CN112142625A - Method for reducing waste residues of N, N' -diisopropylcarbodiimide product - Google Patents
Method for reducing waste residues of N, N' -diisopropylcarbodiimide product Download PDFInfo
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- CN112142625A CN112142625A CN202011122425.1A CN202011122425A CN112142625A CN 112142625 A CN112142625 A CN 112142625A CN 202011122425 A CN202011122425 A CN 202011122425A CN 112142625 A CN112142625 A CN 112142625A
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- caustic soda
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
Abstract
The invention relates to a method for reducing waste residues of N, N' -diisopropylcarbodiimide products, which comprises the following steps: after the solvent is distilled off from the crude DIC product, caustic soda flakes accounting for 0.5 to 1 percent of the total mass of the materials are added into the crude DIC product without the solvent, the temperature is controlled to be between 80 and 90 ℃, the mixture is stirred for 0.2 to 0.8 hour, then the vacuum pressure is controlled to be less than-0.09 MPa, and the DIC is obtained by distillation. Compared with the prior art, the invention has the following advantages: the residual sulfur can be removed by adding the caustic soda flakes, and the caustic soda flakes can not react with the product; adding caustic soda flakes as a catalyst, and after DIC distillation, the purity is over 99.50 percent, the waste residue amount can be reduced by 50 percent, and the waste residue amount is less than 1 percent of the mass of a DCC crude product; the method has the advantages of greatly reducing the investment of environmental protection cost, being simple and reliable to control, and simultaneously taking the caustic soda flakes as the catalyst, changing the product from light yellow to transparent and colorless, and improving the appearance of the product.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a method for reducing N, N' -diisopropylcarbodiimide product waste residues.
Background
N, N' -diisopropyl carbodiimide (DIC) is a good low-temperature biochemical dehydrating agent, is used for synthesizing and dehydrating amikacin and amino acid, is also used for synthesizing acid, anhydride, aldehyde, ketone and the like, and is also used for synthesizing peptide and nucleic acid. Used as a dehydrating agent or a carboxyl activating agent for polypeptide synthesis or coupling of small molecular compounds and polypeptides with carrier proteins. The conventional synthesis method has low yield and high cost, and the process needs to be improved in view of the limitations and the disadvantages.
The existing methods for synthesizing N, N' -diisopropylcarbodiimide mainly comprise the following three methods:
route 1: patent CN109485583A discloses a method for preparing N, N '-diisopropylcarbodiimide, which comprises synthesizing N, N' -diisopropylthiourea from isopropylamine and carbon disulfide in a solvent; carrying out suction filtration and drying on the N, N' -diisopropyl thiourea, and then carrying out primary oxidation; carrying out secondary oxidation reaction, adding a catalyst and an oxidant, and reacting for 1 hour at the temperature of 60-65 ℃; performing desulfurization treatment, adding a sodium sulfide solution into the oxidizing solution, heating to 70-75 ℃, and reacting for 1-2 hours; adding caustic soda flakes for neutralization, washing, removing a water layer, adding a drying agent for drying, evaporating the solvent, and carrying out vacuum rectification to obtain the N, N' -diisopropylcarbodiimide. The method has the advantages of low yield, large amount of waste residues, high production cost and no use of large-scale production.
Route 2: patent CN103382168A discloses a method for synthesizing N, N' -diisopropylcarbodiimide, comprising the following steps: (1) adding carbon disulfide and isopropylamine into an alkaline solution, heating the mixed solution to a set temperature, and reacting at a constant temperature for a set time to obtain a mixed solution A; (2) mixing the mixed solution A and hydrogen peroxide, heating to a preset temperature, and reacting at a constant temperature for a preset time to obtain a mixed solution B; (3) and in an alkaline environment, uniformly mixing the mixed solution B, dichloromethane and isopropylamine, then adding a sodium hypochlorite aqueous solution for oxidation reaction, and separating and purifying to obtain the N, N' -diisopropylcarbodiimide. The method has the advantages of low yield, low product quality, environmental protection, high production cost and no use of large-scale production.
Route 3: patent CN108084055A discloses a method for synthesizing N, N 'diisopropylcarbodiimide by oxidizing N, N' diisopropylthiourea, which comprises oxidizing dimethylamine chloride with sodium hypochlorite to obtain dimethylamine chloride, oxidizing N, N 'diisopropylthiourea with dimethylamine chloride under alkaline condition to obtain N, N' diisopropylcarbodiimide, and the yield is over 93%. The method has the advantages of low yield, high production cost, difficult treatment of a large amount of wastewater generated by oxidation and high production cost.
