CN105884629A - N,N,N'-trimethyl-N'-aminopropyldiaminoethylether - Google Patents
N,N,N'-trimethyl-N'-aminopropyldiaminoethylether Download PDFInfo
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- CN105884629A CN105884629A CN201410756328.6A CN201410756328A CN105884629A CN 105884629 A CN105884629 A CN 105884629A CN 201410756328 A CN201410756328 A CN 201410756328A CN 105884629 A CN105884629 A CN 105884629A
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Abstract
The invention provides two synthetic methods for technologically producing a novel polyurethane catalyst N,N,N'-trimethyl-N'-aminopropyldiaminoethylether. A method I is characterized by using trimethyldiaminoethylether as a raw material to react with acrylonitrile, then hydrogenating the product under the condition of catalysts including skeletal nickel, palladium-carbon, platinum-carbon, ruthenium-carbon, and the like, and carrying out separation, thus obtaining the target product. A method II is characterized by condensing dimethylethanolamine and N-methyl-N-aminopropylethanolamine and carrying out separation, thus obtaining the target product.
Description
Technical field
This technology belongs to polyurethane industrial, relates generally to the synthesis of a kind of catalysts for polyurethanes.
Technical background
At present this product only has Hensel Man of the U.S. at present and produces, and name of product is N, N, N '-trimethyl-N '-aminopropyl diamine benzyl ethyl ether, its commercial disignation NE-300, belong to low smell highly active response type catalyst, domestic there is no production.
Summary of the invention
This technology has two kinds of production technologies
Technique one: with N, N, N '-trimethyl diamine benzyl ethyl ether is raw material and the fine reaction of propylene, after in the presence of the catalyst such as skeleton nickel, palladium charcoal, ruthenium charcoal, platinum charcoal hydrogenation and obtain.
Technique two: with N, N-dimethylethanolamine be raw material and the condensation of N-methyl-N-aminopropyl monoethanolamine obtains.
Embodiment
(1) technique one
1. the preparation of trimethyl diamine benzyl ethyl ether
(1) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, be slowly added into metallic sodium 51 grams under stirring, temperature gradually rises to 145 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, N-methylethanolamine 170 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N, N-dimethylethanolamine with rectifying column, under-0.08Mpa, collects the cut of more than 120 DEG C, obtain 220 grams, with gas chromatographic analysis 96.8%.
(2) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, add sodium methoxide 120 grams, reclaim methyl alcohol simultaneously under stirring, temperature gradually rises to 120 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, N-methylethanolamine 170 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.By filtrate with rectifying column respectively with receiving toluene and N, N-dimethylethanolamine, under-0.08Mpa, collect the cut of more than 120 DEG C, obtain 207 grams, with gas chromatographic analysis 96.5%.
(3) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, add 90 grams of sheet alkali under stirring, divide and go to generate, temperature gradually rises to 135 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, N-methylethanolamine 170 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N, N-dimethylethanolamine with rectifying column, under-0.08Mpa, collects the cut of more than 120 DEG C, obtain 202 grams, with gas chromatographic analysis 96.0%.
(4) putting into N-methylethanolamine 300 grams in 2000ML reaction bulb, be slowly added into metallic sodium 51 grams under stirring, temperature gradually rises to 145 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, N is slowly dripped under stirring, N-dimethylethanolamine 190 grams, control temperature≤40 DEG C, drip complete insulation half an hour, progressively it is warmed up to 90 DEG C, it is incubated half an hour, then cools to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N-methylethanolamine with rectifying column, under-0.08Mpa, collects the cut of more than 120 DEG C, obtain 203 grams, with gas chromatographic analysis 96.0%.
(5) putting into N-methylethanolamine 300 grams in 2000ML reaction bulb, add sodium methoxide 120 grams, collect methyl alcohol under stirring, temperature gradually rises to 120 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, N is slowly dripped under stirring, N-dimethylethanolamine 190 grams, control temperature≤40 DEG C, drip complete insulation half an hour, progressively it is warmed up to 90 DEG C, it is incubated half an hour, then cools to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.By filtrate with rectifying column respectively with receiving toluene and N-methylethanolamine, under-0.08Mpa, collect the cut of more than 120 DEG C, obtain 200 grams, with gas chromatographic analysis 96.5%.
