CN115246778A - Preparation method of fatty alkoxy propylamine - Google Patents
Preparation method of fatty alkoxy propylamine Download PDFInfo
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- CN115246778A CN115246778A CN202210973149.2A CN202210973149A CN115246778A CN 115246778 A CN115246778 A CN 115246778A CN 202210973149 A CN202210973149 A CN 202210973149A CN 115246778 A CN115246778 A CN 115246778A
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- acrylonitrile
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- fatty
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- -1 alkoxy propylamine Chemical compound 0.000 title claims abstract description 45
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003112 inhibitor Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000005086 pumping Methods 0.000 claims abstract description 8
- 238000005070 sampling Methods 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000007868 Raney catalyst Substances 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910000027 potassium carbonate Chemical group 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- DBSIGGYGQQPRCT-UHFFFAOYSA-N 2-dodecoxypropanenitrile Chemical compound CCCCCCCCCCCCOC(C)C#N DBSIGGYGQQPRCT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- ZRJOUVOXPWNFOF-UHFFFAOYSA-N 3-dodecoxypropan-1-amine Chemical compound CCCCCCCCCCCCOCCCN ZRJOUVOXPWNFOF-UHFFFAOYSA-N 0.000 description 2
- JPNCZSADMGXVPA-UHFFFAOYSA-N 3-tridecoxypropan-1-amine Chemical class CCCCCCCCCCCCCOCCCN JPNCZSADMGXVPA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- ZSDJQTJAGTVLDH-UHFFFAOYSA-N N-(11-methyldodecoxy)propan-1-amine Chemical compound C(CCCCCCCCCC(C)C)ONCCC ZSDJQTJAGTVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PLJFCDOXVPENCB-UHFFFAOYSA-N n-dodecoxypropan-1-amine Chemical compound CCCCCCCCCCCCONCCC PLJFCDOXVPENCB-UHFFFAOYSA-N 0.000 description 1
- MPMYVCXAIRNIEO-UHFFFAOYSA-N n-tridecoxypropan-1-amine Chemical compound CCCCCCCCCCCCCONCCC MPMYVCXAIRNIEO-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of fatty alkoxy propylamine, which comprises the following steps: putting fatty alcohol, a catalyst A and a polymerization inhibitor into a reaction kettle, stirring and heating up, dehydrating in vacuum, cooling to 50 ℃ when the moisture content is less than 0.1%, starting to dropwise add acrylonitrile, controlling the reaction temperature, continuing the heat preservation reaction after the acrylonitrile is dropwise added, stopping the reaction when the content of the acrylonitrile is less than 0.3% and the content of the alkoxy propionitrile is more than 97% by sampling and analyzing, and neutralizing, filtering and removing the catalyst; putting the solvent, the catalyst B and the inhibitor into a high-pressure reaction kettle, replacing the solvent, the catalyst B and the inhibitor by nitrogen and hydrogen in sequence, starting stirring to uniformly mix the solvent, the catalyst B and the inhibitor, heating to introduce the hydrogen, slowly pumping alkoxy propionitrile into the high-pressure reaction kettle by a high-pressure pump to react, keeping the temperature after pumping, cooling, filtering and distilling to obtain the fatty alkoxy propylamine. The invention improves the utilization rate of acrylonitrile by preventing the polymerization and hydrolysis of acrylonitrile, so that the content of alkoxy propionitrile is higher; the adopted inhibitor is safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of fatty alkoxy propylamine.
Background
The fatty alkoxy propylamine is one of special fatty amines, is an important chemical raw material, and can be used as a mineral flotation agent, a pigment intermediate, a coating auxiliary agent, an epoxy resin intermediate and the like. The raw material can be prepared by hydrogenation after reaction of fatty alcohol and acrylonitrile, and the reaction principle is as follows:
the fatty alcohol reacts with acrylonitrile to produce alkoxy propionitrile, and alkali is used as a catalyst, and the main reaction is as follows:
the side reactions are as follows:
polymerization of acrylonitrile
Hydrolysis of acrylonitrile
The hydrogenation reaction of alkoxy propionitrile produces fatty alkoxy propylamine, and the main reaction is as follows:
the side reactions are as follows:
deaminizing reaction
Decomposition reaction
Since the high boiling point by-product of macromolecule is generated by deamination reaction without inhibitor in the process of hydrogenation of alkoxy propionitrile, the inhibitor capable of inhibiting deamination reaction is required to be added when the alkoxy propionitrile is hydrogenated, and ether bond in the alkoxy propionitrile is easy to break and decompose when the hydrogenation reaction is performed in the presence of alkali.
