CN112142612A - Method for preparing beta-hydroxyalkyl amide by extraction and purification - Google Patents
Method for preparing beta-hydroxyalkyl amide by extraction and purification Download PDFInfo
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Abstract
The application discloses a method for preparing beta-hydroxyalkyl amide by extraction and purification, which comprises the following steps: (1) adding excessive dialkyl hydramine and an alkaline catalyst into a reaction kettle, and then dropwise adding dialkyl dicarboxylate to prepare a beta-hydroxyalkylamide crude product; (2) adding an extraction solvent into the beta-hydroxyalkylamide crude product, extracting, stirring and standing to form an upper layer liquid and a lower layer liquid, and separating the upper layer liquid from the lower layer liquid; (3) distilling the lower layer liquid to separate residual extraction solvent to obtain beta-hydroxyalkyl amide product; distilling the upper layer liquid, and recovering the extraction solvent and the raw material of the dialkyl hydramine. The method can be used for conveniently separating reaction materials to obtain the beta-hydroxyalkylamide product with higher purity.
Description
Technical Field
The invention relates to a method for preparing beta-hydroxyalkyl amide by extraction and purification.
Background
The beta-hydroxyalkylamide is a thermosetting polyester powder coating curing agent, mainly comprises tetra- (beta-hydroxyethyl) adipamide, tetra- (beta-hydroxypropyl) adipamide and the like, is a curing agent for the thermosetting polyester powder coating with four functionalities and low toxicity, has the advantage of low toxicity compared with the traditional TGIC type curing agent, is a TGIC substitute with the best application performance at present, and has a larger application prospect.
At present, the beta-hydroxyalkylamide is prepared by synthesizing alkanolamine and dicarboxylic acid dialkyl ester serving as raw materials under alkaline conditions, most of the methods adopt stoichiometric ratio raw materials or adopt slightly excessive alkanolamine conditions, and the synthesis reaction conditions can increase the probability of side reaction and reduce the selectivity of the synthesis reaction, especially when the alkanolamine with high steric hindrance and low reaction activity is selected as the raw material, the selectivity of the synthesis reaction is lower. The current scheme that the reaction selectivity is better is to increase the amine-ester ratio of the synthetic raw materials and carry out the synthetic reaction under the condition of a large excess of alkanolamine so as to improve the selectivity of the synthetic reaction, but the problem of separation of unreacted raw materials is also brought by the increase of the amine-ester ratio.
Disclosure of Invention
In order to solve the problem of raw material separation in the process of synthesizing beta-hydroxyalkylamide under the condition of high amine-ester ratio, the application provides a method for purifying beta-hydroxyalkylamide, the method can be used for conveniently separating reaction materials to obtain a beta-hydroxyalkylamide product with high purity, and the specific technical scheme is as follows:
a method for preparing beta-hydroxyalkyl amide by extraction and purification, which comprises the following steps:
(1) adding excessive dialkyl hydramine and an alkaline catalyst into a reaction kettle, and then dropwise adding dialkyl dicarboxylate to prepare a beta-hydroxyalkylamide crude product;
(2) adding an extraction solvent into the beta-hydroxyalkylamide crude product, extracting, stirring and standing to form an upper layer liquid and a lower layer liquid, and separating the upper layer liquid from the lower layer liquid;
(3) distilling the lower layer liquid to separate residual extraction solvent to obtain beta-hydroxyalkyl amide product; distilling the upper layer liquid, and recovering the extraction solvent and the raw material of the dialkyl hydramine.
In the step (1), the alkaline catalyst is preferably any one of NaOH, KOH, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.
The method can synthesize the beta-hydroxyalkylamide crude product under the condition of high amine-ester ratio, and smoothly extract unreacted dialkanolamine raw materials from the crude product. The purity of the produced beta-hydroxyalkylamide product is stabilized to be more than 95 percent, the preparation process flow is simple, the energy consumption is low, and the separated dialkanolamine can be recycled as a raw material.
Specifically, in the step (1), the dialkanolamine is diethanolamine or diisopropanolamine, or a mixture of diethanolamine and diisopropanolamine in any proportion. The above two dialkanolamines or mixtures thereof can be advantageously applied in the present invention to prepare higher purity β -hydroxyalkylamide products.
Specifically, in the step (1), the dicarboxylic acid dialkyl ester is dimethyl adipate or dimethyl phthalate.
Further, the feeding molar ratio of the dialkanolamine to the dicarboxylic acid dialkyl ester is 2.5 to 6.0, and the feeding molar ratio is preferably 2.5 to 5.0. Under the limit, the selectivity of the synthesis reaction can be obviously improved, the occurrence of side reactions is reduced, the difficulty of extraction and separation can be reduced, the product purity is improved, and meanwhile, in the recovery process, the excessive dialkanolamine can be conveniently recovered, so that the recovery process is optimized.
