CN108997143B - Self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine - Google Patents
Self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine Download PDFInfo
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- CN108997143B CN108997143B CN201811010903.2A CN201811010903A CN108997143B CN 108997143 B CN108997143 B CN 108997143B CN 201811010903 A CN201811010903 A CN 201811010903A CN 108997143 B CN108997143 B CN 108997143B
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Abstract
The invention discloses a self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine, which comprises the following steps: 1) adding an acid-binding agent with the same molar weight as dimethylamine into reaction raw materials by taking dimethylamine aqueous solution and dichloroethane as reaction raw materials to carry out heating reaction, wherein the heating reaction temperature is 30-90 ℃, the reaction pressure is 1-3 MPa, and the reaction time is 3-8 h; 2) carrying out post-treatment on the reaction product obtained in the step 1) to obtain an aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine and dichloroethane; and (3) carrying out vacuum rectification on the aqueous solution of the N, N-dimethyl chloroethylamine and the tetramethyl ethylenediamine to respectively obtain the N, N-dimethyl chloroethylamine as a light component and the tetramethyl ethylenediamine as a heavy component. The method of the invention is adopted to produce N, N-dimethyl chloroethyl amine and coproduce tetramethyl ethylene diamine.
Description
Technical Field
The invention belongs to the fine chemical industry, and relates to a co-production preparation method of important intermediates N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine.
Background
N, N-dimethylchloroethylamine with the molecular formula of C4H10ClN, widely used in the industries of medicine, pesticide, surfactant, dye and the like; tetramethylethylenediamine with molecular formula C6H16N2Commonly used as biochemical reagents and epoxy resin crosslinking agents, the structural formulas of which are respectively as follows:
the preparation of the N, N-dimethyl chloroethyl amine mainly adopts the following method:
the method comprises the following steps: patent CN107445847 reports that N, N-dimethylethanolamine is used as a raw material to perform chlorination reaction with thionyl chloride, and the temperature is controlled to be 10-15 ℃ to obtain a finished product of N, N-dimethylchloroethylamine hydrochloride. The process has simple steps and high yield. But hydrogen chloride and sulfur dioxide are generated in the reaction process, so that the atom economy is low and the environmental protection pressure is high.
The second method comprises the following steps: patent CN102875466 reports that N, N-dimethylchloroethylamine is obtained by taking 2-chloroethanol and dimethylamine as raw materials (2-chloroethanol: dimethylamine is 1-1.2: 1 molar ratio) and benzene as a solvent through multi-step reaction, and the yield is 60.8%. Benzene is used as a solvent, so the toxicity is high, and the method has limited significance for industrial production.
The reactions reported in the literature for dimethylamine and dichloroethane are all to produce tetramethylethylenediamine, not N, N-dimethylchloroethylamine. For example, in CN101717339, dimethylamine and dichloroethane were reported to react in methanol solvent, the yield of tetramethylethylenediamine was 98.8%, and the reaction conditions: 0.03-0.08 MPa, reaction temperature: and (2) at 80-90 ℃, reaction time: 2 h; raw material ratio: dimethylamine: dichloroethane (mol) ═ 2.4: 1.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for producing N, N-dimethyl chloroethyl amine, which is simple and clean, has high atom economy and high industrial application value. The method produces N, N-dimethyl chloroethyl amine and coproduces tetramethyl ethylenediamine.
In order to solve the technical problem, the invention provides a self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylene diamine, which comprises the following steps:
1) according to dimethylamine: taking dichloroethane as a reaction raw material, adding an acid-binding agent in an amount equal to the molar amount of dimethylamine into the reaction raw material to perform a heating reaction at the temperature of 30-90 ℃ and under the reaction pressure of 1-3 MPa (introducing nitrogen to maintain the pressure during the reaction), wherein the molar ratio of dichloroethane to dimethylamine is 1: 1-5, and the reaction time is 3-8 h;
2) carrying out post-treatment on the reaction product obtained in the step 1) to obtain an aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine and dichloroethane;
the aqueous solution of N, N-dimethylchloroethylamine and tetramethylethylenediamine was subjected to rectification under reduced pressure (rectification purification), thereby obtaining N, N-dimethylchloroethylamine as a light component and tetramethylethylenediamine as a heavy component, respectively.