Chinese patent CN101058546A discloses a preparation method of 3-alkoxy propylamine, which uses a large amount of liquid ammonia as an inhibitor in the process of hydrogenation of alkoxy propionitrile, and the liquid ammonia has pungent smell, is toxic, explosive, unsafe and environment-friendly, so that a preparation method of fatty alkoxy propylamine with higher yield and higher safety and environment protection is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of fatty alkoxy propylamine. The technological improvement of the fatty alkoxy propylamine improves the yield and simultaneously leads the fatty alkoxy propylamine to be safer and more environment-friendly, a polymerization inhibitor is added in the reaction stage of fatty alcohol and acrylonitrile to prevent the generation of byproducts, a compound alkali is adopted to replace liquid ammonia to be used as an inhibitor in the hydrogenation process, and a method of dropping alkoxy propionitrile by a high-pressure pump is adopted, so that the byproducts are reduced and the quick heat release of the alkoxy propionitrile is controlled.
In order to achieve the purpose, the following technical scheme is provided:
a preparation method of fatty alkoxy propylamine comprises the following steps:
1) Putting fatty alcohol, a catalyst A and a polymerization inhibitor into a reaction kettle, stirring and heating to 100-120 ℃, carrying out vacuum dehydration, cooling to 50 ℃ when the moisture content is less than 0.1%, starting to dropwise add acrylonitrile, controlling the reaction temperature, continuing the heat preservation reaction after the dropwise addition of the acrylonitrile is finished, stopping the reaction when the content of the acrylonitrile is less than 0.3% and the content of alkoxy propionitrile is more than 97% by sampling analysis, neutralizing, filtering and removing the catalyst;
2) Putting the solvent, the catalyst B and the inhibitor into a high-pressure reaction kettle, replacing with nitrogen for 3 times, replacing with hydrogen for 3 times, starting stirring to uniformly mix the solvent, the catalyst B and the inhibitor, heating to introduce the hydrogen, slowly pumping the alkoxy propionitrile into the high-pressure reaction kettle by using a high-pressure pump for reaction, preserving the temperature for 1 hour after all the alkoxy propionitrile is pumped into the high-pressure reaction kettle, cooling, filtering and distilling to obtain the aliphatic alkoxy propylamine.
Further, the aliphatic alcohol in the step 1) is R-OH, wherein R represents a linear or branched alkyl group having 10 to 18 carbon atoms, and the molar ratio of the aliphatic alcohol to the acrylonitrile is 1:1-1.05.
Further, the catalyst A in the step 1) is sodium methoxide, potassium methoxide or potassium tert-butoxide, and the addition amount of the catalyst is 0.02-0.1% of the total feeding amount.
Further, the polymerization inhibitor in the step 1) is hydroquinone, ZJ705 or ZJ701, and the addition amount of the polymerization inhibitor is 5-20ppm of the total feeding amount.
Further, when the acrylonitrile is dripped in the step 1), the reaction temperature is controlled to be 60-80 ℃, and the temperature is maintained for 1-2 hours at 60-80 ℃ after the dripping is finished.
Further, the solvent in step 2) is methanol, ethanol or isopropanol.
Further, the catalyst B in the step 2) is Raney nickel, and the adding amount of the catalyst B is 1-2% of the mass of the aliphatic alkoxy propionitrile.
Further, the inhibitor in the step 2) is a compound of A and B, wherein A is selected from tetramethyl ammonium hydroxide or tetraethyl ammonium hydroxide, B is selected from sodium carbonate or potassium carbonate, the mass ratio of A to B is 1:6-10, and the total addition amount of the compound is 0.1-0.2% of the mass of the alkoxy propionitrile.
Further, in the step 2), when the alkoxy propionitrile is slowly pumped into a high-pressure reaction kettle by a high-pressure pump to react, the feeding speed is 100-200g/h, the reaction temperature is 100-140 ℃, and the reaction pressure is 3-4Mpa.