Preferably, in the preparation step (2), the extraction solvent is a mixture of a main solvent and one or more cosolvents, wherein the main solvent is an amine solvent or an ester solvent, and the cosolvent is an alcohol solvent, an ether solvent or an ester solvent or a mixture thereof; in the extraction solvent, the volume ratio of the main solvent is 55-95.0%, and the volume ratio of the cosolvent is 5.0-45.0%.
Specifically, the alcohol solvent is at least one of methanol, ethanol, isopropanol, propanol or butanol; the ether solvent is dimethyl ether, diethyl ether or dioxane, the amine solvent is at least one of trimethylamine, triethylamine, tripropylamine, N-methyl diisopropylamine or triisopropylamine, and the ester solvent is at least one of methyl ester, ethyl acetate, methyl formate, methyl acrylate, ethyl acrylate, dimethyl adipate, dimethyl succinate or dimethyl carbonate.
The materials are used as the solvent, so that the raw material of the dialkyl hydramine in the product can be smoothly separated, the dialkyl hydramine has a low boiling point, and the dialkyl hydramine is easy to distill and recycle for recycling, and the production cost is reduced. The cosolvent is used for reducing the molecular force between the dialkanolamine and the hydroxyalkyl amide so that the two substances are easier to diffuse and separate in two liquid phases, and the main solvent is generally a solvent with higher solubility to the dialkanolamine and lower solubility to the hydroxyalkyl amide, so that the two substances can be effectively separated.
In order to ensure the extraction effect, the solvent amount of the extraction solvent is too low, the viscosity of a separation system is high, the layering is difficult, and the separation difficulty between liquid phases is increased. Too high solvent amount can bring about the increase of product dissolved amount, resulting in the reduction of separation yield; at the same time, too high a solvent amount also increases the energy cost of the solvent separation. The volume ratio of the extraction solvent to the crude product of the beta-hydroxyalkylamide is 1.0-10.0.
In order to fully dissolve the raw material of the dialkanolamine in the extraction solvent and improve the recovery rate of the product, the standing time is 1 to 3 hours in the extraction and separation processes. Under the condition, the standing time can be ensured to ensure that the two materials are fully separated in the extraction solvent, and simultaneously, the separation difficulty caused by the partial crystallization of the hydroxyalkyl amide can be avoided.
Detailed Description
Example 1
166.3g of diisopropanolamine and 1.15g of potassium hydroxide are added into a glass reactor, stirred and heated to the reaction temperature of 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the reduced pressure condition, and the reaction is continued to be stirred under the reduced pressure for 2 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 250ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 150.3g of beta-hydroxyalkylamide product with the purity of 95.13 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 2
166.3g of diisopropanolamine and 1.15g of potassium hydroxide are added into a glass reactor, stirred and heated to the reaction temperature of 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the reduced pressure condition, and the reaction is continued to be stirred under the reduced pressure for 2 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1250ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand for 60min at room temperature. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 152.3g of beta-hydroxyalkylamide product with the purity of 96.54 percent is obtained. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 3
166.3g of diisopropanolamine and 2.15g of potassium methoxide are added into a glass reactor, stirred and heated to the reaction temperature of 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the reduced pressure condition, and the reduced pressure stirring reaction is continued for 3 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 2500ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 135.6g of beta-hydroxyalkylamide product is obtained, and the purity is 97.57 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 4
Adding 199.5g of diisopropanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure for reaction for 3 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 290ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 153.8g of beta-hydroxyalkylamide product with the purity of 95.46 percent is obtained. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 5
Adding 199.5g of diisopropanolamine and 1.0g of sodium hydroxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure and react for 3 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1450ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 150.7g of beta-hydroxyalkylamide product with the purity of 97.86 percent is obtained. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 6
Adding 199.5g of diisopropanolamine and 1.0g of sodium hydroxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure and react for 4 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 2900ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 137.2g of beta-hydroxyalkylamide product is obtained, and the purity is 98.74 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 7
266.5g of diisopropanolamine and 1.0g of sodium hydroxide are added into a glass reactor, stirred and heated to 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 355ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and the materials are fully stirred and then are kept stand for 60min at room temperature. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 141.3g of beta-hydroxyalkylamide product is obtained, and the purity is 95.41 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 8
266.5g of diisopropanolamine and 1.0g of sodium hydroxide are added into a glass reactor, stirred and heated to 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1775ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 145.3g of beta-hydroxyalkylamide product is obtained, and the purity is 98.33%. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 9
266.5g of diisopropanolamine and 1.0g of sodium hydroxide are added into a glass reactor, stirred and heated to 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 3550ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 137.3g of beta-hydroxyalkylamide product is obtained, and the purity is 98.43 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 10
166.3g of diisopropanolamine and 2.15g of potassium methoxide are added into a glass reactor, stirred and heated to 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 255ml of mixed solvent of ethyl acetate and triethylamine is added, the volume ratio of the ethyl acetate to the triethylamine is 4.0:5.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 155.7g of beta-hydroxyalkylamide product is obtained, and the purity is 95.24%. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 11
166.3g of diisopropanolamine and 2.15g of potassium methoxide are added into a glass reactor, stirred and heated to 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 2550ml of mixed solvent of ethyl acetate and triethylamine is added, the volume ratio of the ethyl acetate to the triethylamine is 4.0:5.0, and after full stirring, the materials are kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 143.3g of beta-hydroxyalkylamide product is obtained, and the purity is 97.13 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 12
