CN111620884A - Synthetic method of triethylene diamine - Google Patents
Synthetic method of triethylene diamine Download PDFInfo
- Publication number
- CN111620884A CN111620884A CN202010604011.6A CN202010604011A CN111620884A CN 111620884 A CN111620884 A CN 111620884A CN 202010604011 A CN202010604011 A CN 202010604011A CN 111620884 A CN111620884 A CN 111620884A
- Authority
- CN
- China
- Prior art keywords
- triethylene diamine
- pressure
- catalyst
- piperazine
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/08—Bridged systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of triethylene diamine, and solves the technical problems of high cost of the existing production process, certain danger of raw materials, no environmental protection, complex synthesis process, low product yield and the like. Which comprises the following steps: (1) adding oxalic acid diester into a reaction bottle, dissolving piperazine with a solvent in advance, adding the dissolved piperazine, adding a catalyst, dropwise adding piperazine dissolved with the solvent at a reaction temperature of 30-80 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake with the solvent, and drying to obtain an intermediate product, namely, oxytetramethylene diamine; (2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding a solvent until the dioxy triethylene diamine is completely dissolved, adding a catalyst, covering and sealing a kettle cover tightly, heating to 150-200 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 2-10 MPa, and continuously filling hydrogen in the reaction process to keep the pressure, thereby obtaining a triethylene diamine crude product; (3) and carrying out post-treatment to obtain a final product triethylene diamine. The method is applied to the synthesis of triethylene diamine.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of triethylene diamine.
Background
Triethylene diamine is an important chemical raw material, is used as a catalyst of polyurethane, and is also used as an oil additive; as corrosion inhibitors in boiler water treatment, but also as catalysts for polyurethane foaming and polymerization, accelerators for epoxy resin curing, catalysts for acrylonitrile, ethylene and alkyl ethylene oxides; as non-nucleophilic bases, the reagents for splitting the beta-keto-and gem-di-vinegar and dehydrohalogenation react with the compounds of organomagnesium, lithium and zinc to form complexes, so as to increase the activity and participate in many reactions.
Currently, there are 2 main methods for industrially synthesizing triethylene diamine according to different raw material routes: synthesized from piperazine derivatives and ethylenediamine as raw material.
The synthesis reaction of triethylene diamine is researched by a two-step synthesis method by taking piperazine as a raw material in Tianjin university, wherein the reaction process comprises the steps of synthesizing crude N-hydroxyethyl piperazine by using ethylene oxide and piperazine, and cyclizing the N-hydroxyethyl piperazine in a fixed bed reactor to obtain the triethylene diamine, wherein the yield is about 82%.
The method is characterized in that ethylenediamine is used as a raw material for synthesis, the northwest university mainly uses ethylenediamine as a raw material, a modified zeolite molecular sieve is used as a catalyst for synthesis of triethylene diamine, piperazine is coproduced, and the conversion rate of ethylenediamine and the selectivity of triethylene diamine are respectively over 97% and 55% through control of reaction conditions and modification of the catalyst, but no industrial case exists.
From the prior preparation process, the process route for preparing the triethylene diamine by using the piperazine derivative as the raw material is mature, the yield is high, and a small-scale industrialized device is available. However, the process is limited because of the low yield and high cost of piperazine derivatives. The ethylene oxide is synthesized by taking the ethylene oxide as a raw material, although the raw material is cheap and easy to obtain, the ethylene oxide is flammable and explosive toxic gas and has certain danger in use, the ethylene oxide and the piperazine water solution are required to be fed together for reaction in the reaction, the reaction temperature is high, and the product yield is low.
Disclosure of Invention
Aiming at the technical problems, the invention provides the synthesis method of the triethylene diamine, which has the advantages of low raw material cost, good safety, simple synthesis process, good selectivity, high total yield, high purity, simple post-treatment and environmental friendliness.