(6) putting into N-methylethanolamine 300 grams in 2000ML reaction bulb, add 90 grams of sheet alkali under stirring, divide and go to generate water, temperature gradually rises to 135 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, N is slowly dripped under stirring, N-dimethylethanolamine 190 grams, control temperature≤40 DEG C, drip complete insulation half an hour, progressively it is warmed up to 90 DEG C, it is incubated half an hour, then cools to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N-methylethanolamine with rectifying column, under-0.08Mpa, collects the cut of more than 120 DEG C, obtain 206 grams, with gas chromatographic analysis 96.2%.
2.N, N, N ' synthesis of-trimethyl-N '-aminopropyl diamine benzyl ethyl ether
null(1) in 1000ML reacts，Throw 300 gram of 98% trimethyl diamine benzyl ethyl ether，Fine 120 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 70 DEG C，It is incubated 30 minutes，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add skeleton nickel 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 120 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 140 DEG C，Cut under gauge pressure-0.095MPa，Obtain 280 grams，With gas chromatographic analysis content more than 97%.
null(2) in 1000ML reacts，Throw 300 gram of 98% trimethyl diamine benzyl ethyl ether，Fine 120 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 70 DEG C，It is incubated 30 minutes，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add 5% palladium carbon catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 108 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 140 DEG C，Cut under gauge pressure-0.095MPa，Obtain 260 grams，With gas chromatographic analysis content more than 96%.
null(3) in 1000ML reacts，Throw 300 gram of 98% trimethyl diamine benzyl ethyl ether，Fine 120 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 70 DEG C，It is incubated 30 minutes，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add 5% platinum carbon catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 110 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 140 DEG C，Cut under gauge pressure-0.095MPa，Obtain 285 grams，With gas chromatographic analysis content more than 96%.
null(4) in 1000ML reacts，Throw 300 gram of 98% trimethyl diamine benzyl ethyl ether，Fine 120 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 70 DEG C，It is incubated 30 minutes，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add 5% ruthenium Pd/carbon catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 130 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 140 DEG C，Cut under gauge pressure-0.095MPa，Obtain 278 grams，With gas chromatographic analysis content more than 98%.
(2) technique two
Prepared by 1.N-methyl-N-aminopropyl monoethanolamine
null(1) in 1000ML reacts，Throw 300 grams of N-methylethanolamines，Fine 250 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 50 DEG C，It is incubated 3 hours，Middle control analysis is terminal without monomethyl-ethanolamine，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add skeletal nickel catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 130 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 120 DEG C，Cut under gauge pressure-0.095MPa，Obtain 350 grams，With gas phase analysis content 98%.
null(2) in 1000ML reacts，Throw 300 grams of N-methylethanolamines，Fine 250 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 50 DEG C，It is incubated 3 hours，Middle control analysis is terminal without monomethyl-ethanolamine，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add 5% palladium carbon catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 118 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 120 DEG C，Cut under gauge pressure-0.095MPa，Obtain 330 grams，With gas phase analysis content 96%.
null(3) in 1000ML reacts，Throw 300 grams of N-methylethanolamines，Fine 250 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 50 DEG C，It is incubated 3 hours，Middle control analysis is terminal without monomethyl-ethanolamine，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add 5% platinum carbon catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 101 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 120 DEG C，Cut under gauge pressure-0.095MPa，Obtain 333 grams，With gas phase analysis content 96%.