The improvement of the self-binding acid integrated production method of the invention is as follows: the acid-binding agent is solid sodium hydroxide, sodium carbonate, sodium bicarbonate, or tetramethylethylenediamine (for preparing N, N-dimethylchloroethylamine, preferably tetramethylethylenediamine).
As a further improvement of the self-binding acid integrated production method, the post-treatment of the step 2) is as follows: standing and layering the reaction product obtained in the step 1) to respectively obtain a water layer (positioned at the lower layer and used for preparing a dimethylamine aqueous solution) and an organic layer;
taking an organic layer, adding hydrochloric acid, layering to form an organic phase on the upper layer and a water phase on the lower layer, and stopping adding hydrochloric acid until the pH value of the water phase is 1-2; the organic phase is dichloroethane (for standby); and taking the water phase, and adding alkali until the pH value of the water phase is 11-12, thereby obtaining the aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine.
As a further improvement of the self-binding acid integrated production method of the present invention, the mass concentration of dimethylamine in the dimethylamine aqueous solution in step 1) is 30-40% (preferably 33 ± 2% when preparing high yield N, N-dimethylchloroethylamine).
As a further improvement of the self-binding acid integrated production method, in the step 2), the alkali for adjusting the pH value of the water phase is ammonia gas and a sodium hydroxide aqueous solution with the mass concentration of 30 +/-5%.
As a further improvement of the self-binding acid integrated production method of the invention, in the step 2): the reduced pressure distillation pressure was 20mmHg, and N, N-dimethylchloroacetamine was obtained as a light component at 60 ℃ and tetramethylethylenediamine was obtained as a heavy component at 75 ℃.
Remarks explanation: the vacuum rectification can also obtain water which can be recycled (can also be used for preparing dimethylamine aqueous solution).
As a further improvement of the self-acid-binding integrated production method, dichloroethane and tetramethylethylenediamine obtained in the step 2) are respectively used for replacing dichloroethane and an acid-binding agent (tetramethylethylenediamine is used as an acid-binding agent) which are used as reaction raw materials, and the steps 1) to 2) are repeated, so that circulation is realized.
As a further improvement of the self-binding acid integrated production process of the present invention,
when high yields of N, N-dimethylchloroethylamine were obtained: the molar ratio of dimethylamine to dichloroethane is 1: 3-5, the reaction pressure is 1-1.5 MPa, the heating reaction temperature is 35 ℃, the reaction time is 5-8 h,
when tetramethylethylenediamine was obtained in high yield: the molar ratio of dimethylamine to dichloroethane is 1:1, the reaction pressure is 3.0MPa, the heating reaction temperature is 80 ℃, and the reaction time is 8 h.
The process flow diagram of the present invention is shown in figure 1.
The invention takes dimethylamine and dichloroethane as raw materials to react to generate N, N-dimethyl chloroethyl amine and tetramethyl ethylenediamine. The reaction formula is as follows:
when dichloroethane and tetramethylethylenediamine obtained in the step 2) are reacted, dichloroethane and tetramethylethylenediamine serving as an acid-binding agent are supplemented, dimethylamine with an equimolar amount with the acid-binding agent (the sum of the tetramethylethylenediamine and the supplemented acid-binding agent) is added, and the molar ratio of the dimethylamine to the dichloroethane (the sum of the dichloroethane and the supplemented acid-binding agent) is controlled to be 1: 1-5; repeating the steps 1) and 2); i.e. a loop is realized.
The invention adopts a reaction-rectification-circulation process, and the process specifically comprises the following steps:
(1) adding a dimethylamine aqueous solution, dichloroethane and an acid-binding agent (with the same molar weight as dimethylamine) into an autoclave for heating reaction, wherein the heating reaction temperature is 30-90 ℃, the reaction pressure is 1-3 MPa, the reaction time is 3-8 h, and nitrogen is introduced for maintaining the pressure during the reaction; wherein the molar ratio of dimethylamine to dichloroethane is 1: 1-5, and the products are N, N-dimethyl chloroethyl amine, tetramethyl ethylenediamine and salts.
Remarks explanation: the salt was in the aqueous layer from the standing layer.
(2) Carrying out post-treatment on the product (mixture) obtained in the step (1) so as to obtain dichloroethane and an aqueous solution containing N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine.
(3) And (3) carrying out vacuum rectification (20mmHg) on the aqueous solution obtained in the step (2) to obtain N, N-dimethyl chloroethyl amine at the temperature of 60 ℃ and obtain tetramethyl ethylenediamine at the temperature of 75 ℃.
