to recover 795.78g of reaction solvent, and through detection, the liquid chromatographic contents of 2-methyl-4-isothiazoline-3-ketone and 5-chloro-2-methyl-4-isothiazoline-3-ketone in reaction products are 53.71% and 44.74% respectively;
adding a certain amount of deionized water and magnesium oxide into the product for neutralization to obtain an aqueous solution of 3-isothiazolinone with the mass percentage of 0.5-15%; the tail gas absorption liquid of each stage can be circularly used for the reaction raw material of the stage; the external evaporation solvent dichloroethane can be recycled.
Example 2
Adding 694g of 99 mass percent methyl acrylate, 163.2g of sulfur powder and 20.82g of 27 mass percent methylamine aqueous solution into a reaction kettle in sequence, controlling the reaction temperature to be 28 +/-2 ℃, slowly introducing 164g of hydrogen sulfide gas, pumping the gas-liquid mixture in the kettle into a reaction packed tower through a material circulating pump, then circularly spraying the gas-liquid mixture into the reaction kettle through the bottom of the reaction kettle, circularly reacting in sequence until no solid matter is shared in the kettle for 4 hours to prepare a 3,3 '-methyl dithiodipropionate crude product, and analyzing the composition of the 3,3' -methyl dithiodipropionate crude product through gas chromatography detection: 3,3' -Dithiodipropionic acid methyl ester content 76.09%; the content of the methyl polythiodipropionate is 16.38 percent; the content of methyl monothiopropionate is 4.58%, wherein hydrogen sulfide tail gas generated in the reaction process enters a first-stage tail gas absorption device through the top of a packed tower;
835g of ethyl acetate solvent is added into the reaction kettle, the temperature in the reaction kettle is controlled to be 25 +/-2 ℃, methane gas is introduced at a constant speed to account for 275g, meanwhile, a gas-liquid mixed material is injected into a packed tower through a circulating pump, the reaction material is sprayed into the reaction kettle through the circulation of the bottom of the tower, the material is completely circulated into the reaction kettle after the circulation reaction is carried out for 10 hours, the temperature of a reaction system is raised to 50 +/-2 ℃, methanol generated by the reaction is evaporated under reduced pressure of-0.05 to-0.06 MPa, a light yellow N, N '-dimethyl-3,3' -dithiodipropionic acid dipropionamide solution is obtained, wherein the methylamine gas tail gas generated in the reaction process enters a secondary tail gas absorption device through the top of the packed tower;
controlling the temperature in the reaction kettle to be 0~5 ℃, controlling the flow rate of chlorine gas to be 1.5L/min, continuously introducing chlorine gas into the product for 1.5 hours, simultaneously pumping the gas-liquid mixed material into a packed tower through a circulating pump to perform in-vitro mixing reaction, and circularly spraying the reaction material into the reaction kettle through the bottom of the tower. After chlorine is introduced, when materials are completely circulated into the reaction kettle, the materials are subjected to heat preservation reaction for 2.5 hours under the condition of room temperature, the temperature of the system is raised to 55 ℃, simultaneously negative pressure of-0.05 MPa is established, the reaction solvent is externally evaporated and recovered, the total amount of 804.27g is calculated, and through detection, the liquid chromatographic contents of 2-methyl-4-isothiazoline-3-ketone and 5-chloro-2-methyl-4-isothiazoline-3-ketone in reaction products are respectively 45.86% and 52.91%;
adding a certain amount of deionized water and magnesium oxide into the product for neutralization to obtain an aqueous solution of 3-isothiazolinone with the mass percentage of 0.5-15%; the tail gas absorption liquid of each stage can be circularly used for the reaction raw material of the stage; the external evaporation solvent dichloroethane can be recycled.
Example 3
Adding 694g of 99 mass percent methyl acrylate, 163.2g of sulfur powder and 13.88g of 27 mass percent methylamine aqueous solution into a reaction kettle in sequence, controlling the reaction temperature to be 25 +/-2 ℃, slowly introducing 136g of hydrogen sulfide gas, pumping the gas-liquid mixture in the kettle into a reaction packed tower through a material circulating pump, then circularly spraying the gas-liquid mixture into the reaction kettle through the bottom of the reaction kettle, circularly reacting in sequence until no solid matter is shared in the kettle for 5 hours to prepare 3,3 '-methyl dithiodipropionate crude product, and analyzing the composition of the 3,3' -methyl dithiodipropionate crude product through gas chromatography detection: 3,3' -Dithiodipropionic acid methyl ester content 75.31%; the content of the methyl polythiodipropionate is 15.28 percent; the content of methyl monothiopropionate is 3.07 percent, wherein hydrogen sulfide tail gas generated in the reaction process enters a first-stage tail gas absorption device through the top of a packed tower;
835g of dichloroethane solvent is added into the reaction kettle, the temperature in the reaction kettle is controlled to be 28 +/-2 ℃, methylamine gas is introduced at a constant speed to account for 286g, meanwhile, a gas-liquid mixed material is injected into a packed tower through a circulating pump, the reaction material is sprayed into the reaction kettle through the circulation of the tower bottom, after the material is completely circulated into the reaction kettle after the circulation reaction is carried out for 12 hours, the temperature of a reaction system is raised to 50 +/-2 ℃, methanol generated by the reaction is evaporated under reduced pressure of-0.05 to-0.06 MPa, and a faint yellow N, N '-dimethyl-3,3' -dithiodipropionic acid dipropionamide solution is obtained, wherein methylamine gas tail gas generated in the reaction process enters a secondary tail gas absorption device through the tower top of the packed tower;
controlling the temperature in the reaction kettle to be 0~5 ℃, controlling the flow rate of chlorine gas to be 1.2L/min, continuously introducing chlorine gas into the product for 2 hours, simultaneously pumping the gas-liquid mixed material into a packed tower through a circulating pump to carry out in-vitro mixing reaction, and circularly spraying the reaction material into the reaction kettle through the bottom of the tower. After chlorine is introduced, when materials are completely circulated into the reaction kettle, after the materials are subjected to heat preservation reaction for 3 hours under the condition of room temperature, raising the temperature of the system to 65 ℃, simultaneously establishing negative pressure of-0.05 MPa, externally evaporating and recovering reaction solvents to totally 796.42g, and detecting that the liquid chromatogram contents of 2-methyl-4-isothiazoline-3-ketone and 5-chloro-2-methyl-4-isothiazoline-3-ketone in reaction products are 33.15% and 64.28% respectively;
adding a certain amount of deionized water and magnesium oxide into the product for neutralization to obtain an aqueous solution of 3-isothiazolinone with the mass percentage of 0.5-15%; the tail gas absorption liquid of each stage can be circularly used for the reaction raw material of the stage; the external evaporation solvent dichloroethane can be recycled.