The production process of the N, N' -diisopropylcarbodiimide is approximately as follows:
isopropyl thiourea is generated by the reaction of isopropyl amine and carbon disulfide, sodium hypochlorite or hydrogen peroxide and the like are used as oxidants for primary oxidation, hydrogen sulfide is oxidized and removed to generate N, N '-diisopropyl carbodiimide and sulfur, liquid alkali or sodium hydrosulfide is used for removing sulfur by secondary oxidation, DIC crude product is obtained by washing and drying, solvent is evaporated out, and N, N' -diisopropyl carbodiimide is obtained by decompression and rectification. After the secondary oxidation, part of sulfur is dissolved in crude DIC product (sulfur can be dissolved in organic solvent such as toluene, benzene, xylene and cyclohexane in reaction system) and is difficult to remove, and finally, the sulfur remains in the product.
The traditional process method is difficult to completely desulfurize, and a high-purity N, N' -diisopropylcarbodiimide product is obtained.
Disclosure of Invention
The invention aims to provide a method for reducing waste residues of N, N' -diisopropylcarbodiimide products aiming at the defects in the prior art.
The invention is realized by the following technical scheme:
a method for reducing waste residues of N, N' -diisopropylcarbodiimide products comprises the following steps: after the solvent is distilled off from the crude DIC product, 0.5 to 1 percent of caustic soda flakes accounting for the mass of the crude DIC product without the solvent is added into the crude DIC product without the solvent, the temperature is controlled to be between 80 and 90 ℃, the mixture is stirred for 0.2 to 0.8 hour, then the vacuum pressure is controlled to be less than-0.09 MPa, and the DIC is obtained by distillation.
Preferably, the amount of the flake base is 0.7% of the mass of the crude DIC product without solvent.
Preferably, the temperature is controlled at 85 ℃.
Preferably, the stirring time is 0.5 hour.
Compared with the prior art, the invention has the following advantages: the residual sulfur can be removed by adding the caustic soda flakes, and the caustic soda flakes can not react with the product; adding caustic soda flakes as a catalyst, and after DIC distillation, the purity is over 99.50 percent, the waste residue amount can be reduced by 50 percent, and the waste residue amount is less than 1 percent of the mass of a DCC crude product; the method has the advantages of greatly reducing the investment of environmental protection cost, being simple and reliable to control, and simultaneously taking the caustic soda flakes as the catalyst, changing the product from light yellow to transparent and colorless, and improving the appearance of the product.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example one
A method for reducing waste residues of N, N' -diisopropylcarbodiimide products comprises the following steps:
adding caustic soda flakes accounting for 0.5 percent of the total mass of the materials into the crude DIC product without solvent, controlling the temperature at 80 ℃, stirring for 0.5h, then carrying out vacuum distillation under the pressure of-0.09 MPa to obtain the DIC. The purity is more than 99.53 percent, the yield is more than 96.5 percent, and the waste residue accounts for 0.70 percent of the mass of the crude DIC product (the waste residue is the bottom material remained in a distillation device after the DIC is distilled out). And after the wastewater generated by oxidation is qualified through MVR distillation detection, the wastewater is used as cooling circulating water.
Example two
A method for reducing waste residues of N, N' -diisopropylcarbodiimide products comprises the following steps:
adding caustic soda flakes accounting for 0.7 percent of the total mass of the materials into the crude DIC product without solvent, controlling the temperature at 85 ℃, stirring for 0.5h, then carrying out vacuum distillation under the pressure of-0.09 MPa to obtain the DIC. The purity is more than 99.55 percent, the yield is more than 96.60 percent, and the waste residue accounts for 0.65 percent of the mass of the crude DIC product. And after the wastewater generated by oxidation is qualified through MVR distillation detection, the wastewater is used as cooling circulating water.