The invention has the beneficial effects that:
1) According to the invention, the polymerization inhibitor is added in the reaction stage of the fatty alcohol and the acrylonitrile, and the moisture of the raw material is controlled, so that the polymerization and hydrolysis of the acrylonitrile are prevented, the utilization rate of the acrylonitrile is improved, and the content of the alkoxy propionitrile is higher;
2) The inhibitor adopted by the invention is safe and environment-friendly, and has no pungent smell;
3) The method adopts the high-pressure pump to slowly drop alkoxy propionitrile instead of a one-pot method, so that the retention time of a large amount of alkoxy propionitrile in a reaction kettle is reduced, byproducts are reduced, and the control of reaction heat is facilitated.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope.
Example 1
Preparation of dodecyloxypropylamine
Step 1
Putting 400g of dodecanol, 0.51g of sodium methoxide (prepared into a methanol solution with the mass concentration of 50%) and 0.003g of ZJ705 into a reaction kettle, stirring and heating up to 110 ℃, carrying out vacuum dehydration for 1.5 hours, detecting the water content in a system to be 0.06%, cooling to 50 ℃, starting to dropwise add 114g of acrylonitrile, dropwise adding for 3 hours, controlling the reaction temperature to be 60 ℃, keeping the temperature at 60 ℃ for 2 hours after the acrylonitrile is dropwise added, sampling and analyzing that the acrylonitrile content is equal to 0.1%, stopping the reaction when the dodecyloxy propionitrile content is 98.2%, neutralizing, and filtering to remove the catalyst. The mol ratio of the dodecanol to the acrylonitrile is 1:1, the addition amount of catalyst sodium methoxide is 0.1 percent of the total charge amount, and the addition amount of polymerization inhibitor ZJ705 is 6ppm of the total charge amount.
Step 2
Putting 100g of methanol, 5g of raney nickel and 0.5g of composite alkali inhibitor into a high-pressure reaction kettle, replacing with nitrogen for 3 times, replacing with hydrogen for 3 times, stirring to uniformly mix the methanol, the catalyst and the inhibitor, heating to introduce hydrogen, slowly pumping 500g of dodecyloxypropionitrile into a high-pressure kettle by a high-pressure pump for reaction, controlling the pumping speed of the high-pressure pump at 200g/h, controlling the reaction temperature at 100 ℃ and the reaction pressure at 4MPa, keeping the temperature for 1 hour after all the alkoxypropionitrile is pumped into the reaction kettle, cooling, filtering and distilling to obtain the dodecyloxypropionine with the content of 98.5 percent. The used inhibitor is a compound of sodium carbonate and tetraethyl ammonium hydroxide, and the mass ratio of the sodium carbonate to the tetraethyl ammonium hydroxide is 6:1.
example 2
Preparation of isomeric tridecyloxypropylamines
Step 1
Putting 400g of isomeric tridecanol, 0.1g of potassium tert-butoxide (prepared into a methanol solution with the mass concentration of 50%) and 0.005g of ZJ701 into a reaction kettle, stirring and heating to 100 ℃, carrying out vacuum dehydration for 2 hours, reducing the water content in a detection system to be equal to 0.05%, cooling to 50 ℃, starting to dropwise add 108g of acrylonitrile, dropwise adding for 4 hours, controlling the reaction temperature to be 70 ℃, keeping the temperature at 70 ℃ for 1 hour after the completion of the dropwise addition of the acrylonitrile, sampling and analyzing the content of the acrylonitrile to be equal to 0.15%, stopping the reaction when the content of tridecyloxy propionitrile is 98.1%, neutralizing, filtering and removing the catalyst. The molar ratio of the fatty alcohol to the acrylonitrile is 1:1.02, the addition amount of the catalyst potassium tert-butoxide is 0.02 percent of the total charge amount, and the addition amount of the polymerization inhibitor ZJ701 is 10ppm of the total charge amount.
Step 2
100g of ethanol, 7.5g of raney nickel and 0.75g of composite alkali inhibitor are put into a high-pressure reaction kettle and replaced by nitrogen for 3 times, then replaced by hydrogen for 3 times, the mixture is stirred to uniformly mix the ethanol, the catalyst and the inhibitor, the temperature is raised and the hydrogen is introduced, 500g of isomeric tridecyloxy propionitrile is slowly pumped into a high-pressure kettle by a high-pressure pump for reaction, the pumping speed of the high-pressure pump is controlled at 150g/h, the reaction temperature is 120 ℃, the reaction pressure is 3.5MPa, the temperature is kept for 1 hour after all the tridecyloxy propionitrile is pumped into the reaction kettle, the temperature is reduced, the filtration and the distillation are carried out, and the content of the isomeric tridecyloxy propylamine is 98.3 percent. The inhibitor is a compound of sodium carbonate and tetramethyl ammonium hydroxide, and the mass ratio of the sodium carbonate to the tetramethyl ammonium hydroxide is 10:1.