(4) Introducing a dimethylamine solution into the obtained dichloroethane and the tetramethylethylenediamine, supplementing dichloroethane and the tetramethylethylenediamine serving as an acid-binding agent, controlling the molar ratio of the dimethylamine to the dichloroethane to be 1: 1-5, and repeatedly carrying out the reaction steps to realize circulation, wherein the molar ratio of the dimethylamine to the dichloroethane is equal to the molar ratio of the dimethylamine to the acid-binding agent (the tetramethylethylenediamine and the supplemented acid-binding agent).
The invention has the following technical advantages:
firstly, the N, N-dimethyl chloroethylamine is produced by adopting easily available and clean dimethylamine and dichloroethane raw materials, and the method has the advantages of simple and clean process, high atom economy and high industrial application value. The ratio of N, N-dimethyl chloroethyl amine to tetramethyl ethylene diamine is controlled by adjusting the process parameters. Simultaneously, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine can be produced, and the proportion of the two products can be adjusted by adjusting the proportion of raw materials, the type of acid-binding agent and process parameters; in particular to the preparation of N, N-dimethyl chloroethyl amine with high yield.
When the yield of the N, N-dimethyl chloroethyl amine is expected to be high, in the step (1), the molar ratio of dimethylamine to dichloroethane is controlled to be 1: 1-5, and the acid-binding agent is tetramethyl ethylene diamine (with the same molar amount as the dimethylamine); the corresponding process has the following preferred parameters: controlling the molar ratio of dimethylamine to dichloroethane to be 1:3, the reaction pressure to be 1.5MPa, the heating reaction temperature to be 35 ℃, and the reaction time to be 5 h. Dichloroethane and tetramethylethylenediamine can also be used as raw materials and acid-binding agents respectively to realize circulation.
When the yield of tetramethylethylenediamine is desired to be high, in the step (1), the molar ratio of dimethylamine to dichloroethane is controlled to be 1: 1-5, and the acid-binding agent is solid sodium hydroxide (in an amount equal to the molar amount of dimethylamine); the corresponding process has the following preferred parameters: the molar ratio of dimethylamine to dichloroethane is controlled to be 1:1, the reaction pressure is 3.0MPa, the heating reaction temperature is 80 ℃, and the reaction time is 8 hours.
And secondly, the dichloroethane in the organic layer and the tetramethyl ethylenediamine serving as a rectification component in the step (2) can be recycled, and continuous production can be realized industrially.
And thirdly, the water generated in the step (2) can be used for preparing the dimethylamine aqueous solution and can be recycled.
Fourthly, the reaction condition is mild, no catalyst is required to be added, the atom economy is high, and the production is clean;
compared with the prior art, the method has the characteristics of no excessive and complete consumption of the raw material dimethylamine and low odor during reaction; the temperature and the pressure of a reaction system are low, and the reaction is safe; the selectivity of the products N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine can be adjusted, and the total yield is high.
Fifthly, a tetramethyl ethylene diamine integrated network; the tetramethylethylenediamine can be used as a co-production product and an acid-binding agent for preparing the N, N-dimethylchloroethylamine, so that the process has a self-contained acid-binding system, the post-treatment operation is simple, solid wastes which are difficult to generate post-treatment after inorganic alkali is used are avoided, and the process is green and environment-friendly.
And sixthly, circulating the raw materials. The water layer after the reaction for preparing the N, N-dimethyl chloroethyl amine is finished can be used for preparing the aqueous solution of the dimethylamine again, and the dichloroethane obtained after the post-treatment of the organic layer can also be used as a raw material to continuously react with the aqueous solution of the dimethylamine. The circular operation not only reduces the discharge of waste water, but also saves a large amount of water resources and dichloroethane, improves the atom economy, and has simple operation and environmental protection.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1, a process for the production of N, N-dimethylchloroethylamine with the co-production of tetramethylethylenediamine. Dichloroethane and a 33% dimethylamine aqueous solution are taken as starting raw materials, and the following steps are sequentially carried out:
(1) synthesizing:
67.5g of dimethylamine aqueous solution (0.5mol, the mass concentration is 33 percent), 148.5g of dichloroethane (1.5mol) and 58g of acid-binding agent tetramethylethylenediamine (0.5mol) are added into a 500ml autoclave, nitrogen is filled into the autoclave to 1.5MPa after the nitrogen in the autoclave is replaced for 3 times, stirring is started, the temperature is raised to 35 ℃ for reaction, the reaction time is 5 hours, and the obtained reaction liquid is collected.