To this end, the invention comprises the following steps:
(1) dissolving piperazine by using a solvent A in advance, adding oxalic acid diester into a reaction container, adding the solvent A until the oxalic acid diester is completely dissolved, adding a catalyst A, then dropwise adding the piperazine dissolved by using the solvent A at a reaction temperature of 30-80 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the solvent A, and drying to obtain an intermediate product, namely bis (oxytriethylenediamine);
the chemical equation is as follows:
wherein R is CH3Or CH3CH2The oxalic acid diester is dimethyl oxalate or diethyl oxalate;
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding a solvent B until the dioxy triethylene diamine is completely dissolved, adding a catalyst B, tightly covering and sealing a kettle cover, heating to 150-200 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 2-10 MPa, and continuously filling the hydrogen in the reaction process to keep the pressure until the pressure is not obviously reduced any more, so as to obtain a triethylene diamine crude product;
the chemical equation is as follows:
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove the solvent B, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine.
Preferably, in the step (1), the solvent A is methanol or ethanol, the solvent A is methanol when the oxalic acid diester is dimethyl oxalate, and the solvent A is ethanol when the oxalic acid diester is diethyl oxalate; the catalyst A is one of sodium methoxide, sodium ethoxide or sodium hydroxide; when the catalyst A is sodium methoxide, the oxalic acid diester is dimethyl oxalate, and the solvent A is methanol; when the catalyst A is sodium ethoxide, the oxalic acid diester is diethyl oxalate, and the solvent A is ethanol; the molar ratio of the oxalic diester to the piperazine is 1.00-1.30: 1, and the mass ratio of the catalyst A to the piperazine is 0.01-0.20: 1.
Preferably, the oxalic acid diester in the step (1) is dimethyl oxalate, and the solvent A is methanol.
Preferably, in step (1), catalyst A is sodium methoxide.
Preferably, in the step (1), the molar ratio of the oxalic acid diester to the piperazine is 1.05-1.15: 1, and the mass ratio of the catalyst A to the piperazine is 0.05-0.10: 1; the molar ratio of the oxalic diester to the piperazine is 1.05: 1, and the mass ratio of the catalyst A to the piperazine is 0.05: 1.
Preferably, the reaction temperature in the step (1) is 40-60 ℃.
Preferably, the solvent B in the step (2) is one of toluene, dioxane, methanol, cyclohexane or tetrahydrofuran; the catalyst B is a Raney metal or noble metal catalyst, the Raney metal is Raney copper or Raney nickel, and the noble metal catalyst is one of palladium carbon, ruthenium carbon, palladium alumina or ruthenium alumina; the mass ratio of the catalyst B to the piperazine is 0.05: 1.
Preferably, the solvent B in the step (2) is cyclohexane or tetrahydrofuran.
Preferably, catalyst B in step (2) is palladium on carbon.
Preferably, the temperature rise is 170-180 ℃, and the pressure is 5 MPa.
The invention has the beneficial effects that:
the reaction step (1) of the invention is an aminolysis reaction, and under an alkaline condition, ester and amine react to generate amide and alcohol. In the synthetic route for synthesizing triethylene diamine by taking piperazine as a raw material, oxalic acid diester replaces high-risk ethylene oxide to serve as a cyclization reagent, so that the safety is higher, the production cost of the oxalic acid diester serving as a reaction intermediate is low along with the maturity of a process for synthesizing ethylene glycol by a coal method, the production cost can be greatly reduced by taking the oxalic acid diester as the cyclization reagent, and the synthetic route is favorable for improving the application range of coal in the aspect of basic chemical engineering as a coal cauldron.
And (3) performing intramolecular hydrogenation dehydration in the reaction step (2) under the action of a catalyst, and performing subsequent separation to obtain triethylene diamine.
The method has the advantages of simple synthesis process, good selectivity, high total yield, high purity, simple post-treatment and environment friendliness, and only contains triethylene diamine and water as a product, and has good industrial prospect.
Detailed Description
The present invention will be further described with reference to specific examples to assist understanding of the invention. The method used in the invention is a conventional production method if no special provisions are made; the starting materials used, unless otherwise specified, are conventional commercial products.
Example 1
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product of 98.11g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 87.6%, and the purity of the triethylenediamine was 99.0% by gas phase detection.
