CN110256287B - Synthesis method of high-content N-fatty alkyl-1, 3-propylene diamine - Google Patents
Synthesis method of high-content N-fatty alkyl-1, 3-propylene diamine Download PDFInfo
- Publication number
- CN110256287B CN110256287B CN201910378669.7A CN201910378669A CN110256287B CN 110256287 B CN110256287 B CN 110256287B CN 201910378669 A CN201910378669 A CN 201910378669A CN 110256287 B CN110256287 B CN 110256287B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acrylonitrile
- reaction
- potassium hydroxide
- hydrogenation
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing high-content N-fatty alkyl-1, 3-propylene diamine, belonging to the field of synthetic methods of compounds in organic chemical industry. The preparation method comprises the following steps: (1) condensation: adding fatty primary amine, acrylonitrile and catalyst softened water into a reaction kettle, sealing the reaction kettle, and reacting after nitrogen replacement; (2) catalytic hydrogenation: adding the nitrile ethyl alkylamine obtained by the condensation reaction in the step (1) into a hydrogenation reaction kettle, adding a hydrogenation catalyst, adding an alkaline metal oxide and a potassium hydroxide aqueous solution, and then performing hydrogen replacement to obtain the high-content N-fatty alkyl-1, 3-propylenediamine. The recovered catalyst is reused. The process is simple, the water solution of calcium oxide and potassium hydroxide is used as inhibitor, and the amount of calcium oxide and potassium hydroxide is based on the amount of palladium carbon or Raney nickel added as catalyst. Good selectivity and high product purity. Greatly reducing the environmental pollution and continuously recycling the recovered catalyst. Is suitable for industrial production.
Description
Technical Field
The invention relates to a method for synthesizing high-content N-fatty alkyl-1, 3-propylene diamine, belonging to the field of synthetic methods of compounds in organic chemical industry.
Background
N-aliphatic alkyl-1, 3-propylenediamine is an important class of organic products. The number of alkyl groups linked to the carbon chain and nitrogen atom can be divided into: coconut oil based propylene diamine, oleyl propylene diamine, dodecyl/tetradecyl propylene diamine, tallow propylene diamine, hydrogenated tallow propylene diamine, stearyl propylene diamine, and the like. The emulsifier is mainly used for asphalt emulsifier, and has the characteristics of strong emulsifying power, small using amount, quick demulsification and the like. It is also used in mineral flotation agent, adhesive, waterproof agent, corrosion inhibition, etc. and is also the intermediate for producing corresponding quaternary ammonium salt. The method is also widely applied to industries such as paint additives, pigment treating agents and the like. The structure is as follows.
R-NH-CH2-CH2-CH2-NH2 R=C12-C18
The conventional synthesis method of N-aliphatic alkyl-1, 3-propylene diamine comprises the following steps: the two-step synthesis method by General Mills and Armour in the U.S. is as follows:
the raw materials for producing the N-aliphatic alkyl-1, 3-propylene diamine are distilled tallow primary amine, acrylonitrile and pure hydrogen, and methanol is used as a catalyst for the ethylation of the acrylonitrile. Cobalt oxide acts as a hydrogenation catalyst and the action of ammonia gas suppresses the second bond linked to the terminal ammonia.
The hydrogenation route uses ammonia gas as an inhibitor, which causes troubles in the later treatment and recycling of three wastes of products.
The company Hoechst A-VHT in Germany produces N-fatty alkyl-1, 3-propylenediamine as follows:
fatty primary amine and acrylonitrile are subjected to condensation reaction, sodium methoxide is used as a catalyst in the reaction, and the next hydrogenation reaction can be continued after the reaction [ 1 ] is completed and water washing is needed. Also ammonia gas is exposed to increased recovery steps at the end of the reaction.