(2) Separation:
standing the reaction solution obtained in the step (1), layering to obtain an aqueous layer (the aqueous layer is composed of water, hydrochloride of tetramethylethylenediamine and the like), and collecting an organic layer (located at the upper layer).
Dripping 35% concentrated hydrochloric acid into the organic layer, and layering the system to form an organic phase positioned on the upper layer and a water phase positioned on the lower layer, wherein the concentrated hydrochloric acid is dripped until the pH value of the water phase is 1, the organic phase is 107g of dichloroethane (which can be taken out for standby after layering), and the water phase is hydrochloride with a dissolved product; taking the water phase, introducing ammonia gas until the pH value of the water phase is 11, thereby obtaining an aqueous solution (hereinafter referred to as an aqueous solution) of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine.
Rectifying the aqueous solution under reduced pressure (20 mmHg); fractions at 60 ℃ and 75 ℃ were collected. The light fraction obtained was 21.5g of N, N-dimethylchloroethylamine and the heavy fraction was 16.7g of tetramethylethylenediamine. The conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 40.1%, and the yield of tetramethylethylenediamine was 57.5%.
The vacuum rectification can also obtain water which can be recycled (can also be used for preparing dimethylamine aqueous solution).
(3) And (3) circulation:
replacing the acid binding agent in the step (1) and dichloroethane used as a reaction raw material with tetramethylethylenediamine obtained by vacuum rectification in the step (2) and dichloroethane obtained by layering in the step (2), and repeating the steps (1) to (2); specifically, the following are:
and (3) putting 5.8g of tetramethylethylenediamine (0.05mol) obtained in the step (2) and 14.85g of dichloroethane (0.15mol) obtained by layering in the step (2) into a 100ml three-necked bottle, adding 6.75g of 33% dimethylamine aqueous solution (0.05mol) into the three-necked bottle, sealing the three-necked bottle, replacing the two with nitrogen for 3 times, introducing nitrogen to 1.5MPa, starting stirring, heating to 35 ℃ for reaction, reacting for 5 hours, and collecting the obtained reaction solution.
(4) And separation:
and (4) standing the reaction solution obtained in the step (3) and layering. And (3) taking the organic layer, dropwise adding 35% concentrated hydrochloric acid, layering the system again, and ending dropwise adding 35% concentrated hydrochloric acid until the pH value of the water phase is 1. The organic phase is dichloroethane; taking the water phase, introducing ammonia gas until the pH value of the water phase is 11, thereby obtaining the aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine.
The resulting aqueous solution was rectified under reduced pressure (20 mmHg). Respectively collecting fractions at 60 ℃ and 75 ℃; the light fraction obtained was 2.16g of N, N-dimethylchloroethylamine and the heavy fraction was 1.66g of tetramethylethylenediamine. The conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 40.2%, and the yield of tetramethylethylenediamine was 57.2%.
Examples 2-1 to 2-4, the reaction temperatures in step (1) and step (3) of example 1 were changed to 50 ℃, 65 ℃, 80 ℃, 95 ℃ respectively, and the rest was the same as example 1; the results are shown in Table 1.
Remarking: the reaction temperature of the step (1) is the same as that of the step (3).
TABLE 1
Examples 2 to 5, the reaction pressure in example 1 was changed to 1MPa, and the remainder was the same as in example 1;
the yield of N, N-dimethylchloroethylamine in the step (2) was 39.2%, and the yield of tetramethylethylenediamine was 58.8%.
The yield of N, N-dimethylchloroethylamine in the step (4) is 39.2%, and the yield of tetramethylethylenediamine is 58.9%.
Examples 2 to 6, the reaction pressure in example 1 was changed to 3MPa, and the remainder was the same as in example 1;
the yield of N, N-dimethylchloroethylamine in the step (2) is 23.2%, and the yield of tetramethylethylenediamine is 75%.
The yield of N, N-dimethylchloroethylamine in the step (4) is 23.0%, and the yield of tetramethylethylenediamine is 75.1%.