Example 2
(1) Dissolving piperazine by using methanol in advance, adding 118g (1.00mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, then slowly dropwise adding 86g (1mol) of piperazine dissolved by using methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using methanol, and drying to obtain an intermediate product, namely the dioxytriethylene diamine;
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 95.42g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 85.2%, and the purity of the triethylenediamine was 99.0% by gas phase detection.
Example 3
(1) Dissolving piperazine by using methanol in advance, adding 135.7g (1.15mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, then slowly dropwise adding 86g (1mol) of piperazine dissolved by using methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product of 98.45g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 87.9%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 4
(1) Dissolving piperazine by using methanol in advance, adding 153.4g (1.30mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product of 98.11g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 87.6%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 5
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 0.86g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine 87.25 g.
The molar yield of the triethylenediamine was calculated to be 77.9%, and the purity of the triethylenediamine was 98.4% by gas phase detection.
Example 6
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 8.6g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product triethylene diamine of 97.89 g.
The molar yield of the triethylenediamine was calculated to be 87.4%, and the purity of the triethylenediamine was 98.5% by gas phase detection.
Example 7
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding methanol until the dimethyl oxalate is completely dissolved, adding 17.2g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 97.33g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 86.9%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 8
(1) Dissolving piperazine by using ethanol in advance, adding 123.9g (1.05mol) of diethyl oxalate into a reaction bottle with a mechanical stirring device, adding ethanol until the diethyl oxalate is completely dissolved, adding 4.3g of sodium ethoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using ethanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using ethanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 94.42g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 84.3%, and the purity of the triethylenediamine was 98.3% by gas phase detection.
Example 9
(1) Dissolving piperazine by using ethanol in advance, adding 123.9g (1.05mol) of diethyl oxalate into a reaction bottle with a mechanical stirring device, adding ethanol until the diethyl oxalate is completely dissolved, adding 0.86g of sodium ethoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using ethanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using ethanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product of 93.18g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 83.2%, and the purity of the triethylenediamine was 99.3% by gas phase detection.
Example 10
(1) Dissolving piperazine by using ethanol in advance, adding 135.7g (1.15mol) of diethyl oxalate into a reaction bottle with a mechanical stirring device, adding ethanol until the diethyl oxalate is completely dissolved, adding 4.3g of sodium ethoxide, then slowly dropwise adding 86g (1mol) of piperazine dissolved by using ethanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using ethanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 95.09g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 84.9%, and the purity of the triethylenediamine was 99.0% by gas phase detection.
Example 11
(1) Dissolving piperazine by using ethanol in advance, adding 123.9g (1.05mol) of diethyl oxalate into a reaction bottle with a mechanical stirring device, adding ethanol until the diethyl oxalate is completely dissolved, adding 4.3g of sodium hydroxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using ethanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing the obtained filter cake by using ethanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 86.69g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 77.4%, and the purity of the triethylenediamine was 98.8% by gas phase detection.
Example 12
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 60 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine 97.44 g.
The molar yield of the triethylenediamine was calculated to be 87.0%, and the purity of the triethylenediamine was 98.5% by gas phase detection.
Example 13
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 30 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product, namely 95.54g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 85.3%, and the purity of the triethylenediamine was 98.3% by gas phase detection.
Example 14
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 80 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 93.07g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 83.1%, and the purity of the triethylenediamine was 98.2% by gas phase detection.
Example 15
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding toluene until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product, namely 96.54g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 86.2%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 16
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding methanol until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine 94.75 g.
The molar yield of the triethylenediamine was calculated to be 84.6%, and the purity of the triethylenediamine was 98.4% by gas phase detection.
Example 17
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxytriethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding dioxane until the dioxytriethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing the kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen in the reaction process to keep the pressure until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product triethylene diamine of 90.05 g.
The molar yield of the triethylenediamine was calculated to be 80.4%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 18
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding cyclohexane until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 97.33g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 86.9%, and the purity of the triethylenediamine was 99.0% by gas phase detection.