The aminopropionitrile is synthesized by the Japan grease company under the existence condition of the fatty primary amine, the acrylonitrile, the reclaimed water and the isopropanol, and the yield reaches 98 percent. The aminopropionitrile is hydrogenated to prepare the N-aliphatic alkyl-1, 3-propylene diamine, and water or alkali is used for preventing the generation of secondary amine as a byproduct. The amount of inhibitor is not substantially detailed in the open literature for controlling selectivity due to technical secrecy, etc.
In synthesis and process improvement of N-dodecyl-1.3 trimethylene diamine in Yanjunfeng and Liu Shi Qin, dodecylamine and acrylonitrile are used as raw materials, and deionized water is used as a catalyst in an acrylonitrile ethylation reaction process to prepare 3-dodecylamine propionitrile. Then, raney nickel is used as a hydrogenation catalyst, and under the action of a self-made composite alkali inhibitor, high-pressure hydrogenation is carried out to synthesize the N-dodecyl-1, 3-trimethylene diamine. The author systematically analyzes the selectivity of the hydrogenation inhibitor and determines that the home-made composite alkali has good effect as the hydrogenation inhibitor. The yield of diamine and the content of crude product can reach more than 93 percent. However, the authors do not disclose the composition and preparation of the complex base. It is difficult to evaluate the results of the synthesis reaction.
Disclosure of Invention
According to the defects of the prior art, the technical problems to be solved by the invention are as follows: the synthesis process of high content N-fatty alkyl-1, 3-propylene diamine includes the first complete reaction of primary amine in water as catalyst, and the subsequent negative pressure dewatering and acrylonitrile reaction. The second hydrogenation step illustrates that the alkaline metal oxides calcium oxide and potassium hydroxide are used as inhibitors, and the method is simple, environment-friendly and effective.
The technical scheme adopted by the invention for solving the technical problems is as follows: provides a method for synthesizing high-content N-fatty alkyl-1, 3-propylene diamine, which comprises the following steps:
(1) Condensation: adding fatty primary amine, acrylonitrile and catalyst softened water into a reaction kettle, sealing the reaction kettle, and reacting after nitrogen replacement; the reaction temperature is 70 +/-2 ℃, the reaction time is 2-4 hours, the vacuum negative pressure of-0.09 MPa is started after the reaction is finished, water and excessive acrylonitrile are removed, nitrile ethyl alkylamine is obtained, and the solution is collected for standby application;
(2) Catalytic hydrogenation: adding the nitrile ethyl alkylamine obtained by the condensation reaction in the step (1) into a hydrogenation reaction kettle, adding a hydrogenation catalyst, adding an alkaline metal oxide and a potassium hydroxide aqueous solution, then performing hydrogen replacement, heating after the replacement is finished, controlling the temperature to be 120-140 ℃, controlling the pressure to be 2.0-3.0MPa, reacting for 2-3 hours, cooling to 70 ℃, filtering, and drying the product at 115 ℃ under normal pressure to obtain the high-content N-aliphatic alkyl-1, 3-trimethylene diamine. The recovered catalyst is reused.
The molar ratio of the primary aliphatic amine to the acrylonitrile in the step (1) is 1:1.1-1.3, and the softened water of the catalyst accounts for 1% -4% of the total mass of the primary aliphatic amine and the acrylonitrile.
The excessive acrylonitrile in the condensation reaction of the primary aliphatic amine and the acrylonitrile can ensure that the reaction is completely carried out, the condensation reaction of the primary aliphatic amine and the acrylonitrile is an exothermic reaction, and the temperature can be controlled to be 70 +/-2 ℃ by adjusting cooling water in a reaction kettle and circulating the cooling water.
And (2) detecting acrylonitrile in the fatty alkyl nitrile ethylamine in the step (1) by chromatography, wherein the acrylonitrile is less than 150mg/kg.
The hydrogenation catalyst in the step (2) is palladium carbon or Raney nickel, and the mass fraction of palladium in the palladium carbon is 5%.