null(4) in 1000ML reacts，Throw 300 grams of N-methylethanolamines，Fine 250 grams of propylene is dripped at 20-40 DEG C，Completion of dropwise addition，Progressively it is warming up to 50 DEG C，It is incubated 3 hours，Middle control analysis is terminal without monomethyl-ethanolamine，The propylene of rear collection excess is fine，Product is through gas chromatographic analysis，Guarantee without propylene fine after，Put in 1000ML autoclave pressure，Add 5% ruthenium Pd/carbon catalyst 20 grams，Concentrated ammonia liquor 100ML，Seal-off pressure still，Replace 3 times with nitrogen，Use hydrogen exchange 3 times again，It is stamped into 1.5MPa，Stirring heats up，When 135 DEG C，Pressure begins to decline，Continue punching press to 3.0MPa，Repeated multiple times operation，Reaction end is not become to pressure，It is incubated 30 minutes，When being cooled to 50 DEG C，Pressure release，Discharging after nitrogen displacement，Filter off catalyst，Decompression distillation，Collect 120 DEG C，Cut under gauge pressure-0.095MPa，Obtain 330 grams，With gas phase analysis content 97%.
2.N, N, N ' synthesis of-trimethyl-N '-aminopropyl diamine benzyl ethyl ether
(1) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, be slowly added into metallic sodium 51 grams under stirring, temperature gradually rises to 145 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, 98%N-methyl-N-aminopropyl monoethanolamine 280 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N, N-dimethylethanolamine with rectifying column, under-0.95Mpa, collects the cut of more than 140 DEG C, obtain 325 grams, with gas chromatographic analysis 96.8%.
(2) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, add sodium methoxide 120 grams, collect methyl alcohol under stirring, temperature gradually rises to 125 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, 98%N-methyl-N-aminopropyl monoethanolamine 280 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N, N-dimethylethanolamine with rectifying column, under-0.95Mpa, collects the cut of more than 140 DEG C, obtain 335 grams, with gas chromatographic analysis 96.5%.
(3) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, add 90 grams of sheet alkali under stirring, divide and go to generate water, temperature gradually rises to 135 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, 98%N-methyl-N-aminopropyl monoethanolamine 280 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, quiet upper half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N, N-dimethylethanolamine with rectifying column, under-0.95Mpa, collects the cut of more than 140 DEG C, obtain 325 grams, with gas chromatographic analysis 96.8%.
(4) putting into 98%N-methyl-N-aminopropyl ethanol 500 grams in 2000ML reaction bulb, be slowly added into metallic sodium 51 grams under stirring, temperature gradually rises to 145 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, dimethylethanolamine 190 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N-methyl-N-aminopropyl ethanol with rectifying column, under-0.95Mpa, collects the cut of more than 140 DEG C, obtain 315 grams, with gas chromatographic analysis 95.8%.
(5) putting into 98%N-methyl-N-aminopropyl ethanol 500 grams in 2000ML reaction bulb, add sodium methoxide 120 grams, collect methyl alcohol under stirring, temperature gradually rises to 120 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, dimethylethanolamine 190 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N-methyl-N-aminopropyl ethanol with rectifying column, under-0.95Mpa, collects the cut of more than 140 DEG C, obtain 335 grams, with gas chromatographic analysis 95%.
(6) putting into 98%N-methyl-N-aminopropyl ethanol 500 grams in 2000ML reaction bulb, add 90 grams of sheet alkali under stirring, divide and go to generate water, temperature gradually rises to 135 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, dimethylethanolamine 190 grams is slowly dripped under stirring, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, cool to 10 DEG C again, dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer at this temperature.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered toluene and N-methyl-N-aminopropyl ethanol with rectifying column, under-0.95Mpa, collects the cut of more than 140 DEG C, obtain 330 grams, with gas chromatographic analysis 96.8%.