Examples 2 to 7, the molar ratio of dimethylamine and dichloroethane in example 1 was changed to 1:1, and the remainder was the same as in example 1;
the yield of the N, N-dimethyl chloroethylamine in the step (2) is 18 percent, and the yield of the tetramethyl ethylene diamine is 80.8 percent.
The yield of N, N-dimethylchloroethylamine in the step (4) was 17.6%, and the yield of tetramethylethylenediamine was 80.9%.
Examples 2 to 8, the molar ratio of dimethylamine and dichloroethane in example 1 was changed to 1:5, and the remainder was the same as in example 1;
the yield of N, N-dimethylchloroethylamine in the step (2) is 40.2%, and the yield of tetramethylethylenediamine is 58.9%.
The yield of the N, N-dimethylchloroethylamine in the step (4) is 40.1%, and the yield of the tetramethylethylenediamine is 59.0%.
Examples 2 to 9, the reaction time in example 1 was changed to 3 hours, and the rest was the same as in example 1;
the yield of the N, N-dimethyl chloroethyl amine in the step (2) is 38.4 percent, and the yield of the tetramethyl ethylene diamine is 60 percent.
The yield of N, N-dimethylchloroethylamine in the step (4) is 38.4%, and the yield of tetramethylethylenediamine is 60.1%.
Examples 2 to 10, the reaction time in example 1 was changed to 8 hours, and the rest was the same as in example 1;
the yield of N, N-dimethylchloroethylamine in the step (2) is 40.2%, and the yield of tetramethylethylenediamine is 57.5%.
The yield of N, N-dimethylchloroethylamine in the step (4) is 40.3%, and the yield of tetramethylethylenediamine is 57.5%.
Examples 2 to 11, the 33% aqueous dimethylamine solution in example 1 was changed to a 15% aqueous dimethylamine solution, and the balance was the same as in example 1;
the yield of the N, N-dimethylchloroethylamine in the step (2) is 28.4%, and the yield of the tetramethylethylenediamine is 69%.
The yield of N, N-dimethylchloroethylamine in the step (4) was 27.8%, and the yield of tetramethylethylenediamine was 68.7%.
Examples 2 to 12, the 33% aqueous dimethylamine solution in example 1 was changed to 45% aqueous dimethylamine solution, and the balance was the same as in example 1;
the yield of the N, N-dimethyl chloroethylamine in the step (2) is 40 percent, and the yield of the tetramethyl ethylene diamine is 57.5 percent.
The yield of N, N-dimethylchloroethylamine in the step (4) is 39.8%, and the yield of tetramethylethylenediamine is 57.6%.
Example 3, a process for producing N, N-dimethylchloroethylamine and co-producing tetramethylethylenediamine, using dichloroethane and a 33% dimethylamine aqueous solution as starting materials, sequentially performs the following steps:
(1) synthesizing:
67.5g of dimethylamine aqueous solution (0.5mol), 148.5g of dichloroethane (1.5mol) and 58g of acid-binding agent tetramethylethylenediamine (0.5mol) are added into a 500ml autoclave, the nitrogen in the autoclave is replaced for 3 times, then nitrogen is filled to 1MPa, stirring is started, the temperature is raised to 35 ℃ for reaction, the reaction time is 8h, and the obtained reaction solution is collected.
(2) Separation:
standing the reaction solution obtained in the step (1), layering, and taking an organic layer. Dripping 35% concentrated hydrochloric acid into the organic layer, layering the system again until the pH of the water phase is 1, finishing dripping, wherein the organic phase is 107g dichloroethane (which can be taken out after layering for later use), and the water phase is hydrochloride with the product dissolved; taking the water phase, introducing ammonia gas until the pH value of the water phase is 11, thereby obtaining the aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine. The resulting aqueous solution was rectified under reduced pressure (20 mmHg). Fractions at 60 ℃ and 75 ℃ were collected. The light fraction obtained was 21.3g of N, N-dimethylchloroethylamine and the heavy fraction was 16.9g of tetramethylethylenediamine. The conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 39.8%, and the yield of tetramethylethylenediamine was 58.2%.
(3) And (3) circulation:
and (3) putting 5.8g of tetramethylethylenediamine (0.05mol) obtained in the step (2) and 14.85g of dichloroethane (0.15mol) obtained by layering in the step (2) into a 100ml three-necked bottle, adding 6.75g of 33% dimethylamine aqueous solution (0.05mol) into the three-necked bottle, sealing the three-necked bottle, performing nitrogen replacement for 3 times, introducing nitrogen to 1MPa, starting stirring, heating to 35 ℃ for reaction, reacting for 8 hours, and collecting the obtained reaction solution.