The adding amount of the hydrogenation catalyst in the step (2) is 1-5% of the adding amount of the nitrile ethyl alkylamine.
The alkaline metal oxide in the step (2) is calcium oxide. Calcium oxide is used as a hydrogenation inhibitor, and the amount of the calcium oxide is 1-3% of the mass of the catalyst.
The mass concentration of the potassium hydroxide aqueous solution in the step (2) is 8-12%.
The addition amount of the potassium hydroxide aqueous solution converted into the potassium hydroxide in the step (2) is 2-4% of the mass of the catalyst palladium carbon or raney nickel.
And (3) replacing the hydrogen in the step (2) by nitrogen for three times and then replacing the hydrogen for three times.
The reaction equation of the synthetic process method of the N-aliphatic alkyl propylene diamine is as follows:
the by-products produced in the process of synthesizing the N-aliphatic alkyl-1, 3-trimethylene diamine mainly comprise amide, acrylonitrile condensate and adduct of trimethylene diamine and acrylonitrile.
The synthesis process of N-fatty alkyl-1, 3-propylene diamine has excessive acrylonitrile condensation reaction and water as condensation catalyst. Palladium carbon or Raney nickel is used as hydrogenation catalyst, potassium hydroxide aqueous solution is used as inhibitor, and N-aliphatic alkyl-1, 3-propylenediamine is produced by reaction.
The invention has the beneficial effects that:
(1) The excessive acrylonitrile ensures that the reaction is thorough, and the reaction by-products are less and the yield is high under the action of water. The removal of excess acrylonitrile at negative pressure also reduces the production of subsequent reaction by-products.
(2) The process is simple, the water solution of calcium oxide and potassium hydroxide is used as inhibitor, and the amount of calcium oxide and potassium hydroxide is based on the amount of palladium carbon or Raney nickel added as catalyst. Good selectivity and high product purity. Greatly reducing the environmental pollution and continuously recycling the recovered catalyst. Is suitable for industrial production.
Detailed Description
The following further describes embodiments of the present invention:
example 1
A method for synthesizing high-content N-aliphatic alkyl-1, 3-trimethylene diamine comprises the following steps:
(1) Condensation: 1120g of soybean oleylamine is put into a closed reaction kettle, replaced by nitrogen for three times, stirred and heated, acrylonitrile is gradually dripped, and the temperature of the reaction kettle is controlled to be 70 +/-2 ℃ by circulating cooling water. After the dripping is finished, the temperature is kept for 1 to 2 hours at 70 plus or minus 2 ℃. The detection and analysis results after 0.5 hour of vacuumizing are as follows:
(2) And hydrogenation: quantitatively putting the cyanoethyl alkylamine into a high-pressure reaction kettle, adding a catalyst, performing nitrogen replacement three times and hydrogen replacement three times, keeping a certain pressure for 15min, and detecting the air tightness of the hydrogenation reaction kettle. And (4) heating, and controlling the temperature to be 120-140 ℃. Controlling the pressure of hydrogen in the kettle to be 2.0-3.0MPa. And (4) closing the hydrogen inlet valve, and keeping the pressure in the kettle for half an hour until the reaction is finished. Filtering and recovering the catalyst. The product was dried at 115 ℃. Analyzing and detecting:
example 2
A method for synthesizing high-content N-aliphatic alkyl-1, 3-propylene diamine comprises the following steps:
(1) Condensation: putting 1200g of hydrogenated tallow primary amine into a closed reaction kettle, replacing three times with nitrogen, starting stirring and heating, gradually dropwise adding acrylonitrile, and controlling the temperature of the reaction kettle to be 70 +/-2 ℃ by circulating cooling water. After the dripping is finished, the temperature is kept for 1 to 2 hours at 70 plus or minus 2 ℃. The detection and analysis results after 0.5 hour of vacuumizing are as follows:
(2) Hydrogenation: quantitatively adding cyanoethyl alkylamine into a high-pressure reaction kettle, adding a catalyst, replacing nitrogen for three times, replacing hydrogen for three times, keeping a certain pressure for 15min, and detecting the air tightness of the hydrogenation reaction kettle. Heating and controlling the temperature to be 120-140 ℃. Controlling the pressure of hydrogen in the kettle to be 2.0-3.0MPa. And (4) closing the hydrogen inlet valve, and keeping the pressure in the kettle for half an hour to finish the reaction. Filtering and recovering the catalyst. The product was dried at 115 ℃. Analyzing and detecting:
the present invention does not require further description of the methods and processes for carrying out dodecylpropylenediamine, stearylpropylenediamine, and the like. This is communicated to the art.