Claims (4)
1. A production method of a 3-isothiazolinone stable aqueous solution is characterized by comprising the following steps:
(1) Synthesis of methyl 3,3' -dithiodipropionate: adding methyl acrylate, sulfur powder and a catalyst into a reaction kettle in sequence, controlling the reaction temperature to be 20-30 ℃, slowly introducing hydrogen sulfide gas while pumping the mixed materials in the kettle into a reaction tower through a material circulating pump for reaction, circularly spraying the reaction materials into the reaction kettle through the bottom of the reaction tower, circularly reacting for 3-5 hours in sequence until no solid exists in the kettle, and preparing a crude product of the methyl 3,3' -dithiodipropionate, wherein hydrogen sulfide tail gas generated in the reaction process enters a primary tail gas absorption device through the top of the reaction tower;
(2) Synthesis of N, N '-dimethyl-3, 3' -dithiodipropionic acid dipropionamide: adding an organic solvent into the reaction product obtained in the step (1), controlling the temperature in a reaction kettle to be 20-30 ℃, introducing methylamine gas at a constant speed, simultaneously pumping a gas-liquid mixed material into a filler tower through a circulating pump for mixing reaction, circularly spraying the reaction material into the reaction kettle through the bottom of the tower, circularly reacting for 10-15 hours, keeping the temperature of a reaction system at 50 +/-2 ℃, and distilling under reduced pressure at-0.05 to-0.06 MPa to remove methanol and part of solvent generated by the reaction to obtain a faint yellow N, N '-dimethyl-3, 3' -dithiodipropionic acid dipropionamide solution, wherein excessive methylamine gas escapes from the top of the reaction tower in the reaction process and enters a secondary tail gas absorption device, and distillate can be recycled through rectification separation;
(3) Synthesis of 3-isothiazolinone aqueous solution: controlling the temperature in the reaction kettle to be 0-5 ℃, introducing a certain amount of chlorine into the product system obtained in the step (2), introducing the chlorine and simultaneously introducing a gas-liquid mixed material into the reaction tower through a circulating pump to perform in-vitro mixing reaction, circularly spraying the reaction material into the reaction kettle through the bottom of the tower, stopping introducing the chlorine after performing the circular reaction for 2 hours, performing heat preservation reaction for 1.5-3 hours at room temperature, heating, performing reduced pressure distillation to recover a reaction solvent, adding deionized water for dilution, and adding magnesium oxide for neutralization to obtain a stable 2-methyl-4-isothiazoline-3-one and 5-chloro-2-methyl-4-isothiazoline-3-one mixed aqueous solution, wherein chlorine tail gas generated in the reaction process enters a three-stage tail gas absorption device through the top of a packed tower;
the mass ratio of any one of dichloroethane or ethyl acetate as an organic solvent in the step (2) to the methyl acrylate in the step (1) is 1.0-2.0: 1;
the tail gas absorption liquid in the step (1) is a mixed system of methyl acrylate, sulfur powder and a catalyst, and the absorption liquid can be recycled for the reaction raw materials in the step (1);
the tail gas absorption liquid in the step (2) is a reaction product in the step (1), and the absorption liquid can be recycled for a reaction raw material in the step (2);
the tail gas absorption liquid in the step (3) is a reaction product in the step (2), and the absorption liquid can be recycled for a reaction raw material in the step (3);
the mass ratio of the methyl acrylate, the sulfur powder, the hydrogen sulfide, the methylamine gas and the chlorine gas in the materials in the steps (1), (2) and (3) is n Acrylic acid methyl ester ：n Sulfur powder ：n Hydrogen sulfide ：n Methylamine ：n Chlorine gas =2： 1.0 ~ 1.5：1.0 ~ 1.8：2.0 ~ 2.5：2 .0 ~ 4.0；
The catalyst in the step (1) is an aqueous solution of ammonium sulfide, sodium sulfide, methylamine or ammonia gas.
2. The method according to claim 1, wherein the amount of the catalyst is 1-10% by mass based on the amount of the fed methyl acrylate.
3. The method according to claim 1, wherein the active content of the 3-isothiazolone aqueous solution in the step (3) is 0.5-20%, wherein the mass ratio of the effective components 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one is 1:0.8 to 3.5.
4. A method according to claim 1, wherein the gas is introduced into the reactor in steps (1), (2) and (3) at a constant velocity under liquid.
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