Example 19
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the oxytetramethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the oxytetramethylene diamine is completely dissolved, adding 4.3g of palladium alumina, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to keep the pressure in the reaction process until the pressure is not obviously reduced any more, so as to obtain a crude product of the oxytetramethylene diamine;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 94.98g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 84.8%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 20
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the oxytetramethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the oxytetramethylene diamine is completely dissolved, adding 4.3g of ruthenium carbon, tightly covering and sealing the kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to keep the pressure in the reaction process until the pressure is not obviously reduced any more, so as to obtain a crude product of the oxytetramethylene diamine;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product of 93.74g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 83.7%, and the purity of the triethylenediamine was 98.5% by gas phase detection.
Example 21
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the oxytetramethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the oxytetramethylene diamine is completely dissolved, adding 4.3g of ruthenium aluminum oxide, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to keep the pressure in the reaction process until the pressure is not obviously reduced any more to obtain a crude product of the oxytetramethylene diamine;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 91.28g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 91.5%, and the purity of the triethylenediamine was 98.7% by gas phase detection.
Example 22
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the oxytetramethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the oxytetramethylene diamine is completely dissolved, adding 4.3g of Raney nickel, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to keep the pressure in the reaction process until the pressure is not obviously reduced any more to obtain a crude product of the oxytetramethylene diamine;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product of 93.63g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 83.6%, and the purity of the triethylenediamine was 98.2% by gas phase detection.
Example 23
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the oxytetramethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the oxytetramethylene diamine is completely dissolved, adding 4.3g of Raney copper, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to keep the pressure in the reaction process until the pressure is not obviously reduced any more to obtain a crude product of the oxytetramethylene diamine;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 83.22g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 74.3%, and the purity of the triethylenediamine was 98.1% by gas phase detection.
Example 24
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 150 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, so as to obtain a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product triethylene diamine 94.86 g.
The molar yield of the triethylenediamine was calculated to be 84.7%, and the purity of the triethylenediamine was 99.0% by gas phase detection.
Example 25
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 180 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, so as to obtain a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product triethylene diamine of 97.89 g.
The molar yield of the triethylenediamine was calculated to be 87.4%, and the purity of the triethylenediamine was 99.3% by gas phase detection.
Example 26
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 200 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 5MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain a final product, namely 95.76g of triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 85.5%, and the purity of the triethylenediamine was 98.9% by gas phase detection.
Example 27
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 3MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain 89.94g of the final product triethylene diamine.
The molar yield of the triethylenediamine was calculated to be 80.3%, and the purity of the triethylenediamine was 98.6% by gas phase detection.
Example 28
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 8MPa, continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, and obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine 97.55 g.
The molar yield of triethylenediamine was calculated to be 87.1%, and the purity of triethylenediamine was 99.1% by gas phase detection.
Example 29
(1) Dissolving piperazine by using methanol in advance, adding 123.9g (1.05mol) of dimethyl oxalate into a reaction bottle with a mechanical stirring device, adding the methanol until the dimethyl oxalate is completely dissolved, adding 4.3g of sodium methoxide, slowly dropwise adding 86g (1mol) of piperazine dissolved by using the methanol at the temperature of 40 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the methanol, and drying to obtain an intermediate product, namely bis (oxytriethylene diamine);
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding tetrahydrofuran until the dioxy triethylene diamine is completely dissolved, adding 4.3g of palladium carbon, tightly covering and sealing a kettle cover, heating to 175 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 10MPa, and continuously filling the hydrogen into the high-pressure valve to maintain the pressure in the reaction process until the pressure is not obviously reduced any more, thereby obtaining a triethylene diamine crude product;
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove tetrahydrofuran, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine 97.78 g.
The molar yield of the triethylenediamine was calculated to be 87.3%, and the purity of the triethylenediamine was 99.0% by gas phase detection.
From examples 1 to 4, it is understood that when dimethyl oxalate is selected as a reactant under the condition that other reaction conditions are consistent, the molar yield of triethylene diamine is improved as the molar ratio of dimethyl oxalate to piperazine is increased. When the molar ratio of dimethyl oxalate to piperazine is 1.05-1.15: 1, the molar yield of triethylene diamine is the highest; when the molar ratio of the dimethyl oxalate to the piperazine is more than 1.05, the molar ratio is continuously improved, and the molar yield of the triethylene diamine is not obviously increased any more. Therefore, a molar ratio of dimethyl oxalate to piperazine equal to 1.05 is the best choice.