Claims (1)
1. A synthetic method of high-content N-aliphatic alkyl-1, 3-propylene diamine is characterized in that the synthetic method comprises the following steps:
(1) Condensation, namely adding primary aliphatic amine, acrylonitrile and catalyst softened water into a reaction kettle, sealing the reaction kettle, and reacting after nitrogen replacement; the reaction temperature is 70 soil and 2 ℃, the reaction time is 2-4 hours, the vacuum negative pressure of-0.09 MPa is started to remove water and excessive acrylonitrile after the reaction is finished, the nitrile ethyl alkylamine is obtained, and the solution is collected for standby:
(2) Adding the nitrile ethyl alkylamine obtained by condensation reaction in the step (1) into a hydrogenation reaction kettle, adding a hydrogenation catalyst, adding an alkaline metal oxide and a potassium hydroxide aqueous solution, then performing hydrogen replacement, heating after the replacement is finished, controlling the temperature to be 120-140 ℃, controlling the pressure to be 2.0-3.0MPa, reacting for 7.0-9.5 hours, cooling to 70 ℃, filtering, and drying the product at 115 ℃ under normal pressure to obtain the high-content N-fatty alkyl-1, 3-propylene diamine; recovering the catalyst for continuous use;
the molar ratio of the primary aliphatic amine to the acrylonitrile is 1.1-1.3, and the softened water of the catalyst accounts for 1% -4% of the mass sum of the primary aliphatic amine and the acrylonitrile;
detecting acrylonitrile in the nitrile ethyl alkylamine of the step (1) by chromatography, wherein the acrylonitrile content is less than 150mg/kg;
the hydrogenation catalyst in the step (2) is palladium carbon or Raney nickel, and the mass fraction of palladium in the palladium carbon is 5%;
the adding amount of the hydrogenation catalyst in the step (2) is 1-5% of the adding amount of the nitrile ethyl alkylamine; the alkaline metal oxide in the step (2) is calcium oxide; the addition amount of the calcium oxide is 1-3% of the mass of the catalyst;
the mass concentration of the potassium hydroxide aqueous solution in the step (2) is 8-12%;
the addition amount of the potassium hydroxide aqueous solution converted into the potassium hydroxide in the step (2) is 2-4% of the mass of the catalyst palladium carbon or Raney nickel; replacing the hydrogen in the step (2) by nitrogen for three times and then by hydrogen for three times;
wherein, the reaction equation of the synthetic method of the N-fatty alkyl-1, 3-propylene diamine is as follows:
the by-products produced in the production process mainly comprise amide, acrylonitrile condensate, addition product of trimethylene diamine and acrylonitrile, excessive acrylonitrile condensation reaction and water as a condensation catalyst; pd/C or Raney nickel is used as a hydrogenation catalyst, potassium hydroxide aqueous solution is used as an inhibitor, and N-aliphatic alkyl-1, 3-propylenediamine is generated through reaction.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910378669.7A CN110256287B (en) | 2019-05-08 | 2019-05-08 | Synthesis method of high-content N-fatty alkyl-1, 3-propylene diamine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910378669.7A CN110256287B (en) | 2019-05-08 | 2019-05-08 | Synthesis method of high-content N-fatty alkyl-1, 3-propylene diamine |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110256287A CN110256287A (en) | 2019-09-20 |
CN110256287B true CN110256287B (en) | 2023-03-10 |
Family
ID=67914430