166.3g of diisopropanolamine and 2.15g of potassium methoxide are added into a glass reactor, stirred and heated to 100 ℃, 87.0g of dimethyl adipate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 600ml of mixed solvent of methanol, ethyl acetate and triethylamine is added, the volume ratio of the methanol to the ethyl acetate to the triethylamine is 3.0:30.0:50.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 130.5g of beta-hydroxyalkylamide product is obtained, and the purity is 98.33%. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 13
Adding 199.5g of diisopropanolamine and 1.0g of sodium hydroxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure and react for 3 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1450ml of mixed solvent of ethanol and triethylamine is added, the volume ratio of the ethanol to the triethylamine is 1.0:19.0, and after the materials are fully stirred, the materials are kept stand at room temperature for 60 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 151.4g of beta-hydroxyalkylamide product with the purity of 97.91 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 14
Adding 131.3g of diethanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to the reaction temperature, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir and react for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 220ml of mixed solvent of methanol and triethylamine is added, the volume ratio of the methanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 155.3g of beta-hydroxyalkylamide product is obtained, and the purity is 98.46%. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 15
Adding 131.3g of diethanolamine and 1.15g of potassium hydroxide into a glass reactor, stirring and heating to reaction temperature, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir and react for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1100ml of mixed solvent of ethanol and triethylamine is added, the volume ratio of the ethanol to the triethylamine is 1.0:19.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 158.4g of beta-hydroxyalkylamide product with the purity of 98.87 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 16
Adding 131.3g of diethanolamine and 1.15g of potassium hydroxide into a glass reactor, stirring and heating to reaction temperature, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir and react for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1100ml of mixed solvent of ethyl acetate and triethylamine is added, the volume ratio of the ethyl acetate to the triethylamine is 3.0:7.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 157.9g of beta-hydroxyalkylamide product is obtained, and the purity is 98.76%. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 17
Adding 131.3g of diethanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to the reaction temperature, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir and react for 2 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1100ml of mixed solvent of ethyl acetate and triethylamine is added, the volume ratio of the ethyl acetate to the triethylamine is 2.0:8.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 60 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 150.9g of beta-hydroxyalkylamide product with the purity of 98.91 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 18
Adding 199.5g of diisopropanolamine and 1.0g of sodium hydroxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure and react for 4 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1450ml of mixed solvent of dioxane and triethylamine is added, the volume ratio of the dioxane to the triethylamine is 2.0:18.0, and after the materials are fully stirred, the materials are kept stand at room temperature for 120 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 135.2g of beta-hydroxyalkylamide product with the purity of 96.47 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 19
Adding 199.5g of diisopropanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure for reaction for 4 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 2900ml of mixed solvent of dioxane and triethylamine is added, the volume ratio of the dioxane to the triethylamine is 2.0:18.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 120 min. After the standing is finished, the upper layer liquid is separated, the lower layer liquid is continuously decompressed and distilled to remove the residual solvent, and then the material is discharged, 136.2g of beta-hydroxyalkylamide product is obtained, and the purity is 98.32%. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 20
Adding 199.5g of diisopropanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure for reaction for 4 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 870ml of mixed solvent of methanol and ethyl acetate is added, the volume ratio of the methanol to the ethyl acetate is 1.0:9.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 120 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 157.3g of beta-hydroxyalkylamide product with the purity of 96.44 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 21
Adding 199.5g of diisopropanolamine and 2.35g of potassium ethoxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure and react for 4 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 870ml of mixed solvent of ethanol and ethyl acetate is added, the volume ratio of the ethanol to the ethyl acetate is 1.0:9.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 120 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 157.3g of beta-hydroxyalkylamide product with the purity of 96.44 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 22
266g of diisopropanolamine and 1.15g of potassium hydroxide are added into a glass reactor, stirred and heated to 100 ℃, 97.1g of dimethyl phthalate is dripped into the reactor under the condition of reduced pressure, and the reaction is continued to be stirred and reacted for 3 hours under reduced pressure after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1300ml of mixed solvent of methanol, ethyl acetate and triethylamine is added, the volume ratio of the ethyl acetate to the triethylamine is 4.0:15.0:25.0, and the materials are fully stirred and then are kept stand at room temperature for 120 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 297.2g of beta-hydroxyalkylamide product with the purity of 97.41 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 23
Adding 199.5g of diisopropanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to 100 ℃, dripping 87.0g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure for reaction for 4 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 600ml of mixed solvent of ethanol and dimethyl carbonate is added, the volume ratio of the ethanol to the dimethyl carbonate is 1.0:9.0, and after the mixture is fully stirred, the mixture is kept stand for 180min at room temperature. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 151.3g of beta-hydroxyalkylamide product with the purity of 95.88 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Example 24
Adding 199.5g of diisopropanolamine, 131.3g of diethanolamine and 2.15g of potassium methoxide into a glass reactor, stirring and heating to 100 ℃, dripping 174.1g of dimethyl adipate into the reactor under the reduced pressure condition, and continuing to stir under reduced pressure for reaction for 3 hours after the feeding is finished.
