CN113999183B - Preparation method of trichloroisocyanuric acid - Google Patents
Preparation method of trichloroisocyanuric acid Download PDFInfo
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- CN113999183B CN113999183B CN202111317635.0A CN202111317635A CN113999183B CN 113999183 B CN113999183 B CN 113999183B CN 202111317635 A CN202111317635 A CN 202111317635A CN 113999183 B CN113999183 B CN 113999183B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/36—Only oxygen atoms having halogen atoms directly attached to ring nitrogen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A novel preparation method of trichloroisocyanuric acid relates to the field of chemical product production, and comprises the following steps: adding chlorinated isocyanate and an organic solvent into a reaction vessel, adding an initiator, controlling the temperature of the system between 10 ℃ and reflux temperature, and separating and purifying the reaction system to obtain the trichloroisocyanuric acid product.
Description
Technical Field
The invention relates to the field of chemical product production, in particular to a preparation method of trichloroisocyanuric acid.
Background
The trichloroisocyanuric acid is a high-efficiency, safe and broad-spectrum novel chlorine preparation, has the characteristics of high active chlorine content, strong sterilization bleaching power, long free chlorine release time in water, stable storage, convenient use and the like, can replace traditional disinfectants such as bleaching powder, bleaching essence, peracetic acid, hydrogen peroxide, 84 disinfectant and the like, and is widely applied to sterilization and disinfection of drinking water, swimming pools, tableware, hotels, hospitals, food processing industry, aquaculture, public environment and the like, and is also applied to aspects of industrial water treatment agent, industrial cleaning, bleaching agent and the like in printing and dyeing industry. The patent (CN 86104526) takes urea as a raw material, cyanuric acid is generated by condensation at high temperature, the cyanuric acid reacts with alkali liquor to prepare a trisodium cyanurate solution, and then the trisodium cyanurate solution reacts with chlorine to obtain trichloroisocyanuric acid. The patent (CN 102329275 a) first chlorinates cyanuric acid to prepare dichloroisocyanuric acid, then prepares an aqueous solution of sodium dichloroisocyanurate, and uses liquid chlorine to react with the aqueous solution of sodium dichloroisocyanurate to produce trichloroisocyanuric acid. The process has the defects of complex process, more waste water, the need of using corrosive toxic gas chlorine, and the easiness of generating nitrogen trichloride, explosion risk when the nitrogen trichloride reaches a certain concentration, and poor process safety. The patent (CN 101899015 a) first hydrolyzes chlorine with water and then reacts the hydrolysis product with calcium carbonate and cyanuric acid to form trichloroisocyanuric acid, although the risk of chlorine reacting with cyanuric acid to form nitrogen trichloride is avoided. However, chlorine is also used, and impurities contained in the solid of the product cannot be removed, so that it is difficult to produce trichloroisocyanuric acid containing impurities up to the standard.
The above processes are all to synthesize trichloroisocyanuric acid by chloridizing reaction through cyanuric acid approach.
Disclosure of Invention
The invention develops a method for preparing trichloroisocyanuric acid by a free radical cyclization way, which has the characteristics of simple process, mild condition, good safety and high atom economy.
The technical scheme adopted by the invention is as follows:
a process for producing trichloroisocyanuric acid, which comprises the following steps:
the method comprises the following steps:
under the inert gas environment, adding chlorinated isocyanate and an organic solvent into a reaction container, adding an initiator, controlling the temperature of the system to be between 10 ℃ and reflux temperature for reaction, and separating and purifying the reaction system after the reaction is finished to obtain the trichloroisocyanuric acid product.
In some embodiments, the organic solvent may be selected from tetrahydrofuran, benzene, toluene, n-hexane, cyclohexane, acetonitrile, or mixtures thereof. In some embodiments, the organic solvent is tetrahydrofuran or acetonitrile.
In some embodiments, the mass ratio of the chlorinated isocyanate to the organic solvent is about 1:1 to about 1:10, preferably about 1:2 to about 1:4.
in some embodiments, the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, potassium persulfate, ammonium persulfate, benzoyl peroxide, di-tert-butyl peroxide, and the preferred initiator is azobisisobutyronitrile, and the molar ratio of chlorinated isocyanate to initiator is 1:0.001 to 1:1, preferably 1:0.01 to 1:0.05. the reaction temperature is 10 to 100 ℃, preferably about 40 to about 60 ℃.
In some embodiments, the separation and purification is recrystallised from acetone and water
In some embodiments the separation and purification uses acetone and water to recrystallize the initiator and organic solvent as a combination of azobisisobutyronitrile and acetonitrile.
The invention has the beneficial effects that:
the method is characterized in that chlorinated isocyanate is selected as a raw material, the trichloroisocyanuric acid is prepared by one-step cyclization through free radical initiation, and the optimal reaction conditions are obtained through optimization and screening of the reaction conditions, so that the yield of one-step cyclization reaches 96%.