EXAMPLE III
A method for reducing waste residues of N, N' -diisopropylcarbodiimide products comprises the following steps:
adding caustic soda flakes accounting for 0.8 percent of the total mass of the materials into the crude DIC product without solvent, controlling the temperature at 85 ℃, stirring for 0.5h, then carrying out vacuum distillation under the pressure of-0.09 MPa to obtain the DIC. The purity is more than 99.65 percent, the yield is more than 96.65 percent, and the waste residue accounts for 0.50 percent of the mass of the DIC crude product. And after the wastewater generated by oxidation is qualified through MVR distillation detection, the wastewater is used as cooling circulating water.
Example four
A method for reducing waste residues of N, N' -diisopropylcarbodiimide products comprises the following steps:
adding caustic soda flakes accounting for 1 percent of the total mass of the materials into the crude DIC product without solvent, controlling the temperature at 90 ℃, stirring for 0.5h, then carrying out vacuum distillation under the pressure of-0.09 MPa to obtain the DIC. The purity is more than 99.60 percent, the yield is more than 96.55 percent, and the waste residue accounts for 0.65 percent of the mass of the DIC crude product. And after the wastewater generated by oxidation is qualified through MVR distillation detection, the wastewater is used as cooling circulating water.
The present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention, and the contents of the changes still fall within the scope of the present invention.
Claims (4)
1. A method for reducing waste residues of N, N' -diisopropylcarbodiimide products is characterized by comprising the following steps:
after the solvent is distilled off from the crude DIC product, 0.5 to 1 percent of caustic soda flakes accounting for the mass of the crude DIC product without the solvent is added into the crude DIC product without the solvent, the temperature is controlled to be between 80 and 90 ℃, the mixture is stirred for 0.2 to 0.8 hour, then the vacuum pressure is controlled to be less than-0.09 MPa, and the DIC is obtained by distillation.
2. The method for reducing the waste residue of N, N' -diisopropylcarbodiimide products according to claim 1, wherein: the dosage of the caustic soda flakes is 0.7 percent of the mass of the crude DIC product without solvent.
3. The method for reducing the waste residue of N, N' -diisopropylcarbodiimide products according to claim 1, wherein: the temperature was controlled at 85 ℃.
4. The method for reducing the waste residue of N, N' -diisopropylcarbodiimide products according to claim 1, wherein: the stirring time was 0.5 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011122425.1A CN112142625A (en) | 2020-10-20 | 2020-10-20 | Method for reducing waste residues of N, N' -diisopropylcarbodiimide product |
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| CN202011122425.1A CN112142625A (en) | 2020-10-20 | 2020-10-20 | Method for reducing waste residues of N, N' -diisopropylcarbodiimide product |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1171733A (en) * | 1968-04-23 | 1969-11-26 | Chimica Profarmaco Spa Ind | Improvements in or relating to the preparation of carbodiimides. |
| JPH08231491A (en) * | 1995-02-24 | 1996-09-10 | Sumikin Chem Co Ltd | Production of 1,3-dicyclohexylcarbodiimide |
| CN103382168A (en) * | 2013-07-31 | 2013-11-06 | 浙江普康化工有限公司 | Synthetic method for N,N'-diisopropyl carbodiimide |
| CN109485583A (en) * | 2018-10-09 | 2019-03-19 | 淄博天堂山化工有限公司 | The preparation method of N, N '-diisopropylcarbodiimide |
| CN110903217A (en) * | 2019-12-11 | 2020-03-24 | 山东汇海医药化工有限公司 | Method for reducing waste residues of N, N' -dicyclohexylcarbodiimide product |
-
2020
- 2020-10-20 CN CN202011122425.1A patent/CN112142625A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1171733A (en) * | 1968-04-23 | 1969-11-26 | Chimica Profarmaco Spa Ind | Improvements in or relating to the preparation of carbodiimides. |
| JPH08231491A (en) * | 1995-02-24 | 1996-09-10 | Sumikin Chem Co Ltd | Production of 1,3-dicyclohexylcarbodiimide |
| CN103382168A (en) * | 2013-07-31 | 2013-11-06 | 浙江普康化工有限公司 | Synthetic method for N,N'-diisopropyl carbodiimide |
| CN109485583A (en) * | 2018-10-09 | 2019-03-19 | 淄博天堂山化工有限公司 | The preparation method of N, N '-diisopropylcarbodiimide |
| CN110903217A (en) * | 2019-12-11 | 2020-03-24 | 山东汇海医药化工有限公司 | Method for reducing waste residues of N, N' -dicyclohexylcarbodiimide product |
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