example 3
Preparation of cetearyloxypropionitrile
Step 1
Putting 400g of hexadecanol and octadecanol (the mass ratio of the hexadecanol to the octadecanol is 3:7), 0.5g of potassium methoxide (prepared into a methanol solution with the mass concentration of 50%) and 0.01g of hydroquinone into a reaction kettle, stirring and heating up to 120 ℃, dehydrating in vacuum for 1 hour, detecting the water content in the system to be equal to 0.07 percent, cooling to 60 ℃, beginning to dropwise add 85g of acrylonitrile, controlling the reaction temperature to be 80 ℃, keeping the temperature at 80 ℃ for 1 hour after the acrylonitrile is dropwise added, stopping the reaction after sampling and analyzing the acrylonitrile content to be equal to 0.12 percent and the hexadecanol and octadecanol propionitrile content to be 98.5 percent, neutralizing, filtering and removing the catalyst. The molar ratio of the fatty alcohol to the acrylonitrile is 1:1.05, the addition of catalyst potassium methoxide is 0.1 percent of the total feeding amount, and the addition of polymerization inhibitor hydroquinone is 20ppm of the total feeding amount.
Step 2
100g of isopropanol, 10g of raney nickel and 1g of composite alkali inhibitor are put into a high-pressure reaction kettle to be replaced by nitrogen for 3 times, then replaced by hydrogen for 3 times, the stirring is started to uniformly mix the isopropanol, the catalyst and the inhibitor, the temperature is raised, the hydrogen is introduced, 450g of hexadecyl-octadecyl propionitrile is slowly pumped into the high-pressure kettle by a high-pressure pump to react, the pumping speed of the high-pressure pump is controlled at 100g/h, the reaction temperature is 140 ℃, the reaction pressure is 3Mpa, the temperature is kept for 1 hour after all the hexadecyl-octadecyl alkoxy propionitrile is pumped into the reaction kettle, and the temperature is reduced, filtered and distilled to obtain the isotridecyloxy propylamine with the content of 98.4 percent. The used inhibitor is a compound of potassium carbonate and tetraethyl ammonium hydroxide, and the mass ratio of the potassium carbonate to the tetraethyl ammonium hydroxide is 8:1.
comparative example 1
Preparation of isomeric tridecyloxypropylamines
Step 1
Putting 400g of isomeric tridecanol and 0.1g of potassium hydroxide (prepared into 50 mass percent aqueous solution) into a reaction kettle, heating to 50 ℃, beginning to dropwise add 108g of acrylonitrile, dropwise adding for 4 hours, controlling the reaction temperature to 70 ℃, keeping the temperature at 70 ℃ for 1 hour after the completion of the dropwise adding of the acrylonitrile, sampling and analyzing that the content of the acrylonitrile is equal to 0.15 percent and the content of the tridecyloxypropionitrile is 95.2 percent, stopping the reaction, neutralizing, filtering and removing the catalyst. The molar ratio of the fatty alcohol to the acrylonitrile is 1:1.02, and the addition amount of the catalyst potassium hydroxide is 0.02 percent of the total feeding amount.
Step 2
500g of isomeric tridecyloxypropionitrile, 7.5g of raney nickel and 0.75g of sodium hydroxide inhibitor are put into a high-pressure reaction kettle and are replaced by nitrogen for 3 times, then replaced by hydrogen for 3 times, the mixture is stirred and mixed evenly, the temperature is increased to introduce the hydrogen, the reaction temperature is 120 ℃, the reaction pressure is 2.5Mpa, the pressure is not reduced after the reaction is carried out for 5 hours, the temperature is reduced, the filtration and the distillation are carried out, the content of isomeric tridecyloxypropionitrile is 68.1 percent, and the analysis shows that the isomeric tridecyloxypropionitrile has partial decomposition in the hydrogenation process.
Comparative example 2
Preparation of dodecyloxypropylamine
Step 1
Putting 400g of dodecanol and 0.5g of sodium hydroxide (prepared into 32 mass percent aqueous solution) into a reaction kettle, heating to 50 ℃, dropwise adding 114g of acrylonitrile for 3 hours, controlling the reaction temperature to be 60 ℃, keeping the temperature at 60 ℃ for 2 hours after the acrylonitrile is dropwise added, sampling and analyzing that the content of the acrylonitrile is equal to 0.13 percent and the content of the alkoxy propionitrile is 95.5 percent, stopping the reaction, neutralizing, filtering and removing the catalyst. The molar ratio of the fatty alcohol to the acrylonitrile is 1:1, the addition amount of the catalyst sodium hydroxide is 0.1 percent of the total feeding amount.