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910378669.7A Active CN110256287B (en) | 2019-05-08 | 2019-05-08 | Synthesis method of high-content N-fatty alkyl-1, 3-propylene diamine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110256287B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116410636B (en) * | 2023-02-24 | 2024-03-15 | 深圳市纳能科技有限公司 | Color-adjustable fluorocarbon heat reflection coating with anti-corrosion and anti-fouling functions and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000012454A1 (en) * | 1998-08-27 | 2000-03-09 | Alberto Haces | Novel polycationic lipids |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4070859B2 (en) * | 1998-01-05 | 2008-04-02 | 花王株式会社 | Method for producing high-quality polyamine |
-
2019
- 2019-05-08 CN CN201910378669.7A patent/CN110256287B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000012454A1 (en) * | 1998-08-27 | 2000-03-09 | Alberto Haces | Novel polycationic lipids |
Non-Patent Citations (1)
Title |
---|
3-十八胺基丙腈的合成;任飞等;《日用化学工业》;20070630;第37卷(第3期);176-178 * |
Also Published As
Publication number | Publication date |
---|---|
CN110256287A (en) | 2019-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102936214B (en) | Method for clean preparation H acid | |
CN110831922B (en) | Method for producing chain-extended hydroxyethylethyleneamines, ethyleneamines or mixtures thereof | |
CN110256287B (en) | Synthesis method of high-content N-fatty alkyl-1, 3-propylene diamine | |
CN110072841B (en) | Method for producing hydroxyethylethylene amines | |
CN104193653A (en) | Novel synthesis method of N, N'-dicyclohexylcarbo-diimide | |
CA3071926C (en) | Process for preparing ethyleneamine compounds | |
CN113004171B (en) | Preparation method of 3-methoxypropylamine | |
US4967008A (en) | Polyamines and their preparation | |
CN104098474A (en) | Device and method for producing methyl aniline through performing continuous liquid-phase catalytic hydrogenation reduction on nitrotoluene | |
CN111004156A (en) | Method for synthesizing fatty acyl amino acid surfactant by direct method | |
CN101912745A (en) | Sulfamic acid amphoteric surfactant and synthesis method thereof | |
CN110498746B (en) | Method for improving quality of fatty tertiary amine | |
US3222402A (en) | Preparation of n-aliphatic trimethylene diamines | |
CN110776430B (en) | Preparation method of tri (2-aminoethyl) amine | |
CN113600097B (en) | Preparation method of asymmetric gemini imidazoline phosphate surfactant | |
RU2783708C2 (en) | Method for production of ethylenamine compounds | |
JPH0249299B2 (en) | ||
US4492803A (en) | Method for producing bis[β-(N,N-dimethylamino)alkyl]-ether | |
CN101397256B (en) | Method for producing fatty primary amine by using fatty acid as raw material | |
US4463192A (en) | Process for the reduction of an N-hydrocarbyl substituted oxazolidine with carbon monoxide to form the corresponding N-hydrocarbyl substituted alkanolamine | |
CN215102466U (en) | Aliphatic nitrile synthesis and wastewater treatment device | |
CN113603608B (en) | Glycosyl propylamine compound, preparation method and application thereof as flotation agent | |
CN107325003A (en) | A kind of method that Liquid-phase Hydrogenation Process synthesizes o-chloraniline | |
CN112174801B (en) | Method for coproducing glycolic acid and 1,1,1, 2-tetrafluoroethane by one-pot method | |
Hajipour et al. | Butyltriphenylphosphonium tetraborate (BTPPTB) as a selective reducing agent for the reduction of imines, enamines and oximes and reductive alkylation of aldehydes or ketones with primary amines in methanol or under solid-phase conditions |
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 |