(4) Separation:
standing the reaction solution obtained in the step (3) and layering. And (3) taking the organic layer, dropwise adding 35% concentrated hydrochloric acid, layering the system again, and ending dropwise adding the concentrated hydrochloric acid until the pH value of the water phase is 1. The organic phase is dichloroethane; taking the water phase, introducing ammonia gas until the pH value of the water phase is 11, thereby obtaining the aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine.
The resulting aqueous solution was rectified under reduced pressure (20 mmHg). Fractions at 60 ℃ and 75 ℃ were collected. The light fraction obtained was 2.14g of N, N-dimethylchloroethylamine and the heavy fraction was 1.7g of tetramethylethylenediamine. The conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 39.7%, and the yield of tetramethylethylenediamine was 59.5%.
Example 4 a process for the production of N, N-dimethylchloroethylamine with the co-production of tetramethylethylenediamine. Dichloroethane and a 33% dimethylamine aqueous solution are taken as starting raw materials, and the following steps are sequentially carried out:
(1) synthesizing:
6.75g of dimethylamine aqueous solution (0.05mol), 14.85g of dichloroethane (0.15mol) and 2.0g of acid-binding agent sodium hydroxide (0.05mol) are added into a 100ml autoclave, the nitrogen in the autoclave is replaced for 3 times, then the nitrogen is filled to 3MPa, the stirring is started, the temperature is raised to 35 ℃ for reaction, the reaction time is 3h, and the obtained reaction solution is collected.
(2) Separation:
standing the reaction solution obtained in the step (1) and layering. And taking an organic layer, dropwise adding 35% concentrated hydrochloric acid into the organic layer, layering the system again, and ending dropwise adding the concentrated hydrochloric acid until the pH value of the water phase is 1. The organic phase is dichloroethane; taking the water phase, and dropwise adding a 30% sodium hydroxide aqueous solution until the pH value of the water phase is 11, thereby obtaining an aqueous solution of N, N-dimethylchloroethylamine and tetramethylethylenediamine.
The resulting aqueous solution was rectified under reduced pressure (20 mmHg). Fractions at 60 ℃ and 75 ℃ were collected. The light fraction obtained was 0.66g of N, N-dimethylchloroethylamine and the heavy fraction was 2.53g of tetramethylethylenediamine. The conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 12.2%, and the yield of tetramethylethylenediamine was 87.4%.
Example 5 a process for the production of N, N-dimethylchloroethylamine with the co-production of tetramethylethylenediamine. Dichloroethane and a 33% dimethylamine aqueous solution are taken as starting raw materials, and the following steps are sequentially carried out:
(1) synthesizing:
6.75g of dimethylamine aqueous solution (0.05mol), 4.95g of dichloroethane (0.05mol) and 2.0g of acid-binding agent sodium hydroxide (0.05mol) are added into a 50ml autoclave, the nitrogen in the autoclave is replaced for 3 times, then the nitrogen is filled to 3MPa, the stirring is started, the temperature is increased to 80 ℃ for reaction, the reaction time is 8h, and the obtained reaction solution is collected.
(2) Separation:
standing the reaction solution obtained in the step (1) and layering. And (3) taking the organic layer, dropwise adding 35% concentrated hydrochloric acid, layering the system again, and ending dropwise adding the concentrated hydrochloric acid until the pH value of the water phase is 1. The organic phase is dichloroethane; taking the water phase, and dropwise adding a 30% sodium hydroxide aqueous solution until the pH value of the water phase is 11, thereby obtaining an aqueous solution of N, N-dimethylchloroethylamine and tetramethylethylenediamine.
The resulting aqueous solution was rectified under reduced pressure (20 mmHg). Fractions at 60 ℃ and 75 ℃ were collected. The light fraction obtained was 0.07g of N, N-dimethylchloroethylamine and the heavy fraction was 2.83g of tetramethylethylenediamine. The conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 1.3%, and the yield of tetramethylethylenediamine was 97.5%.