Step 2
500g of dodecyloxy propionitrile, 7.5g of raney nickel and 0.75g of sodium carbonate inhibitor are put into a high-pressure reaction kettle and are replaced by nitrogen for 3 times, then hydrogen is used for replacing for 3 times, the mixture is uniformly mixed, the temperature is increased and hydrogen is introduced, the reaction temperature is 120 ℃, the reaction pressure is 3Mpa, the pressure is not reduced after 5 hours of reaction, the temperature is reduced, filtration and distillation are carried out, the content of the dodecyloxy propylamine is 85.2 percent, and analysis shows that the sodium carbonate can not well inhibit the generation of high boiling point.
Claims (9)
1. The preparation method of the fatty alkoxy propylamine is characterized by comprising the following steps:
1) Putting fatty alcohol, a catalyst A and a polymerization inhibitor into a reaction kettle, stirring and heating to 100-120 ℃, carrying out vacuum dehydration, cooling to 50 ℃ when the moisture content is less than 0.1%, starting to dropwise add acrylonitrile, controlling the reaction temperature, continuing the heat preservation reaction after the dropwise addition of the acrylonitrile is finished, stopping the reaction when the content of the acrylonitrile is less than 0.3% and the content of alkoxy propionitrile is more than 97% by sampling analysis, neutralizing, filtering and removing the catalyst;
2) Putting the solvent, the catalyst B and the inhibitor into a high-pressure reaction kettle, replacing with nitrogen for 3 times, replacing with hydrogen for 3 times, starting stirring to uniformly mix the solvent, the catalyst B and the inhibitor, heating to introduce the hydrogen, slowly pumping the alkoxy propionitrile into the high-pressure reaction kettle by using a high-pressure pump for reaction, preserving the temperature for 1 hour after all the alkoxy propionitrile is pumped into the high-pressure reaction kettle, cooling, filtering and distilling to obtain the aliphatic alkoxy propylamine.
2. The method for preparing fatty alkoxypropylamine according to claim 1, wherein the fatty alcohol in step 1) is R-OH, wherein R represents a linear or branched alkyl group having 10 to 18 carbon atoms, and the molar ratio of the fatty alcohol to acrylonitrile is 1:1-1.05.
3. The method for preparing fatty alkoxypropylamine of claim 1, wherein the catalyst A in step 1) is sodium methoxide, potassium methoxide or potassium tert-butoxide, and the addition amount of the catalyst is 0.02-0.1% of the total charge amount.
4. The method for preparing fatty alkoxypropylamine of claim 1, wherein the polymerization inhibitor used in step 1) is hydroquinone, ZJ705 or ZJ701, and the amount of the polymerization inhibitor added is 5-20ppm of the total amount charged.
5. The method for preparing fatty alkoxypropylamine as claimed in claim 2, wherein the reaction temperature is controlled to 60-80 ℃ when the acrylonitrile is added dropwise in step 1), and the temperature is maintained at 60-80 ℃ for 1-2 hours after the addition.
6. The method of claim 1, wherein the solvent used in step 2) is methanol, ethanol or isopropanol.
7. The method for preparing fatty alkoxypropylamine of claim 1, wherein the catalyst B in step 2) is Raney nickel, and the amount added is 1-2% of the fatty alkoxypropionitrile by mass.
8. The method for preparing fatty alkoxypropylamine according to claim 1, wherein the inhibitor in step 2) is a compound of A and B, A is selected from tetramethylammonium hydroxide or tetraethylammonium hydroxide, B is selected from sodium carbonate or potassium carbonate, the mass ratio of A to B is 1:6-10, and the total addition amount of the compound is 0.1-0.2% of the mass of alkoxypropionitrile.
9. The method for preparing fatty alkoxypropylamine as claimed in claim 1, wherein in step 2), the alkoxypropionitrile is slowly pumped into the high-pressure reactor by the high-pressure pump, and the reaction is carried out at a flow rate of 100-200g/h, a reaction temperature of 100-140 ℃ and a reaction pressure of 3-4MPa.
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