As is clear from examples 1, 5, 6 and 7, when sodium methoxide was selected as the catalyst in step (1) on the premise that the other reaction conditions were consistent, the molar yield of triethylenediamine increased as the mass ratio of sodium methoxide to piperazine increased. When the mass ratio of the sodium methoxide to the piperazine is 0.05-0.10: 1, the molar yield of the triethylene diamine is highest; when the mass ratio of sodium methoxide to piperazine is more than 0.05, the mass ratio is continuously improved, and the molar yield of the triethylene diamine is not obviously increased any more. Therefore, a mass ratio of sodium methoxide to piperazine equal to 0.05 is the best choice.
As is apparent from examples 1, 8, 9, 10 and 11, the molar yield of triethylene diamine in step (1) was higher when sodium methoxide or sodium ethoxide was used as a catalyst than when sodium hydroxide was used as a catalyst, and the molar yield of triethylene diamine was the highest when dimethyl oxalate was used as a reactant and methanol was used as a solvent, on the premise that other reaction conditions were consistent.
From examples 1, 12, 13 and 14, it can be seen that, on the premise of other consistent reaction conditions, the molar yield of triethylene diamine in step (1) is gradually increased with the increase of reaction temperature, because the reaction speed is slow at low temperature and the reaction is incomplete; when the temperature is higher than 60 ℃, the temperature is continuously increased, impurities generated in the reaction are increased, and the yield of the triethylene diamine is reduced, so that the molar yield of the triethylene diamine is the highest within the temperature range of 40-60 ℃.
As is clear from examples 1, 15, 16, 17 and 18, the molar yield of triethylene diamine was the highest when cyclohexane and tetrahydrofuran were selected as the solvent in step (2) under otherwise identical reaction conditions.
It is understood from examples 1, 19, 20, 21, 22 and 23 that the molar yield of triethylenediamine is the highest when palladium on carbon is selected as the catalyst in step (2) under otherwise identical reaction conditions.
As can be seen from examples 1, 24, 25 and 26, on the premise that other reaction conditions are consistent, the molar yield of triethylene diamine in step (2) is gradually increased with the increase of the reaction temperature, because the reaction speed is slow at low temperature and the reaction is incomplete; when the temperature is higher than 180 ℃, the temperature is continuously increased, impurities generated in the reaction are increased, and the yield of the triethylene diamine is reduced, so that the molar yield of the triethylene diamine is the highest within the temperature range of 175-180 ℃.
From examples 1, 27, 28 and 29, it is understood that the molar yield of triethylenediamine increases with the increase of the reaction pressure in step (2) under the condition that other reaction conditions are consistent, and when the pressure is higher than 5MPa, the molar yield of triethylenediamine does not increase significantly any more, and therefore, the pressure equal to 5MPa is the best choice.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that the embodiments may be modified or changed without departing from the spirit of the present invention within the scope of the claims.
Claims (10)
1. A synthetic method of triethylene diamine is characterized by comprising the following steps:
(1) dissolving piperazine by using a solvent A in advance, adding oxalic acid diester into a reaction container, adding the solvent A until the oxalic acid diester is completely dissolved, adding a catalyst A, then dropwise adding the piperazine dissolved by using the solvent A at a reaction temperature of 30-80 ℃, stirring for 1-2 hours after dropwise adding, filtering, washing an obtained filter cake by using the solvent A, and drying to obtain an intermediate product, namely bis (oxytriethylenediamine);
the chemical equation is as follows:
wherein R is CH3Or CH3CH2Namely, the oxalic acid diester is dimethyl oxalate or diethyl oxalate;
(2) adding the dioxy triethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding a solvent B until the dioxy triethylene diamine is completely dissolved, adding a catalyst B, tightly covering and sealing a kettle cover, heating to 150-200 ℃, filling hydrogen into a high-pressure valve until the pressure reaches 2-10 MPa, and continuously filling the hydrogen in the reaction process to keep the pressure until the pressure is not obviously reduced any more, so as to obtain a triethylene diamine crude product;
the chemical equation is as follows:
(3) and (3) opening an exhaust valve of the high-pressure reaction kettle to exhaust, opening a kettle cover, cooling to room temperature, filtering the triethylene diamine crude product prepared in the step (2) to remove the catalyst, rectifying to remove the solvent B, adding ethanol, pulping, filtering, and drying the obtained filter cake to obtain the final product triethylene diamine.