Example 6-1, the acid-binding agent in example 4 was changed to sodium carbonate, and the rest was the same as example 1;
the yield of N, N-dimethylchloroethylamine in the step (2) is 5.0%, and the yield of tetramethylethylenediamine is 93.8%.
Example 6-2, the acid-binding agent in example 4 was changed to sodium bicarbonate, and the rest was the same as example 1;
the yield of N, N-dimethylchloroethylamine in the step (2) is 8.1%, and the yield of tetramethylethylenediamine is 91.1%.
In comparative example 1-1, the amount of tetramethylethylenediamine as an acid-binding agent was changed from 0.5mol to 0.25mol, and the rest was the same as in steps 1) to 2) of example 1.
The results obtained were: the conversion of dimethylamine was 94%, the yield of N, N-dimethylchloroethylamine was 12.8%, and the yield of tetramethylethylenediamine was 80.4%.
In comparative example 1-2, the amount of tetramethylethylenediamine as an acid-binding agent was changed from 0.5mol to 0.75mol, and the rest was the same as in steps 1) to 2) of example 1.
The results obtained were: the conversion of dimethylamine was 100%, the yield of N, N-dimethylchloroethylamine was 37.6%, and the yield of tetramethylethylenediamine was 62.4%.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
- The self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine is characterized by comprising the following steps of:1) according to dimethylamine: dichloroethane =1: 1-5 molar ratio, dimethylamine aqueous solution and dichloroethane are used as reaction raw materials, an acid-binding agent with the same molar quantity as dimethylamine is added into the reaction raw materials for heating reaction, the heating reaction temperature is 30-90 ℃, the reaction pressure is 1-3 MPa, and the reaction time is 3-8 h;the acid-binding agent is tetramethylethylenediamine, and the mass concentration of dimethylamine in the dimethylamine aqueous solution is 30-40%;2) carrying out post-treatment on the reaction product obtained in the step 1), wherein the post-treatment comprises the following steps: standing and layering the obtained reaction product to respectively obtain a water layer and an organic layer; taking an organic layer, adding hydrochloric acid, layering to form an organic phase on the upper layer and a water phase on the lower layer, and stopping adding hydrochloric acid until the pH value of the water phase is 1-2; the organic phase is dichloroethane; taking a water phase, and adding alkali until the pH value of the water phase is 11-12, so as to obtain an aqueous solution of N, N-dimethyl chloroethyl amine and tetramethyl ethylene diamine;and (3) carrying out vacuum rectification on the aqueous solution of the N, N-dimethyl chloroethylamine and the tetramethyl ethylenediamine to respectively obtain the N, N-dimethyl chloroethylamine as a light component and the tetramethyl ethylenediamine as a heavy component.
- 2. The self-acid-binding integrated production method of N, N-dimethylchloroethylamine and tetramethylethylenediamine according to claim 1, characterized by: in the step 2), the alkali for adjusting the pH value of the water phase is ammonia gas and a sodium hydroxide aqueous solution with the mass concentration of 30 +/-5%.
- 3. The self-acid-binding integrated production method of N, N-dimethylchloroethylamine and tetramethylethylenediamine according to claim 2, characterized by: in the step 2), the pressure of the reduced pressure distillation is 20mmHg, N-dimethyl chloroethyl amine is obtained as a light component at the temperature of 60 ℃, and tetramethyl ethylene diamine is obtained as a heavy component at the temperature of 75 ℃.
- 4. The self-acid-binding integrated production method of N, N-dimethylchloroethylamine and tetramethylethylenediamine according to any one of claims 1 to 3, characterized by comprising: replacing dichloroethane and an acid-binding agent which are used as reaction raw materials with dichloroethane and tetramethylethylenediamine obtained in the step 2), and repeating the steps 1) to 2), thereby realizing circulation.
- 5. The self-acid-binding integrated production method of N, N-dimethylchloroethylamine and tetramethylethylenediamine according to any one of claims 1 to 3, characterized by comprising:when high yields of N, N-dimethylchloroethylamine were obtained: the molar ratio of dimethylamine to dichloroethane is 1: 3-5, the reaction pressure is 1-1.5 MPa, the heating reaction temperature is 35 ℃, the reaction time is 5-8 h,when tetramethylethylenediamine was obtained in high yield: the molar ratio of dimethylamine to dichloroethane is 1:1, the reaction pressure is 3.0MPa, the heating reaction temperature is 80 ℃, and the reaction time is 8 h.
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