Detailed Description
The invention is further illustrated by the following examples:
example 1
In a dry 1000mL three-necked flask, a magnetic stirrer was added, a thermometer and a reflux condenser were equipped, the reaction apparatus was evacuated, nitrogen was charged, and after repeating three times, chlorinated isocyanate (155 g,2 mol), azobisisobutyronitrile (6.6 g,0.02 eq) and acetonitrile (465 g) were sequentially added under the protection of nitrogen, and the oil bath was warmed to an internal temperature of 50℃for 10 hours. After the reaction is completed, the solvent is recovered by decompression concentration, the residue is recrystallized by acetone and water, and 142.5g of trichloroisocyanuric acid product is obtained by drying, the effective chlorine content is 91.2%, and the yield is 95.9% based on chlorinated isocyanate.
Example 2
In a dry 1000mL three-necked flask, a magnetic stirrer was added, a thermometer and a reflux condenser were equipped, the reaction apparatus was evacuated, nitrogen was charged, and after repeating three times, chlorinated isocyanate (155 g,2 mol), benzoyl peroxide (9.7 g,0.02 eq) and acetonitrile (465 g) were sequentially added under the protection of nitrogen, and the temperature of the oil bath was raised to an internal temperature of 50℃to react for 10 hours. After the reaction is completed, the solvent is removed by decompression concentration, the residue is recrystallized by acetone and water, 131.8g of trichloroisocyanuric acid product is obtained by drying, the effective chlorine content is 90.2%, and the yield is 85% based on chlorinated isocyanate.
Example 3
In a dry 1000mL three-necked flask, a magnetic stirrer was added, a thermometer and a reflux condenser were equipped, the reaction apparatus was evacuated, nitrogen was charged, and after repeating three times, chlorinated isocyanate (155 g,2 mol), di-t-butyl peroxide (5.8 g,0.02 eq) and tetrahydrofuran (465 g) were sequentially added under the protection of nitrogen, and the reaction was carried out for 10 hours while heating the oil bath to an internal temperature of 50 ℃. After the reaction is completed, the solvent is recovered by decompression concentration, the residue is recrystallized by acetone and water, and the obtained product is dried to obtain 135.3g of trichloroisocyanuric acid, wherein the effective chlorine content is 90.8%, and the yield is 87.3% based on chlorinated isocyanate.
Example 4
In a dry 1000mL three-necked flask, a magnetic stirrer was added, a thermometer and a reflux condenser were equipped, the reaction apparatus was evacuated, nitrogen was charged, and after repeating three times, chlorinated isocyanate (155 g,2 mol), azobisisobutyronitrile (6.6 g,0.02 eq) and tetrahydrofuran (465 g) were sequentially added under the protection of nitrogen, and the oil bath was warmed to an internal temperature of 50℃to react for 10 hours. After the reaction is completed, the solvent is recovered by decompression concentration, the residue is recrystallized by acetone and water, 138.9g of trichloroisocyanuric acid product is obtained by drying, the effective chlorine content is 90.5%, and the yield is 89.6% based on chlorinated isocyanate.
Claims (9)
1. A process for producing trichloroisocyanuric acid, which comprises the following steps:
the method comprises the following steps:
under the inert gas environment, adding chlorinated isocyanate and an organic solvent into a reaction container, adding an initiator, controlling the temperature of the system to be between 10 ℃ and reflux temperature for reaction, and separating and purifying the reaction system after the reaction is finished to obtain a product trichloroisocyanuric acid; the initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, potassium persulfate, ammonium persulfate, benzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxide; the organic solvent is selected from tetrahydrofuran, benzene, toluene, n-hexane, cyclohexane, acetonitrile or a mixture thereof.
2. The production process according to claim 1, wherein the organic solvent is tetrahydrofuran or acetonitrile.
3. The production process according to claim 1, wherein the mass ratio of the chlorinated isocyanate to the organic solvent is 1: 1-1: 10.
4. the production process according to claim 3, wherein the mass ratio of the chlorinated isocyanate to the organic solvent is 1: 2-1: 4.
5. the production process according to claim 1, wherein the separation and purification are performed by recrystallization from acetone and water.
6. The process according to claim 1, wherein the molar ratio of chlorinated isocyanate to initiator is 1: 0.001-1: 1.
7. the process according to claim 6, wherein the molar ratio of chlorinated isocyanate to initiator is 1: 0.01-1: 0.05.
8. the production process according to claim 1, wherein the reaction temperature is 40-60 ℃.
9. The process according to claim 1, wherein the initiator and the organic solvent are azobisisobutyronitrile in combination with acetonitrile.
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| CN202111317635.0A CN113999183B (en) | 2021-11-09 | 2021-11-09 | Preparation method of trichloroisocyanuric acid |
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| CN202111317635.0A CN113999183B (en) | 2021-11-09 | 2021-11-09 | Preparation method of trichloroisocyanuric acid |
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| CN113999183B true CN113999183B (en) | 2023-06-30 |
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