After the reaction is finished, the temperature of the materials is reduced to 65 ℃, 1500ml of mixed solvent of ethyl acetate and triethylamine is added, the volume ratio of the ethyl acetate to the triethylamine is 2.0:3.0, and after the mixture is fully stirred, the mixture is kept stand at room temperature for 180 min. After the standing is finished, separating the upper layer liquid, continuously distilling the lower layer liquid under reduced pressure to remove the residual solvent, and discharging to obtain 318.0g of beta-hydroxyalkylamide product with the purity of 98.47 percent. And distilling the upper layer liquid, and recovering the solvent and the diisopropanolamine.
Claims (9)
1. A method for preparing beta-hydroxyalkyl amide by extraction and purification, which comprises the following steps:
(1) adding excessive dialkyl hydramine and an alkaline catalyst into a reaction kettle, and then dropwise adding dialkyl dicarboxylate to prepare a beta-hydroxyalkylamide crude product;
(2) adding an extraction solvent into the beta-hydroxyalkylamide crude product, extracting, stirring and standing to form an upper layer liquid and a lower layer liquid, and separating the upper layer liquid from the lower layer liquid;
(3) distilling the lower layer liquid to separate residual extraction solvent to obtain beta-hydroxyalkyl amide product; distilling the upper layer liquid, and recovering the extraction solvent and the raw material of the dialkyl hydramine.
2. The method of claim 1, wherein in step (1), the alkaline catalyst is any one of NaOH, KOH, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide.
3. The method of claim 1, wherein in step (1), the dialkanolamine is diethanolamine or diisopropanolamine, or a mixture of diethanolamine and diisopropanolamine in any ratio.
4. The method according to claim 1, wherein in the step (1), the dicarboxylic acid dialkyl ester is dimethyl adipate or dimethyl phthalate.
5. The method according to claim 1, wherein the molar ratio of the dialkyl alcohol amine to the dialkyl dicarboxylate is 2.5-6.0.
6. The method according to claim 1, wherein in the preparation step (2), the extraction solvent is a mixture of a main solvent and one or more auxiliary solvents, wherein the main solvent is an amine solvent or an ester solvent, and the auxiliary solvent is an alcohol solvent, an ether solvent or an ester solvent or a mixture thereof;
in the extraction solvent, the volume ratio of the main solvent is 55-95.0%, and the volume ratio of the cosolvent is 5.0-45.0%.
7. The method of claim 6, wherein the alcoholic solvent is at least one of methanol, ethanol, isopropanol, propanol or butanol; the ether solvent is dimethyl ether, diethyl ether or dioxane, the amine solvent is at least one of trimethylamine, triethylamine, tripropylamine, N-methyl diisopropylamine or triisopropylamine, and the ester solvent is at least one of methyl ester, ethyl acetate, methyl formate, methyl acrylate, ethyl acrylate, dimethyl adipate, dimethyl succinate or dimethyl carbonate.
8. The method of claim 1, wherein the volume ratio of the extraction solvent to the crude β -hydroxyalkylamide product is from 1.0 to 10.0.
9. The method of claim 1, wherein the standing time is 1-3 hours during the extraction and separation.
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| EP4299656A1 (en) | 2022-07-01 | 2024-01-03 | Evonik Operations GmbH | Preparation of propoxylated benzenedicarboxylic acid amides and corresponding polyurethane foam |
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