2. The method for synthesizing triethylenediamine according to claim 1, wherein in step (1), the solvent a is methanol or ethanol, and when the oxalic acid diester is dimethyl oxalate, the solvent a is methanol, and when the oxalic acid diester is diethyl oxalate, the solvent a is ethanol; the catalyst A is one of sodium methoxide, sodium ethoxide or sodium hydroxide; when the catalyst A is sodium methoxide, the oxalic acid diester is dimethyl oxalate, and the solvent A is methanol; when the catalyst A is sodium ethoxide, the oxalic acid diester is diethyl oxalate, and the solvent A is ethanol; the molar ratio of the oxalic diester to the piperazine is 1.00-1.30: 1, and the mass ratio of the catalyst A to the piperazine is 0.01-0.20: 1.
3. The method for synthesizing triethylenediamine according to claim 2, wherein the oxalic acid diester in step (1) is dimethyl oxalate, and the solvent a is methanol.
4. The method for synthesizing triethylenediamine according to claim 2, wherein in step (1), the catalyst a is sodium methoxide.
5. The method for synthesizing triethylene diamine according to claim 2, wherein the molar ratio of oxalic acid diester to piperazine in step (1) is 1.05-1.15: 1, and the mass ratio of catalyst A to piperazine is 0.05-0.10: 1; the molar ratio of the oxalic diester to the piperazine is 1.05: 1, and the mass ratio of the catalyst A to the piperazine is 0.05: 1.
6. The method for synthesizing triethylenediamine according to claim 1, wherein the reaction temperature in step (1) is 40-60 ℃.
7. The method for synthesizing triethylenediamine according to claim 1, wherein the solvent B in step (2) is one of toluene, dioxane, methanol, cyclohexane, or tetrahydrofuran; the catalyst B is a Raney metal or a noble metal catalyst, the Raney metal is Raney copper or Raney nickel, and the noble metal catalyst is one of palladium carbon, ruthenium carbon, palladium alumina or ruthenium alumina; the mass ratio of the catalyst B to the piperazine is 0.05: 1.
8. The method for synthesizing triethylenediamine according to claim 7, wherein the solvent B in step (2) is cyclohexane or tetrahydrofuran.
9. The method for synthesizing triethylenediamine according to claim 7, wherein the catalyst B in step (2) is palladium on carbon.
10. The method for synthesizing triethylenediamine according to claim 1, wherein in step (2), the temperature is raised to 170 to 180 ℃ and the pressure is 5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010604011.6A CN111620884B (en) | 2020-06-29 | 2020-06-29 | Synthetic method of triethylene diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010604011.6A CN111620884B (en) | 2020-06-29 | 2020-06-29 | Synthetic method of triethylene diamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111620884A true CN111620884A (en) | 2020-09-04 |
| CN111620884B CN111620884B (en) | 2021-06-04 |
Family
ID=72257722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010604011.6A Active CN111620884B (en) | 2020-06-29 | 2020-06-29 | Synthetic method of triethylene diamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111620884B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560863A (en) * | 2022-01-27 | 2022-05-31 | 青岛科技大学 | Triethylene diamine quaternary ammonium salt, preparation method of triethylene diamine quaternary ammonium base and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772293A (en) * | 1971-12-13 | 1973-11-13 | Air Prod & Chem | Single step synthesis of trietylene diamine |
| US4757143A (en) * | 1986-06-09 | 1988-07-12 | Texaco Inc. | Catalytic method for the manufacture of triethylenediamine |
| CN107163054A (en) * | 2017-05-16 | 2017-09-15 | 绍兴兴欣化工有限公司 | A kind of synthetic method of triethylene diamine |