Claims (9)
1. the technique of a synthesis N, N, N '-trimethyl-N '-aminopropyl diamine benzyl ethyl ether: it is characterized in that, in 1000ML reacts, throwing 300 gram 98% 3
Methyl bisamine benzyl ethyl ether, drips fine 120 grams of propylene, completion of dropwise addition at 20-40 DEG C, is progressively warming up to 70 DEG C, is incubated 30 minutes, after
The propylene collecting excess is fine, and product is through gas chromatographic analysis, it is ensured that without propylene fine after, put in 1000ML autoclave pressure, addition skeleton nickel 20 grams,
Concentrated ammonia liquor 100ML (or considerable amount of ammonia), seal-off pressure still, replace 3 times with nitrogen, then with hydrogen exchange 3 times, be stamped into 1.5MPa,
Stirring heat up, when 120 DEG C, pressure begins to decline, continue punching press to 3.0MPa, repeated multiple times operation, do not become reaction end to pressure, insulation
30 minutes, when being cooled to 50 DEG C, pressure release, discharging after nitrogen displacement, filter off catalyst, decompression distillation, collect 140 DEG C, gauge pressure-0.095MPa
Under cut, obtain 280 grams, with gas chromatographic analysis content more than 97%.
2. the method for claim 1.The preparation of trimethyl diamine benzyl ethyl ether:
(1) putting into N, N-dimethylethanolamine 300 grams in 2000ML reaction bulb, be slowly added into metallic sodium 51 grams under stirring, temperature is progressively
Rise to 145 DEG C, be incubated 30 minutes, lower the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or benzene, hexamethylene
Alkane, hexahydrotoluene or petroleum ether) 900ML, slowly drip N-methylethanolamine 170 grams under stirring, control temperature≤40 DEG C, drip
Bi Baowen half an hour, progressively it is warmed up to 90 DEG C, is incubated half an hour, then cools to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams, static half little
Time, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene
100ML washs.Filtrate is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N, N-dimethyl ethanol with rectifying column
Amine, collects the cut of more than 120 DEG C under-0.08Mpa, obtains 220 grams, with gas chromatographic analysis 96.8%.
(2) in 2000ML reaction bulb, put into N, N-dimethylethanolamine 300 grams, add sodium methoxide 120 grams under stirring, reclaim methyl alcohol simultaneously,
Temperature gradually rises to 120 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or
Benzene, hexamethylene, hexahydrotoluene or petroleum ether) 900ML, slowly drip N-methylethanolamine 170 grams under stirring, control temperature≤40
DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, then cool to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams,
Static half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter
Cake toluene 100ML washs.Filtrate is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N, N-bis-with rectifying column
Methylethanolamine, collects the cut of more than 120 DEG C under-0.08Mpa, obtains 207 grams, with gas chromatographic analysis 96.5%.
(3) in 2000ML reaction bulb, put into N, N-dimethylethanolamine 300 grams, under stirring, add 90 grams of sheet alkali, divide and go to generate, temperature
Gradually rise to 135 DEG C, be incubated 30 minutes, lower the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or benzene,
Hexamethylene, hexahydrotoluene or petroleum ether) 900ML, slowly drip N-methylethanolamine 170 grams under stirring, control temperature≤40 DEG C, drip
Adding complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, then cool to 10 DEG C, dropping liquid caustic soda 360 grams, static at this temperature
Half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake is used
Toluene 100ML washs.Filtrate is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N, N-dimethyl with rectifying column
Monoethanolamine, collects the cut of more than 120 DEG C under-0.08Mpa, obtains 202 grams, with gas chromatographic analysis 96.0%.
(4) putting into N-methylethanolamine 300 grams in 2000ML reaction bulb, be slowly added into metallic sodium 51 grams under stirring, temperature gradually rises
To 145 DEG C, it is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or benzene, hexamethylene,
Hexahydrotoluene or petroleum ether) 900ML, slowly drip N, N-dimethylethanolamine 190 grams under stirring, control temperature≤40 DEG C, drip
Bi Baowen half an hour, progressively it is warmed up to 90 DEG C, is incubated half an hour, then cools to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams, static half little
Time, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene
100ML washs.Filtrate is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N-methylethanolamine with rectifying column,
Under-0.08Mpa, collect the cut of more than 120 DEG C, obtain 203 grams, with gas chromatographic analysis 96.0%.
(5) in 2000ML reaction bulb, put into N-methylethanolamine 300 grams, add sodium methoxide 120 grams under stirring, collect methyl alcohol, temperature
Gradually rise to 120 DEG C, be incubated 30 minutes, lower the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or benzene,
Hexamethylene, hexahydrotoluene or petroleum ether) 900ML, slowly drip N, N-dimethylethanolamine 190 grams under stirring, control temperature≤40
DEG C, drip complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, then cool to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams,
Static half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter
Cake toluene 100ML washs.Filtrate is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N-methyl with rectifying column
Monoethanolamine, collects the cut of more than 120 DEG C under-0.08Mpa, obtains 200 grams, with gas chromatographic analysis 96.5%.
(6) in 2000ML reaction bulb, put into N-methylethanolamine 300 grams, under stirring, add 90 grams of sheet alkali, point go to generate water, temperature by
Step rises to 135 DEG C, is incubated 30 minutes, lowers the temperature stand-by.2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or benzene, ring
Hexane, hexahydrotoluene or petroleum ether) 900ML, slowly drip N, N-dimethylethanolamine 190 grams under stirring, control temperature≤40 DEG C,
Dripping complete insulation half an hour, be progressively warmed up to 90 DEG C, be incubated half an hour, then cool to 10 DEG C, dropping liquid caustic soda 360 grams, quiet at this temperature
Only half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake
Wash with toluene 100ML.Filtrate is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N-methyl second with rectifying column
Hydramine, collects the cut of more than 120 DEG C under-0.08Mpa, obtains 206 grams, with gas chromatographic analysis 96.2%.
3. the method for claim 1.Its all catalyst can be skeleton nickel, palladium charcoal, platinum charcoal or ruthenium charcoal.
4. the technique of a synthesis N, N, N '-trimethyl-N '-aminopropyl diamine benzyl ethyl ether: it is characterized in that putting into N, N-diformazan in 2000ML reaction bulb
Ethylethanolamine 300 grams, is slowly added into metallic sodium 51 grams under stirring, temperature gradually rises to 145 DEG C, is incubated 30 minutes, lowers the temperature stand-by.
2000ML reaction bulb puts into thionyl chloride 320 grams and toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) 900ML, stirs shape
Slowly drip 98%N-methyl-N-aminopropyl monoethanolamine 280 grams under state, control temperature≤40 DEG C, drip complete insulation half an hour, be progressively warmed up to
90 DEG C, it is incubated half an hour, then cools to 10 DEG C, at this temperature dropping liquid caustic soda 360 grams, static half an hour, branch vibration layer.Organic layer is added
Entering in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to 30 DEG C of filtrations, filter cake toluene 100ML washs.By filtrate rectifying
Tower is separately recovered toluene (or benzene, hexamethylene, hexahydrotoluene or petroleum ether) and N, N-dimethylethanolamine, collects 140 under-0.95Mpa
Cut more than DEG C, obtains 325 grams, with gas chromatographic analysis 96.8%.
5. a method as claimed in claim 4.The preparation of dimethylethanolamine sodium salt, is with dimethylethanolamine and metallic sodium, sodium methoxide (or
Caustic alcohol, sodium tert-butoxide), NaOH 100--150 DEG C reaction obtain.
6. a method as claimed in claim 4.The preparation of N-methyl-N-aminopropyl monoethanolamine:
(1) in 1000ML reacts, 300 grams of N-methylethanolamines are thrown, fine 250 grams of propylene of dropping at 20-40 DEG C, completion of dropwise addition, progressively
Being warming up to 50 DEG C, be incubated 3 hours, middle control analysis is terminal without monomethyl-ethanolamine, and the propylene of rear collection excess is fine, and product divides through gas-chromatography
Analysis, it is ensured that without propylene fine after, put in 1000ML autoclave pressure, addition skeletal nickel catalyst 20 grams, concentrated ammonia liquor 100ML (or considerable amount of ammonia),
Seal-off pressure still, replaces 3 times with nitrogen, then with hydrogen exchange 3 times, is stamped into 1.5MPa, stirring intensification, and when 130 DEG C, pressure begins to decline,
Continue punching press to 3.0MPa, repeated multiple times operation, do not become reaction end to pressure, be incubated 30 minutes, when being cooled to 50 DEG C, pressure release, nitrogen
Discharging after displacement, filters off catalyst, decompression distillation, collects 120 DEG C, and the cut under gauge pressure-0.095MPa obtains 350 grams, uses gas phase analysis
Content 98%.
(2) in 1000ML reacts, 300 grams of N-methylethanolamines are thrown, fine 250 grams of propylene of dropping at 20-40 DEG C, completion of dropwise addition, progressively
Being warming up to 50 DEG C, be incubated 3 hours, middle control analysis is terminal without monomethyl-ethanolamine, and the propylene of rear collection excess is fine, and product divides through gas-chromatography
Analysis, it is ensured that without propylene fine after, in input 1000ML autoclave pressure, add 5% palladium carbon catalyst 20 grams, concentrated ammonia liquor 100ML (or considerable amount of ammonia
Gas), seal-off pressure still, to replace 3 times with nitrogen, then with hydrogen exchange 3 times, be stamped into 1.5MPa, stirring intensification, when 118 DEG C, pressure is opened
Begin decline, continue punching press to 3.0MPa, repeated multiple times operation, do not become reaction end to pressure, be incubated 30 minutes, when being cooled to 50 DEG C, let out
Pressure, discharging after nitrogen displacement, filter off catalyst, decompression distillation, collect 120 DEG C, the cut under gauge pressure-0.095MPa, obtain 330 grams, use
Gas phase analysis content 96%.
(3) in 1000ML reacts, 300 grams of N-methylethanolamines are thrown, fine 250 grams of propylene of dropping at 20-40 DEG C, completion of dropwise addition, progressively
Being warming up to 50 DEG C, be incubated 3 hours, middle control analysis is terminal without monomethyl-ethanolamine, and the propylene of rear collection excess is fine, and product divides through gas-chromatography
Analysis, it is ensured that without propylene fine after, in input 1000ML autoclave pressure, add 5% platinum carbon catalyst 20 grams, concentrated ammonia liquor 100ML (or considerable amount of ammonia
Gas), seal-off pressure still, to replace 3 times with nitrogen, then with hydrogen exchange 3 times, be stamped into 1.5MPa, stirring intensification, when 101 DEG C, pressure is opened
Begin decline, continue punching press to 3.0MPa, repeated multiple times operation, do not become reaction end to pressure, be incubated 30 minutes, when being cooled to 50 DEG C, let out
Pressure, discharging after nitrogen displacement, filter off catalyst, decompression distillation, collect 120 DEG C, the cut under gauge pressure-0.095MPa, obtain 333 grams, use
Gas phase analysis content 96%.
(4) in 1000ML reacts, 300 grams of N-methylethanolamines are thrown, fine 250 grams of propylene of dropping at 20-40 DEG C, completion of dropwise addition, progressively
Being warming up to 50 DEG C, be incubated 3 hours, middle control analysis is terminal without monomethyl-ethanolamine, and the propylene of rear collection excess is fine, and product divides through gas-chromatography
Analysis, it is ensured that without propylene fine after, in input 1000ML autoclave pressure, add 5% ruthenium Pd/carbon catalyst 20 grams, concentrated ammonia liquor 100ML (or considerable amount of ammonia
Gas), seal-off pressure still, to replace 3 times with nitrogen, then with hydrogen exchange 3 times, be stamped into 1.5MPa, stirring intensification, when 135 DEG C, pressure is opened
Begin decline, continue punching press to 3.0MPa, repeated multiple times operation, do not become reaction end to pressure, be incubated 30 minutes, when being cooled to 50 DEG C, let out
Pressure, discharging after nitrogen displacement, filter off catalyst, decompression distillation, collect 120 DEG C, the cut under gauge pressure-0.095MPa, obtain 330 grams, use
Gas phase analysis content 97%.
7. the technique of a synthesis N, N, N '-trimethyl-N '-aminopropyl diamine benzyl ethyl ether: put into 98%N-methyl-N-in 2000ML reaction bulb
Aminopropyl ethanol 500 grams, is slowly added into metallic sodium 51 grams under stirring, temperature gradually rises to 145 DEG C, is incubated 30 minutes, lowers the temperature stand-by.
2000ML reaction bulb puts into thionyl chloride 320 grams and toluene 900ML, under stirring, slowly drips dimethylethanolamine 190 grams, control
Temperature≤40 DEG C processed, drip complete insulation half an hour, are progressively warmed up to 90 DEG C, are incubated half an hour, then cool to 10 DEG C, drip at this temperature
Liquid caustic soda 360 grams, static half an hour, branch vibration layer.Organic layer is joined in the reaction bulb of above-mentioned sodium alkoxide, back flow reaction 4 hours, cool to
30 DEG C of filtrations, filter cake toluene 100ML washs.Filtrate is separately recovered first and N-methyl-N-aminopropyl ethanol with rectifying column, at-0.95Mpa
The cut that lower collection is more than 140 DEG C, obtains 315 grams, with gas chromatographic analysis 95.8%.
8. a method as claimed in claim 7.The preparation of N-methyl-N-aminopropyl caustic alcohol: be with N-methyl-N-aminopropyl ethanol and metallic sodium,
Sodium methoxide (or caustic alcohol, sodium tert-butoxide), NaOH obtain 100--150 DEG C of reaction.
9. a method as claimed in claim 7.Solvent for use is benzene, toluene, hexamethylene, hexahydrotoluene or petroleum ether.
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| CN108250088A (en) * | 2018-01-04 | 2018-07-06 | 四川之江高新材料股份有限公司 | The preparation method of the double amino-ethyl ethers of N, N, N`- trimethyl-N`- ethoxys |
| CN116253651A (en) * | 2023-03-10 | 2023-06-13 | 恒光新材料(江苏)股份有限公司 | Method for co-producing TMAEEEPA and BDMAEE |
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| CN102786427A (en) * | 2012-08-22 | 2012-11-21 | 浙江大学 | Synthetic method of bis-(2-dimethylaminoethyl)ether |
| JP2013151635A (en) * | 2011-06-16 | 2013-08-08 | Tosoh Corp | Raw material blending composition for manufacturing polyurethane foam |
| CN104507904A (en) * | 2012-02-10 | 2015-04-08 | 罗地亚经营管理公司 | Process for the production of aminopropylmethylethanolamine |
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| JP2013151635A (en) * | 2011-06-16 | 2013-08-08 | Tosoh Corp | Raw material blending composition for manufacturing polyurethane foam |
| CN102285892A (en) * | 2011-09-27 | 2011-12-21 | 史小鸣 | Synthesis of symmetric dimethylaminoethyl ether |
| CN104507904A (en) * | 2012-02-10 | 2015-04-08 | 罗地亚经营管理公司 | Process for the production of aminopropylmethylethanolamine |
| CN102786427A (en) * | 2012-08-22 | 2012-11-21 | 浙江大学 | Synthetic method of bis-(2-dimethylaminoethyl)ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250088A (en) * | 2018-01-04 | 2018-07-06 | 四川之江高新材料股份有限公司 | The preparation method of the double amino-ethyl ethers of N, N, N`- trimethyl-N`- ethoxys |
| CN108250088B (en) * | 2018-01-04 | 2020-10-30 | 四川之江高新材料股份有限公司 | Preparation method of N, N, N '-trimethyl-N' -hydroxyethyl bisaminoethylether |
| CN116253651A (en) * | 2023-03-10 | 2023-06-13 | 恒光新材料(江苏)股份有限公司 | Method for co-producing TMAEEEPA and BDMAEE |
| CN116253651B (en) * | 2023-03-10 | 2024-04-02 | 恒光新材料(江苏)股份有限公司 | Method for co-producing TMAEEEPA and BDMAEE |
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