| CN108912120A (en) * | 2018-07-18 | 2018-11-30 | 西安近代化学研究所 | A kind of preparation method of triethylene diamine coproduction N- aminoethyl piperazine |
-
2020
- 2020-06-29 CN CN202010604011.6A patent/CN111620884B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772293A (en) * | 1971-12-13 | 1973-11-13 | Air Prod & Chem | Single step synthesis of trietylene diamine |
| US4757143A (en) * | 1986-06-09 | 1988-07-12 | Texaco Inc. | Catalytic method for the manufacture of triethylenediamine |
| CN107163054A (en) * | 2017-05-16 | 2017-09-15 | 绍兴兴欣化工有限公司 | A kind of synthetic method of triethylene diamine |
| CN108912120A (en) * | 2018-07-18 | 2018-11-30 | 西安近代化学研究所 | A kind of preparation method of triethylene diamine coproduction N- aminoethyl piperazine |
Non-Patent Citations (5)
| Title |
|---|
| J.W.LABADIE，D.D.DIXON: "Selective catalytic syntheses of mixed alkyl amines", 《JOURNAL OF MOLECULAR CATALYSIS》 * |
| YONG WANG,ET AL.: "Intermolecular condensation of ethylenediamine to 1,4-diazabicyclo[2,2,2]octane over TS-1 catalysts", 《JOURNAL OF CATALYSIS》 * |
| 李海涛: "三乙烯二胺合成技术述评", 《化学工业与工程技术》 * |
| 杨国忠: "三乙烯二胺的合成及应用", 《精细与专用化学品》 * |
| 王昱官: "三乙烯二胺合成工艺现状分析", 《辽宁化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560863A (en) * | 2022-01-27 | 2022-05-31 | 青岛科技大学 | Triethylene diamine quaternary ammonium salt, preparation method of triethylene diamine quaternary ammonium base and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111620884B (en) | 2021-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108610324B (en) | Preparation method of vinyl sulfate | |
| CN113004171B (en) | Preparation method of 3-methoxypropylamine | |
| CN111620884B (en) | Synthetic method of triethylene diamine | |
| CN101928222B (en) | Synthesis method of N, N, N', N'-tetraisopropyl ethylene diamine | |
| CN107335436B (en) | Method for preparing 1, 4-pentanediol by catalytic hydrogenation of levulinic acid compounds | |
| CN110407725B (en) | Preparation method of 2-mercaptoethanol | |
| CN104710402A (en) | Dicyclohexyl crown ether synthesis method | |
| CN103497157A (en) | 2-imidazolidone synthesis method | |
| CN106749117A (en) | A kind of preparation method of 3 amino methyl tetrahydrofuran | |
| CN109422654B (en) | Method for synthesizing fatty aminomethylated compounds | |
| CN106831595B (en) | A kind of benzyl imidazole ionic liquid and the method using its catalytically synthesizing cyclic carbonate ester | |
| CN115160148A (en) | High-selectivity method for synthesizing N-allylbenzylamine | |
| CN109824520B (en) | Preparation method of cis-4-methylcyclohexylamine | |
| CN114835661A (en) | Industrial preparation method of a-acetyl-r-butyrolactone | |
| CN111393402B (en) | N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide | |
| CN112679342A (en) | Preparation method of trans, trans-4, 4' -dicyclohexyl dicarboxylic acid | |
| CN112375045B (en) | Synthetic method of piperazine | |
| CN116178136B (en) | Preparation method of 2-hexyl decanoic acid | |
| CN113072449B (en) | Synthesis method of 4,4, 4-trifluoroacetylacetic acid ethyl ester | |
| CN105037192A (en) | One-step method for synthesizing p-formylamino benzene alkyl ether as octane booster | |
| CN111018664B (en) | Synthesis method of 2-alkyl-1, 3-propanediol compound | |
| CN115073309A (en) | Preparation method of o-hydroxybenzylamine | |
| CN109369618B (en) | Method for preparing 2-chloro-5- ((2- (nitromethylene) imidazoline-1-yl) methyl) pyridine in one pot | |
| CN102070458B (en) | Method for synthesizing aliphatic amine compound | |
| CN110857284B (en) | Method for synthesizing N-methyl aliphatic amine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |