CN101121666A - Process for producing amino compound - Google Patents
Process for producing amino compound Download PDFInfo
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- CN101121666A CN101121666A CNA2007101368025A CN200710136802A CN101121666A CN 101121666 A CN101121666 A CN 101121666A CN A2007101368025 A CNA2007101368025 A CN A2007101368025A CN 200710136802 A CN200710136802 A CN 200710136802A CN 101121666 A CN101121666 A CN 101121666A
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- amine
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- polyvalent alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It relates to a process for producing an amino compound in which by reacting a polyhydric alcohol or an amino alcohol with ammonia or a primary amine or a secondary amine, a corresponding tertiary amine, amino alcohol or the like is produced. It is intended to provide a process for producing an amino compound by which the running cost can be suppressed because a noble metal such as palladium or ruthenium is not used as a catalyst and an amino compound such as a tertiary amine which is industrially useful can be produced at a high reaction rate, high yield and high selectivity. The invention is provided with a structure in which a polyhydric alcohol and ammonia or a primary amine or a secondary amine are reacted in the presence of a catalyst containing copper, nickel, calcium, an alkali metal or an alkaline earth metal (except for calcium) as an essential component.
Description
Technical field
The present invention relates to use polyvalent alcohol or amino alcohol and ammonia or primary amine or secondary amine to react, thus the aminocompound preparation method of the tertiary amine of preparation correspondence or amino alcohol etc.
Background technology
As the N of one of aminocompound, N, N ', N '-tetramethyl--α, ω-alkylene diamine are the industrial important tertiary amines shown in the general formula (A), are used as the catalyzer when making polyurethane foam, mainly contain n=2,3 or 6 kind is manufactured and sell.
Me
2N-(CH
2)
n-NMe
2 ...(A)
In addition, intermediate amino alcohol shown in the general formula (B) is called as the reactive polyurethane catalyzer, compare with the tertiary amine shown in the general formula (A), have littler abominable pungent odour and eye mucosa pungency, therefore improved operating environment, simultaneously, because it has active hydrogen (hydroxyl), therefore with as the isocyanate reaction of urethane raw, be combined in the skeleton of urethane resin, suppressed the evaporation of catalysts for polyurethanes, thereby can improve the anti-sprayability of urethane resin or polyurethane foam, the halfcystine of anti-vinyl property (PVC ニ Le シ ス テ イ Application), thermotolerance, thereby be the important aminocompound that has obtained high evaluation.
Me
2N-(CH
2)
n-OH ...(B)
,, the reduction methylation reaction method that makes the corresponding primary amine shown in the general formula (C) is arranged herein as the conventional preparation method of tertiary amine shown in the general formula (A), and the ammoxidation method of the polyvalent alcohol shown in the chemical equation (D).In addition, herein the illustration dibasic alcohol as polyvalent alcohol.
H
2N-(CH
2)
n-NH
2 ...(C)
HO-(CH
2)
n-OH→Me
2N-(CH
2)
n-NMe
2+2H
2O ...(D)
Also have, the ammoxidation of chemical equation (D) is to be undertaken by the step reaction of chemical equation (E), (F), and known concerning catalyzer in the past, the speed of the step of second shown in the chemical equation (F) reaction is slow usually
HO-(CH
2)
n-OH+Me
2NH→Me
2N-(CH
2)
n-OH+H
2O ...(E)
Me
2N-(CH
2)
n-OH+Me
2NH→Me
2N-(CH
2)
n-NMe
2+H
2O ...(F)
For first kind of reduction methylation reaction method, for example, as described in patent documentation 1, need make formaldehyde excessive during reaction, therefore the aftertreatment to unreacting acetal has formed burden, industrial be on the other hand disadvantageous, the formation reaction water only except that tertiary amine of the ammoxidation method shown in the back a kind of chemical equation (D) is industrial favourable preparation method from the Green Chemistry angle therefore.
Therefore, developed and used polyvalent alcohol, prepared the method for aminocompounds such as tertiary amine by ammoxidation as starting raw material.
As technology in the past, for example, disclose in the patent documentation 2 " in the presence of catalyzer; polyvalent alcohol and ring-type primary amine or secondary amine are reacted under 150～300 ℃ temperature and make the method for tertiary amine, above-mentioned catalyzer is to the carboxylate salt of (a) copper or as the copper acetylacetonate complex of the intramolecularly complex compound of copper with the mixture of hydrogen and amine or other reductive agent; (b) be selected from the periodic table of elements the 8th family's element; the carboxylate salt of the metal of manganese and zinc or as in the acetylacetonate complex of intramolecularly complex compound more than a kind or 2 kinds; and (c) an alkali metal salt of carboxylic acid or carboxylic acid or the mixture more than a kind or 2 kinds in the alkali earth metal salt reduce to handle obtain ".
Disclose in the patent documentation 3 " in the presence of copper-nickel-the 8th family platinum element catalyst; for polyvalent alcohol and primary amine or secondary amine; Yi Bian remove water generation reaction; Yi Bian make it to react under normal atmosphere to the 5 atmospheric pressure and under 150 ℃～250 ℃ the temperature, thus the method for manufacturing tertiary amine ".
Disclose in patent documentation 4 and the patent documentation 5 " in the presence of copper-nickel-the 8th family platinum element catalyst; for dibasic alcohol and primary amine; and remove water generation reaction, and meanwhile under 150 ℃～250 ℃ temperature, make it to react, thus the manufacturing technology of manufacturing amino alcohol ".
[patent documentation 1] spy opens the 2000-159731 communique
[patent documentation 2] special public clear 60-11020 communique
[patent documentation 3] special fair 3-4534 communique
[patent documentation 4] spy opens flat 5-39338 communique
[patent documentation 5] spy opens flat 5-93031 communique
Summary of the invention
But there is following problem in above-mentioned conventional art.
(1) do not put down in writing the embodiment for preparing tertiary amine by polyvalent alcohol in the patent documentation 2, therefore inventor's record to specifications, use copper stearate, nickel stearate, barium stearate as the catalyzer raw material, with 1,6-hexylene glycol (polyvalent alcohol) replaces morpholine, reacts with dimethylamine (secondary amine), has implemented this supplementary test, this moment, catalyzer condensed, and failed to realize at a high speed effectively ammoxidation.These catalyzer raw materials are not activated in the high polyvalent alcohol of polarity effectively, even activation in addition, the stability of catalyzer is also not enough, therefore catalyzer is sufficiently activated, and can not carry out amination efficiently to polyvalent alcohol.
(2) put down in writing use copper-nickel-ruthenium class catalyzer among the embodiment 13 of patent documentation 3, to 1, the 6-hexylene glycol carries out amidized embodiment, but the 8th family's platinum element price height in the patent documentation 3 in the disclosed catalyzer, exist catalyzer manufacturing cost height, industrial disadvantageous problem.In addition, when the activity of such catalysts of this patent is carried out supplementary test, can confirm as the catalytic activity (speed of response) of the per unit weight copper on catalyzer manufacturing cost basis lowly from its result, lack productivity.
(3) also use palladium grade in an imperial examination 8 family's platinum elements as promotor in patent documentation 4 and the patent documentation 5 in the disclosed technology, therefore also existed the manufacturing cost height of catalyzer, industrial disadvantageous problem.In addition, because catalyst activity is low, therefore the usage quantity with respect to the catalyzer of polyvalent alcohol has reached this huge amount of 2～4wt%, exists the problem that needs high running cost.
(4) as the ammoxidation of the polyvalent alcohol that is undertaken by step reaction, the reactivity of the step of second shown in the chemical equation (F) reaction is extremely low, therefore patent documentation 2 disclosed activity of such catalysts to the patent documentation 5 is low, it is long that the needed time is finished in reaction, also can produce a large amount of by products (aldol condensation thing) in addition, therefore can not prepare targeted amine and amino alcohol with high yield and good selectivity.
The objective of the invention is to solve above-mentioned problem in the past, provide and do not use precious metals such as palladium or ruthenium in the catalyzer, therefore can suppress running cost, simultaneously can be under high speed of response prepare the aminocompound preparation method of industrial useful aminocompounds such as tertiary amine with high yield and good selectivity.
In order to solve above-mentioned problem in the past, aminocompound preparation method of the present invention has following formation.
The preparation method of the 1st described aminocompound of the present invention has following formation, promptly, with copper, nickel, calcium, basic metal or alkaline-earth metal (except the calcium) as the catalyzer of essential composition in the presence of, polyvalent alcohol and ammonia or primary amine or secondary amine are reacted.
Adopt this formation can obtain following effect.
(1) by reacting in the presence of as catalyzer that must composition, can under high speed of response, prepare industrial useful aminocompounds such as tertiary amine with high yield and good selectivity with copper, nickel, calcium, basic metal or alkaline-earth metal (except the calcium).Particularly for ammoxidation, the speed of response of the step of second shown in the chemical equation (F) reaction is extremely low, but compared with the past as can be known, and the present invention has significantly improved the speed of response of second step reaction, has reached high reactivityization.
(2) because catalyzer has high reactivity, thus the reaction conditions gentleness, can adopt little amount of catalyst to finish reaction at short notice simultaneously, cost is low, and productivity is obviously excellent.
(3) do not use precious metals such as palladium or ruthenium metal in the catalyzer, therefore can suppress the running cost of catalyzer.
(4) suppressed significantly can improve the selectivity that generates amine because of containing the raw material amine that precious metal causes and generating the not homogenizing reaction of amine.
Herein, as the starting raw material polyvalent alcohol, can use 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1, dibasic alcohol such as 12-dodecanediol, 12-hydroxyl octadecandiol, ethylene glycol, triethylene glycol, propylene glycol, 3 yuan of alcohol such as glycerine etc.Decamethylene-glycol can prepare by the sebacic acid made by the oxidation of Viscotrol C alkali or its dimethyl ester are carried out hydrogen reduction, and 12-hydroxyl octadecandiol can prepare by ricinolic acid is carried out hydrogenation.
The starting raw material amino alcohol is the intermediate of the step reaction of chemical equation (E), (F), can use above-mentioned polyvalent alcohol is carried out amination and the compound with amino and hydroxyl that forms, for example can enumerate monoethanolamine, diethanolamine, methyldiethanolamine, Mono Methyl Ethanol Amine, dimethylethanolamine, diethylethanolamine, diisopropyl ethanolamine, dibutyl thanomin.
Raw material amine as starting raw material can use ammonia, general formula R
1NH
2Primary amine, the general formula R of expression
2N
2The secondary amine that H represents.
Herein, R
1For ester ring type heterocycles such as the alkyl of straight chain, side chain or the ester ring type of carbon number 1～6, morpholinyls,, can enumerate methylamine, ethamine, propylamine, hexahydroaniline etc. as primary amine.R2 is the straight chained alkyl of carbon number 1～4, as secondary amine, can enumerate dimethylamine, diethylamine, dipropyl amine, dibutylamine etc.In addition, as other raw material amine, can enumerate cyclic amine such as heteroaromatic amine, tetramethyleneimine, piperidines, piperazine, pyrrolidone such as aliphatic cyclic amines such as aromatic amine, hexahydroaniline, chaff amine such as benzylamine.
As with copper, nickel, calcium, basic metal or alkaline-earth metal (except the calcium) catalyzer raw material, can use the mixture more than a kind or 2 kinds in the carboxylate salt of more than a kind or 2 kinds and (d) basic metal more than a kind or 2 kinds, in the complex compound of the carboxylate salt of (c) calcium or calcium more than a kind or 2 kinds, in the intramolecularly complex compound of the carboxylate salt of (b) nickel or nickel in the intramolecularly complex compound of the carboxylate salt of (a) copper or copper or alkaline-earth metal (except the calcium) as the catalyzer of essential composition.
In order to implement ammoxidation, at first must make the reduction activation of catalyzer raw material.For example, the heatable catalyst raw material is dissolved in starting raw material polyvalent alcohol or the amino alcohol it, imports hydrogen or other reductive agent and makes its reduction activation (handling hereinafter referred to as reduction activation), imports raw material amine then and carries out ammoxidation.In addition, the heatable catalyst raw material makes it to be dissolved in the higher alcohols equal solvent, after carrying out reduction activation and handling, imports starting raw material polyvalent alcohol or amino alcohol and raw material amine and carries out ammoxidation.Handling the catalyzer that obtains by reduction activation is the uniform colloidal catalyzer of outward appearance (copper/nickel shot directly is about 1nm).
In the catalyzer raw material, (a) the intramolecularly complex compound of the carboxylate salt of copper and copper is reduced to metallic copper in the reduction activation treating processes.Carboxylic acid as the carboxylate salt that forms copper, as long as have carboxyl in the molecule, it can be fragrant same clan carboxylic acid, it also can be branching chain carboxylic acid, also can be to have a plurality of carboxyls and other substituent carboxylic acid on the straight chained alkyl, for example can enumerate caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, stearic acid, oleic acid etc.Preferred carbon number is the carboxylic acid more than 6, and preferred especially carbon number is the carboxylic acid more than 12.
For carbon number is carboxylic acid below 5, because the influence of free carboxylic acid easily causes the aggegation of metallic colloid, makes active the reduction in the reduction, is worthless therefore.As the intramolecularly complex compound of copper, for example can enumerate acetylacetonate complex and dimethyl glyoxime complex compound etc., the general chelate compound of sulfur-bearing not.
In addition, in the catalyzer raw material, (b) the intramolecularly complex compound of the carboxylate salt of nickel or nickel also is reduced in the reducing activity treating processes.As carboxylate salt, intramolecularly complex compound, can illustration and above-mentioned carboxylic acid, the identical organic ligand of above-mentioned intramolecularly complex compound.Also have, as carboxylic acid, preferred carbon number is the kind more than 6.Because for carbon number is carboxylic acid below 5, the free carboxylic acid easily causes the aggegation of metallic colloid in the reduction, makes active the reduction.
In addition, in the catalyzer raw material, (c) complex compound of the carboxylate salt of calcium or calcium is reduced in ammoxidation gradually, demonstrates strong katalysis with copper and nickel.As carboxylic acid, can the illustration material identical with above-mentioned carboxylic acid.As calcium complex, for example can enumerate acetylacetonate complex, dimethyl glyoxime complex compound etc., not contain the general chelate compound of inorganic anion.
Also have, as carboxylic acid, preferred carbon number is the carboxylic acid more than 6.Identical with the situation of copper, nickel, this is because make carboxylic acid free, easily causes the aggegation of copper/nickel metallic colloid, makes active the reduction.
In the catalyzer raw material, (d) carboxylate salt of basic metal or alkaline-earth metal (except the calcium) is not reduced in reduction activation processing and ammoxidation, plays the function of stabilizer of copper-nickel-calcium class colloid catalyst.Wherein, the carboxylate salt of the carboxylate salt of alkaline-earth metal, particularly barium is effective.Reason is to compare with copper and nickel, and barium is not easy to be reduced especially, plays special effective function as the stablizer that keeps catalyst activity.
As carboxylate salt, can illustration material same as described above, for example can enumerate barium stearate, barium laurate, sodium stearate etc.Wherein, be fit to using carbon number is 8～30, preferred 10～24, particularly 18～24 stearic acid, docosoic, Lignoceric acid etc.It obtains easily, and the inventor's experimental result shows: carbon number is 8～30 carboxylate salt, and the inhibition copper that the long-chain effect of its carboxyl is caused/nickel metallic colloid agglutinative effect height has been given high catalyst activity.
Also have, the carboxylate salt of copper, nickel, basic metal, alkaline-earth metal can adopt the known method of record in the special public clear 59-27617 communique etc. to make.
Other reductive agent as beyond the hydrogen that the catalyzer raw material is carried out use in the reduction activation processing can use Al (C
2H
5)
3, (C
2H
5)
2Al (OC
2H
5) etc.
In addition, as the solvent of catalyst-solvent raw material, can use high boiling higher alcohols and liquid paraffin etc.By in solvent, making the reduction activation of catalyzer raw material, can make the catalyst solution of high density.In this catalyst solution, can also carry out the ammoxidation of polyvalent alcohol or amino alcohol.
In the reduction activation of catalyzer raw material is handled, the catalyzer raw material is put in polyvalent alcohol or amino alcohol, the solvent, when heating up, supply with reductive agents such as hydrogen continuously.Divalent copper reduces near 160 ℃, and catalyzer is finished activation less than 200 ℃ the time.After the reduction activation processing, carry out ammoxidation, simultaneously, the tone that contains the reaction mixture of colloidal catalyzer transforms to black from faint yellow (transparent), changes even colloidal catalyzer russet again into, has reached high reactivity.Initially tour, existing the mobile period that changes to high activated catalyst to black state from faint yellow, is a kind of inductive phase.Along with the chain length of polyvalent alcohol or higher alcohols etc. shortens (for example 1,9-nonanediol, 1,8-ethohexadiol etc.), polarity uprises, and presents elongated tendency inductive phase, so the chain length of polyvalent alcohol is long more, and it is easy more to react, and is worthless.In addition, considering from the boiling point aspect, also is long more favourable more as the chain length of the higher alcohols of solvent.Because utilize the difference of boiling point, can make resultant of reaction (aminocompound) oxidation and carry out fractionation by distillation.
After carrying out the reduction activation processing, reactor is set at 100～250 ℃, preferred 150～220 ℃, more preferably 180～220 ℃, in polyvalent alcohol and solvent, imports gas shape raw material amine such as primary amine or secondary amine, the beginning ammoxidation.Along with temperature of reaction is lower than 180 ℃, speed of response presents downward trend, and along with temperature of reaction is lower than 150 ℃, this trend becomes obviously, along with temperature of reaction is lower than 100 ℃, obviously lacks productivity, is worthless therefore.Along with temperature of reaction is higher than 220 ℃, side reaction presents the tendency of acceleration, if be higher than 250 ℃, then occur obviously quickening, and or not preferred therefore.
Amination is adapted at-0.5～10MPa, and is preferred-0.05～1MPa, more preferably carries out under the scope of 0.1～0.5MPa.Because ammoxidation is a dehydration reaction, so pressurized conditions can cause speed of response low.
In ammoxidation, if import raw material amine such as primary amine or secondary amine, then water begins to distillate after several minutes inductive phase, can confirm the carrying out that reacts.Reaction also can be carried out under the condition that does not import hydrogen.This is because the active hydrogen that is generated by dehydrogenations such as polyvalent alcohol or amino alcohols can be used to react.But, preferably import hydrogen, in the presence of hydrogen, react.This is that the hydrogen of Dao Ruing also helps reaction water is transported to outside the reaction system simultaneously because can shorten the reaction times a little.Owing to can efficiently water be transported to outside the system, therefore can expend to import to and be used for hydrogen, nitrogen or the rare gas etc. of output-response water in the reaction system, also can in anti-device, import rare gas elementes such as nitrogen or rare gas and replace hydrogen or mix with hydrogen.
When water generates, distillate as the oil content of resultant, therefore can carry out oily water separation according to a conventional method, oil content is turned back to carry out ammoxidation in the reactor in case of necessity.The carrying out of reaction can be followed the tracks of by amine value, hydroxyl value or gas chromatographic analysis.
If ammoxidation finishes, then distillating also of water stops.Though depend on temperature of reaction, catalyst concn, amine feed speed, ammoxidation was finished with 2～10 hours.
As catalyst concn, be benchmark with the metallic copper, suitable is 0.001～10wt% (with respect to starting raw material alcohol), is preferably 0.01～5wt%, more preferably 0.05～2wt%.Along with concentration is lower than 0.05wt%, speed of response occurs and reduce, if be lower than 0.001wt%, obviously lack productivity, be worthless therefore.Along with concentration is higher than 2wt%, occur to promote the trend of side reaction, if surpass 10wt% then this situation becomes significantly, so be worthless.
As the composition of catalyzer, press atomic ratio measuring, preferably copper: nickel: basic metal or alkaline-earth metal (except the calcium)=5: 1: 1: 1.In addition, in catalyzer was formed, basic metal or alkaline-earth metal (except the calcium) were preferably 0.1～10 with respect to the ratio of calcium by atomic ratio measuring.This is because if above-mentioned ratio less than 0.1, and then the stability of metallic colloid class sharply descends, and has promoted the cohesion of metallic colloid, catalyst deactivation, if surpass 10, then speed of response first mate degree descends.
In addition, in catalyzer was formed, calcium was preferably 0.1～0.5 with respect to the ratio of copper with atomic ratio measuring.This is because if above-mentioned ratio less than 0.1 or surpass 0.5, and then speed of response first mate degree descends.
In ammoxidation, as the feed speed (L/ hour) of the time per unit of the raw material amine in the supply response device (ammonia, primary amine, secondary amine) under standard state (25 ℃, 0.1MPa), per 1 mole is 0.01～100 mole/hour with respect to the hydroxyl of starting raw material alcohol, be preferably 0.1～10 mole/hour, be preferably 0.2～5 mole/hour especially.If 0.01 mole/hour of less than, then anti-speed is slow, obviously lacks productivity, is not preferred therefore.When surpassing 100 moles/hour, raw material amine causes that the situation of poisoning of catalyst is remarkable, cause speed of response and yield to descend, but also promoted uneven voltinism biglyyer, and or not preferred therefore.
Ammoxidation can be any means in intermittent type, the continous way.Under step situation, for example can use conventional stirring stratotype reactor, ejector-type stirring-type reactor or loop reactor etc.Under the situation of continous way, do not need special whipping appts, can the using gas stirring-type etc. reactor.
As the aminocompound that obtains by the present invention, can enumerate N, N, N ', N '-tetramethyl--1,6-hexamethylene-diamine, N, N, N ', N '-tetramethyl--1,8-eight methylene diamine, N, N, N ', N '-tetramethyl--nonamethylene diamines, N, N, N ', N '-tetramethyl--1, the inferior decyl diamines of 10-, N, N, N ', N '-tetramethyl--1,12-ten dimethylene diamines, 12-hydroxy-n, N-dimethyl stearyl diamines and 12-N, N-dimethyl-N ', N '-tertiary amines such as dimethyl stearic amine, as the amino alcohol of the intermediate of these tertiary amines.These aminocompounds are suitable as the catalyzer of preparation urethane and polyurethane foam.
After ammoxidation is finished, can reaction mixture, and by being adsorbed in filtering separation catalyzer on the sorbent materials such as gac.But, must make catalyzer keep reduced state during absorption.
But colloidal catalyzer (copper/nickel shot directly is about 1nm) can not separate by filter operation usually, and therefore preferred distillation procedure by routine is separated into cut and residue.Have catalyzer in the residue, it directly can be reused for down secondary response, therefore under the situation of curing catalysts, do not need the filtration step of necessary catalyzer, the operation excellence.
Catalyzer of the present invention is in that handle the back through reduction activation extremely stable to polar solvent, can confirm to become acetone soln and place for 1 week and also do not condense.And in order to improve anti-polarity, stablizer (basic metal or alkaline-earth metal (except the calcium) composition) amount that increases in the catalyst component also is effective.In addition, even react repeatedly, activity of such catalysts does not reduce substantially yet.
The 2nd preparation method that described invention is the 1st a described aminocompound of the present invention, this method has following formation: above-mentioned catalyzer be utilize hydrogen or other reductive agent with in the intramolecularly complex compound of the carboxylate salt of (a) copper or copper more than a kind or 2 kinds, (b) in the intramolecularly complex compound of the carboxylate salt of nickel or nickel more than a kind or 2 kinds, (c) in the complex compound of the carboxylate salt of calcium or calcium more than a kind or 2 kinds, (d) mixture more than a kind or 2 kinds in the carboxylate salt of basic metal or alkaline-earth metal (except the calcium) reduces processing in above-mentioned polyvalent alcohol or above-mentioned amino alcohol or solvent.
Adopt this formation, except the effect of the 1st acquisition, also can obtain following effect.
(1) because the catalyzer raw material is a metallic soap, therefore do not need miscellaneous technologies such as preparation, washing, drying, pulverizing, classification of necessary metal hydroxides when making curing catalysts, productivity is obviously excellent.
(2) reducing the catalyzer of handling with polyvalent alcohol etc. is colloidal, therefore is fit to adopt any means in intermittent type and the continous way, also adapts to small-scale production, freedom excellence simultaneously easily.
The 3rd preparation method that described invention is the 2nd a described aminocompound of the present invention, this method has following formation: in the above-mentioned solvent lower than above-mentioned polyvalent alcohol or above-mentioned amino alcohol polarity, above-mentioned catalyzer is reduced processing, in the above-mentioned solvent that contains above-mentioned catalyzer, supply with above-mentioned polyvalent alcohol and/or above-mentioned amino alcohol continuously, and above-mentioned ammonia or above-mentioned primary amine or above-mentioned secondary amine (raw material amine), make its reaction.
Adopt this formation, except the effect of the 2nd acquisition, also can obtain following effect.
(1) in solvent, make catalyst reduction activation after, little by little continuously a small amount of base feed polyvalent alcohol or raw material amine such as amino alcohol and secondary amine in the solvent that contains catalyzer, react, even then high polar polyvalent alcohol (for example, as carbon number 1 of 2～8 polyvalent alcohol, 6-hexylene glycol or 1,8-ethohexadiol etc.) or amino alcohol, the colloidal catalyzer is not vulnerable to the polarity effect of polyvalent alcohol etc. yet, therefore is not easy aggegation, can keep high reactivity.Therefore, even raw material is high polar carbon number is 2～8 polyvalent alcohol or amino alcohol, also can make completely dissolve inductive phase, in base feed in solvent, promptly begin ammoxidation, productivity significantly improves, also may make diversified amine simultaneously, this was considered to impossible in the past, so applicability is obviously excellent.Relative therewith, be to carry out reduction activation in 2～8 the polyvalent alcohol to handle as the catalyzer raw material being dissolved in the high carbon number of polarity as can be known, then to the method for wherein supplying with raw material amine such as secondary amine, show the tendency of the catalyzer generation cohesion in the polyvalent alcohol, can not realize original activity, present the inductive phase that reaches a few hours sometimes.
Herein, as solvent, can use than the low higher alcohols of the polarity of raw polyol or amino alcohol or whiteruss etc.Especially preferably low polarity and long-chain (carbon number be 12～40, be preferably 18～24) monohydroxy-alcohol (stearyl alcohol, behenyl alcohol, tetracosanol etc.) or the whiteruss higher than the boiling point of goal response resultant (aminocompound).Owing to can make resultant of reaction (aminocompound) and separated from solvent by distillation, so productivity is obviously excellent.
Handle by in solvent, the catalyzer raw material being carried out reduction activation, can prepare catalyzer and solve homogeneously in high concentration catalyst solution in the solvent.When using higher alcohols, in the presence of the process catalyzer of reduction activation, carry out the amination of higher alcohols as solvent.Because this disappears the hydroxyl of solvent higher alcohols, make only to observe the polyvalent alcohol with hydroxyl or the amination of amino alcohol.
According to the consideration mode identical, in this catalyst solution, supply with polyvalent alcohol or amino alcohol and amine continuously and can carry out ammoxidation with fixed-bed process.The aminocompound that is obtained is lower than the boiling point of catalyst solution, utilizes this point aminocompound can be distillated continuously.
The 4th described invention of the present invention is the preparation method of the 2nd or 3 described aminocompound, and this method has following formation: the boiling point of above-mentioned solvent is than the boiling point height of resultant of reaction.
Adopt this formation, except the effect of the 3rd acquisition, also can obtain following effect.
(1) the different of solvent and resultant of reaction (aminocompound) boiling point be can utilize, resultant of reaction and separated from solvent made by distillation, so the productivity excellence.
As mentioned above, adopt the manufacture method of aminocompound of the present invention, can obtain following beneficial effect.
If adopt the 1st invention, then
(1) can provide following aminocompound preparation method, this method can prepare industrial useful aminocompounds such as tertiary amine with high yield and good selectivity by reacting in the presence of as catalyzer that must composition with copper, nickel, calcium, basic metal or alkaline-earth metal (except the calcium) under high speed of response.
(2) can provide because catalyzer has high reactivity, so the reaction conditions gentleness, can adopt little amount of catalyst to finish the obviously excellent aminocompound preparation method of productivity of reaction at short notice simultaneously.
(3) can provide precious metals such as not using palladium or ruthenium metal in the catalyzer, therefore can suppress the aminocompound preparation method of the running cost of catalyzer.
(4) the not homogenizing reaction that has suppressed significantly because of the amine that contains raw material amine that precious metal causes and generation can be provided, the optionally excellent aminocompound preparation method who generates amine can be improved.
If adopt the 2nd described invention, then except the effect of 1 acquisition,
Therefore (1) also can provide because the catalyzer raw material is a metallic soap, not need miscellaneous technologies such as preparation, washing, drying, pulverizing, classification of necessary metal hydroxides when making curing catalysts, the aminocompound preparation method that productivity is obviously excellent.
(2) can provide also that to reduce the catalyzer of handling with polyvalent alcohol etc. be colloidal, therefore be fit to adopt any means in intermittent type and the continous way, also adapt to small-scale production, the excellent aminocompound preparation method of freedom simultaneously easily.
If adopt the 3rd described invention, then except the effect of the 2nd acquisition,
(1) can also provide following aminocompound preparation method, in the method, owing to can make highly active colloidal catalyzer stably be present in the solvent, so in solvent, supply with polyvalent alcohol or amine continuously as starting raw material, then can't cause catalyzer aggegation to take place because of the polar that is subjected to polyvalent alcohol etc. influences, can not cause active decline, therefore in base feed in solvent, promptly begin ammoxidation, productivity significantly improves, also may make diversified amine simultaneously, this was considered to impossible in the past, so applicability is obviously excellent.
If adopt the 4th described invention, then except the effect of the 2nd or 3 acquisition,
(1) can also provide and to utilize the different of solvent and resultant of reaction (aminocompound) boiling point, make resultant of reaction and separated from solvent by distillation, the aminocompound preparation method of productivity excellence.
The simple declaration of accompanying drawing
The mode chart of the preparation facilities of the aminocompound of [Fig. 1] demonstration embodiment 1.
Nomenclature
The preparation facilities of 1 aminocompound
2 reactors
The 2a supply-pipe
3 heating units
4 agitators
5 air supply parts
6 reductive agents (hydrogen) supply-pipe
7 unstripped gass (raw material amine) supply-pipe
8 raw alcohol supply-pipes
9 vent pipes
10 vapour pipes
11 water coolers
12 outlet pipes
13 susceptors
14 take pipe
15 vapor pipes
16 contain the solution of catalyzer
17 resultant of reaction and reaction water
Embodiment
Followingly describe implementing best mode of the present invention with reference to accompanying drawing.
(embodiment 1)
Fig. 1 is the mode chart of preparation facilities that shows the aminocompound of embodiment 1.
Among the figure, the 1st, starting raw material is reacted continuously, thereby the preparation facilities for preparing aminocompound continuously, the 2nd, reactor, 2a links to each other with reactor 2, in reactor 2, supply with the supply-pipe of following solvents and catalyzer raw material, the 3rd, be arranged at the heating units such as well heater on the outer wall of reactor 2, the 4th, be arranged at the agitator in the reactor 2, the 5th, the atomizer air supply parts such as (porous nozzles) of importing unstripped gas and reductive agent in reactor 2, the 6th, in air supply part 5, import the reductive agent supply-pipe of reductive agent such as hydrogen, the 7th, in air supply part 5, import gas shape ammonia, primary amine, the unstripped gas supply-pipe of raw material amine such as secondary amine, the 8th, the raw alcohol supply-pipe of raw alcohols such as importing polyvalent alcohol or amino alcohol in reactor 2, the 9th, discharge contains the vent pipe of the solvent of the catalyzer that uses from reactor 2, the 10th, link to each other with the top of reactor 2 and the steam that produces is drawn into the vapour pipe of reactor 2 outsides, the 11st, be disposed on the vapour pipe 10 and make in the reactor 2 water cooler of the vapor condensation that produces, the 12nd, the effusive outlet pipe of agglomerative resultant of reaction (aminocompound), the 13rd, link to each other with outlet pipe 12 and receive the receiver pope of effusive resultant of reaction (aminocompound), the 14th, link to each other with susceptor 13, take out the pipe of taking of resultant of reaction (aminocompound), the 15th, vapor pipe, the 16th, contain the higher alcohols of delay in the reactor 2 and the solution that contains catalyzer of whiteruss equal solvent and catalyzer, the 17th, the resultant of reaction (aminocompound) and the reaction water of being detained in the susceptor 13.Being separated into reaction water in susceptor 13 is lower floor, and resultant of reaction is the upper strata.
In addition, in the present embodiment, the solvent that contains the solution 16 of catalyzer can use lower than the polarity of raw alcohol, and long-chain monohydroxy-alcohol or whiteruss such as stearyl alcohol higher than the boiling point of goal response resultant (aminocompound), behenyl alcohol, tetracosanol.
For the preparation method who has as above the aminocompound in the embodiment 1 that constitutes, below describe with reference to accompanying drawing.
At first, from supply-pipe 2a donor solvent to reactor 2, in reactor 2, drop into catalyzer raw materials such as copper stearate, nickel stearate, calcium stearate, barium stearate then.One side revolving stirrer 4, with heating unit 3 reactor 2 heated up on one side, supply with reductive agents continuously from air supply part 5 simultaneously, make catalyzer in solvent, carry out reduction activation, generation contains the solution 16 of catalyzer.
After carrying out the reduction activation processing, preferably reactor 2 is set at 180～220 ℃, from the little by little continuous base feed alcohol to the solution 16 that contains catalyzer slightly of raw alcohol supply-pipe 8, from the raw material amine of air supply part 5 continuous supply gas shape to the solution 16 that contains catalyzer, in the solution 16 that contains catalyzer, begin to carry out the ammoxidation of alcohol simultaneously.
Than the solvent boiling point in the solution 16 that contains catalyzer low resultant of reaction (aminocompound) and reaction water generating gasification, be discharged into the outside of reactor 2 from vapour pipe 10, condense by water cooler 11, thereby can make resultant of reaction (aminocompound) continuously.
If adopt the aminocompound preparation method of above-described embodiment 1, then can obtain following effect.
(1) in solvent, make catalyst reduction activation after, if little by little continuously a small amount of pure and mild raw material amine of base feed in the solvent 16 that contains catalyzer, react, even then raw alcohol be high polar polyvalent alcohol (for example, be 1 of 2～8 polyvalent alcohol as carbon number, 6-hexylene glycol or 1,8-ethohexadiol etc.), the colloidal catalyzer is not vulnerable to the polarity effect of raw alcohol yet, therefore is not easy aggegation, can keep high reactivity.Therefore, can make completely dissolve inductive phase, promptly beginning ammoxidation in the base feed in the solution 16 that contains catalyzer, productivity significantly improves.On the other hand, for being dissolved in, the catalyzer raw material carries out the reduction activation processing in the high raw alcohol of polarity (carbon number is 2～8 polyvalent alcohol), then to the method for base feed amine wherein, wherein show the tendency of catalyzer generation cohesion in polyvalent alcohol, can not realize original activity, present the inductive phase that reaches a few hours time sometimes, lack productivity, and generating a large amount of high boiling substances in the resultant of reaction, yield is low.
(2) owing to contain the boiling point height of the boiling point of the solvent in the solution 16 of catalyzer, therefore utilize the boiling point of solvent and resultant of reaction different, make resultant of reaction and separated from solvent, so productivity is obviously excellent by distillation than resultant of reaction (aminocompound).
Embodiment
Below, embodiments of the invention are specifically described.Also have, the present invention is not limited to these embodiment.In addition, the evaluation of the aminocompound that is generated is undertaken by gas-chromatography and GC/MS (gas-chromatography/mass analysis).
(embodiment 1)
Be provided with condenser and the separator that separates generation water, the reaction mixture sampling device, exhaust exit pipe, unstripped gas ingress pipe (sintered glass system atomizer), agitator, in the 500mL flask of thermometer, add 200g as 1 of polyvalent alcohol, the 12-dodecanediol, interpolation is as the copper stearate 2.0g (metallic copper is 0.1wt% with respect to polyvalent alcohol) of catalyzer raw material, nickel stearate 0.4g (metallic nickel is 0.02wt% with respect to polyvalent alcohol), calcium stearate 0.4g (calcium metal is 0.02wt% with respect to polyvalent alcohol), barium stearate 0.4g (barium metal is 0.02wt% with respect to polyvalent alcohol), rotating mixer then,, heat up to replacing in the flask with nitrogen.Until 100 ℃ 4 kinds of metallic soaps as the catalyzer raw material are dissolved equably.When reaching 100 ℃ nitrogen is switched to hydrogen, handle to carry out reduction activation by flow velocity drum hydrogen gas bubbles in flask of under meter 22L/ hour.Peculiar green at 170～190 ℃ of following divalent copper and mickels is desalinated gradually, and the catalyzer raw material is reduced to the uniform colloidal catalyzer of outward appearance.Temperature of reaction is remained 210 ℃, the dimethylamine of secondary amine flow velocity and the hydrogen (flow velocity 22L/ hour) with 28L/ hour under normal pressure is formed gas mixture, carry out air feed continuously.
Soon, be accompanied by distillating of water, ammoxidation begins to carry out.During the reaction beginning, the reaction mixture tone in the flask is a black, and along with reaction is carried out, the catalyzer in the flask becomes the complete colloidal of brown, and speed of response sharply rises.To reaction mixture (removing reaction water) sampling, carry out gas chromatographic analysis by 1 hour interval, calculate transformation efficiency, resultant ratio, yield, speed of response.As speed of response,, calculate speed of response respectively with respect to the unit mole feed speed of per unit mole of copper, dimethylamine for second step reaction shown in the reaction of the first step shown in the chemical equation (E), the chemical equation (F)
(mole·h
-1·mole
(Cu) -1·[mole
(DMA) -1·h
-1]
-1)。
In addition, the analysis condition of gas-chromatography is as follows.
Device category: the GC-14B that Shimadzu Seisakusho Ltd. makes, capillary column: 0.32mm * 30m, carrier gas: nitrogen, 30mL/ branch, weighting agent: DB-17, column temperature: 100～270 ℃, kept 13 minutes heat-up rate down at 270 ℃: 10 ℃/minute, detector: FID, sample solution concentration: 10%, splitting ratio: 20.
(embodiment 2)
Use is as the decamethylene-glycol of polyvalent alcohol, supplies with dimethylamine with 28L/ hour flow velocity, in addition, carries out ammoxidation by the mode identical with embodiment 1.
(embodiment 3)
Use is as 1 of polyvalent alcohol, and the 9-nonanediol is supplied with dimethylamine with 28L/ hour flow velocity, in addition, carries out ammoxidation by the mode identical with embodiment 1.
(embodiment 4)
Use is as 1 of polyvalent alcohol, and the 8-ethohexadiol is supplied with dimethylamine with 28L/ hour flow velocity, in addition, carries out ammoxidation by the mode identical with embodiment 1.
(embodiment 5)
Be provided with condenser and the separator that separates generation water, the reaction mixture sampling device, exhaust exit pipe, the unstripped gas ingress pipe, agitator, in the 500mL flask of thermometer, add the behenyl alcohol (carbon number 22) of 200g as solvent, interpolation is as the copper stearate 4.0g (metallic copper is 0.2wt% with respect to the solvent higher alcohols) of catalyzer raw material, nickel stearate 0.8g (metallic nickel is 0.04wt% with respect to higher alcohols), calcium stearate 0.8g (calcium metal is 0.04wt% with respect to higher alcohols), barium stearate 0.8g (barium metal is 0.04wt% with respect to higher alcohols), rotating mixer then,, heat up to replacing in the flask with nitrogen.Until 100 ℃ 4 kinds of metallic soaps as the catalyzer raw material are dissolved equably.When reaching 100 ℃ nitrogen is switched to hydrogen, in flask, rouse hydrogen gas bubbles, carry out reduction activation and handle with flow velocity by under meter 22L/ hour.Peculiar green at 170～190 ℃ of following divalent copper and mickels is desalinated gradually, and the catalyzer raw material is reduced to the uniform colloidal catalyzer of outward appearance.Temperature of reaction is remained 210 ℃, secondary amine dimethylamine flow velocity and hydrogen (flow velocity 22L/ hour) with 28L/ hour under normal pressure is formed gas mixture, and air feed is 3 hours continuously, behenyl alcohol generation amination, obtain having generated N, the catalyst solution of N-dimethyl mountain Yu amine.In addition, the transformation efficiency of behenyl alcohol is 100%.
In remaining 210 ℃ catalyst solution, add continuously as 1 of polyvalent alcohol with 0.48 mole/hour feed speed, the 6-hexylene glycol will form gas mixture as dimethylamine feed speed and hydrogen with 1.0 moles/hour under normal pressure of secondary amine simultaneously, carry out bubbling and continuous air feed.In addition, the feed speed of hydrogen is 22L/ hour.
Beginning to supply with 1, in the time of the 6-hexylene glycol, be accompanied by distillating of water, ammoxidation begins immediately.Do not observe inductive phase fully.Reaction mixture is distillated outside the reaction system consistently with reaction water.Reach constant back (mean residence time is 2.1 hours), distilled reaction mixture (removing reaction water) is taken a sample and gas chromatographic analysis, calculate transformation efficiency, resultant ratio, yield, speed of response.
(embodiment 6)
Use 12-hydroxyl stearyl alcohol as polyvalent alcohol, supply with dimethylamine, in addition, carry out ammoxidation by the mode identical with embodiment 1 with 17L/ hour flow velocity.
(embodiment 7)
As the catalyzer raw material, add copper stearate 2.0g (metallic copper is 0.1wt% with respect to polyvalent alcohol), nickel stearate 0.4g (metallic nickel is 0.02wt% with respect to polyvalent alcohol), (calcium metal is 0.005wt% with respect to polyvalent alcohol to calcium stearate 0.1g, calcium metal is 0.05 with respect to the ratio of metallic copper), barium stearate 0.4g (barium metal is 0.02wt% with respect to polyvalent alcohol), in addition, carry out ammoxidation by the mode identical with embodiment 1.
(embodiment 8)
As the catalyzer raw material, add copper stearate 2.0g (metallic copper is 0.1wt% with respect to polyvalent alcohol), nickel stearate 0.4g (metallic nickel is 0.02wt% with respect to polyvalent alcohol), (calcium metal is 0.01wt% with respect to polyvalent alcohol to calcium stearate 0.2g, calcium metal is 0.1 with respect to the ratio of metallic copper), barium stearate 0.4g (barium metal is 0.02wt% with respect to polyvalent alcohol), in addition, carry out ammoxidation by the mode identical with embodiment 1.
(embodiment 9)
As the catalyzer raw material, add copper stearate 2.0g (metallic copper is 0.1wt% with respect to polyvalent alcohol), nickel stearate 0.4g (metallic nickel is 0.02wt% with respect to polyvalent alcohol), (calcium metal is 0.04wt% with respect to polyvalent alcohol to calcium stearate 1.0g, calcium metal is 0.5 with respect to the ratio of metallic copper), barium stearate 0.4g (barium metal is 0.02wt% with respect to polyvalent alcohol), in addition, carry out ammoxidation by the mode identical with embodiment 1.
(embodiment 10)
As the catalyzer raw material, add copper stearate 2.0g (metallic copper is 0.1wt% with respect to polyvalent alcohol), nickel stearate 0.4g (metallic nickel is 0.02wt% with respect to polyvalent alcohol), (calcium metal is 0.06wt% with respect to polyvalent alcohol to calcium stearate 1.2g, calcium metal is 0.6 with respect to the ratio of metallic copper), barium stearate 0.4g (barium metal is 0.02wt% with respect to polyvalent alcohol), in addition, carry out ammoxidation by the mode identical with embodiment 1.
(comparative example 1)
As the catalyzer raw material, add copper stearate 2.0g (metallic copper is 0.1wt% with respect to polyvalent alcohol), nickel stearate 0.4g (metallic nickel is 0.02wt% with respect to polyvalent alcohol), barium stearate 0.4g (barium metal is 0.02wt% with respect to polyvalent alcohol), in addition, carry out ammoxidation by the mode identical with embodiment 1.Comparative example 1 does not add calcium stearate in the catalyzer raw material, different with embodiment 1 in this.
(comparative example 2)
According to the embodiment 1 of record in the patent documentation 3, preparation is by the copper-nickel-platinum family element three-way catalyst (Cu: Ni: Ru=4: 1: 0.01, carrier was a y-type zeolite, and charge capacity is 50wt% based on metal oxide) of synthetic zeolite load.
In being provided with for the 500mL flask that separates the condenser that generates water and separator, reaction mixture sampling device, exhaust exit pipe, unstripped gas ingress pipe, agitator, thermometer, add 200g as 1 of polyvalent alcohol, the catalyzer (metallic copper is 0.1wt% with respect to polyvalent alcohol) of 10-decanediol and 0.62g preparation, stir on one side,, heat up to replacing in the flask with nitrogen in one side.When reaching 100 ℃ nitrogen is switched to hydrogen, make hydrogen pass through under meter, and be blown in the flask, until being warmed up to 210 ℃ with 22L/ hour flow velocity.Make temperature of reaction remain 210 ℃, secondary amine dimethylamine flow velocity and hydrogen (flow velocity 22L/ hour) with 27L/ hour under normal pressure is formed gas mixture, carry out continuous air feed, utilize gas-chromatography to follow the tracks of reaction.
(comparative example 3)
Except support of the catalyst is MS-13X, by carrying out the ammoxidation of decamethylene-glycol with comparative example 2 identical conditions.
Listed the mass fraction of the various metallographic phase of catalyzer raw material among the embodiment 1～10 in the table 1, compiled reaction times of having listed embodiment 1～6 and comparative example 1～3, the transformation efficiency from the polyvalent alcohol to the aminocompound (%), ratio (%), the ratio (%) of two tertiary amines, ratio (%), high boiling substance ratio (%), low-boiling point material ratio (%), the ammoxidation the first step and the speed of response (moleh in second step of monodentate tertiary amine in the table 2 through the polyvalent alcohol in the reaction times afterreaction mixture (removing reaction water) of sampling for polyvalent alcohol
-1Mole
(Cu) -1[mole
(DMA) -1H
-1]
-1) (with respect to the speed of response of the unit mole feed speed of per unit mole of copper, dimethylamine).In addition, in table 1, as the content that is expressed as two tertiary amines, in embodiment 1 and comparative example 1 is N, N, N ', N '-tetramethyl--1, the inferior dodecyl diamines of 12-is at embodiment 2, in comparative example 2 and the comparative example 3 is N, N, N ', N '-tetramethyl--1, the inferior decyl diamines of 10-, in embodiment 3, be N, N, N ', N '-tetramethyl--1, the nonamethylene diamines of 9-is N in embodiment 4, N, N ', N '-tetramethyl--octamethylene diamines is N in embodiment 5, N, N ', N '-tetramethyl--hexamethylene diamines, in embodiment 6, be 12-N, N-dimethylamino-1-N ', N '-dimethyl stearic amine is as the content that is expressed as monodentate tertiary amine, in embodiment 1 and comparative example 1 is 12-N, N-dimethylamino-1-lauryl alcohol is at embodiment 2, in comparative example 2 and the comparative example 3 is 10-N, N-dimethylamino-decyl alcohol-1, in embodiment 3, be 9-N, N-dimethylamino-nonyl alcohol-1 is 8-N in embodiment 4, N-dimethylamino-octanol-1, in embodiment 5, be 6-N, N-dimethylamino-hexanol-1 is 12-N in embodiment 6, N-dimethylamino stearyl alcohol.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Cu | 0.1 | 0.1 | 0.1 | 0.1 | 0.2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Ni | 0.02 | 0.02 | 0.02 | 0.02 | 0.04 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| Ca | 0.02 | 0.02 | 0.02 | 0.02 | 0.04 | 0.02 | 0.005 | 0.01 | 0.04 | 0.06 |
| Ba | 0.02 | 0.02 | 0.02 | 0.02 | 0.04 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
Table 2
| Reaction times (hour) | Transformation efficiency (%) | Alcohol (%) | Two tertiary amines (%) | Monodentate tertiary amine (%) | High boiling substance (%) | Low-boiling point material (%) | Ammoxidation speed | ||
| The first step | Second step | ||||||||
| Embodiment 1 | 7.0 | 99.9 | 0.1 | 84.2 | 10.8 | 4.2 | 0.6 | 160 | 112 |
| Embodiment 2 | 7.0 | 100 | 0 | 88.3 | 5.7 | 5.4 | 0.2 | 211 | 127 |
| 9.0 | 100 | 0 | 90.9 | 2.4 | 5.8 | 0.6 | |||
| 10.0 | 100 | 0 | 92.8 | 1.7 | 5.3 | 0.1 | |||
| Embodiment 3 | 19.0 | 99.9 | 0.1 | 83.6 | 7.2 | 7.2 | 0.1 | 64 | 75 |
| 21.0 | 99.9 | 0.1 | 84.2 | 5.7 | 7.5 | 0.1 | |||
| Embodiment 4 | 19.0 | 100 | 0 | 80.4 | 9.8 | 7.1 | 0.3 | 97 | 68 |
| Embodiment 5 | 2.1 | 99.5 | 0.5 | 85.9 | 11.8 | 1.2 | 0.2 | 305 | 262 |
| Embodiment 6 | 16.0 | 94.7 | 5.3 | 33.1 | 61.6 | 0 | 0 | 13 | 4 |
| Comparative example 1 | 35.0 | 94.0 | 6.0 | 70.4 | 12.3 | 9.8 | 0.8 | 40 | 37 |
| Comparative example 2 | 6.0 | 34.0 | 66.0 | 2.9 | 29.1 | 1.2 | 0 | 49 | 3 |
| Comparative example 3 | 12.0 | 94.0 | 6.1 | 45.3 | 43.7 | 4.3 | 0 | 81 | 46 |
If the embodiment in the table 21 is compared with comparative example 1, then among the embodiment 1 reaction the 7th hour the time transformation efficiency be 99.9%, two tertiary amines and monodentate tertiary amine are respectively 84.2%, 10.8% (amounting to 95.0%), high boiling substance and low-boiling point material are respectively 4.2%, 0.6%, relative therewith, in the comparative example 1 reaction the 35th hour the time transformation efficiency be 94.0%, two tertiary amines and monodentate tertiary amine are respectively 70.4%, 12.3% (amounting to 82.7%), high boiling substance and low-boiling point material are respectively 9.8%, 0.8%, the transformation efficiency height of embodiment 1 can obtain the highly selective to the target tertiary amine as can be known.In addition we know, for the first step and the speed of response in second step, compare with comparative example 1, embodiment 1 reacts by 3～4 times high speed of response.
Comparative example 1 does not add the calcium stearate as the catalyzer raw material, and catalyzer is copper-nickel-barium three-way catalyst, so catalytic activity is reduced to below 1/3 of catalyzer of embodiment 1 significantly, can clearly confirm the superiority of calcareous colloid catalyst.
Then, if embodiment 2 is compared with comparative example 2, then among the embodiment 2 reaction the 7th hour the time transformation efficiency be 100%, two tertiary amines and monodentate tertiary amine are respectively 88.3%, 5.7% (amounting to 94.0%), relative therewith, the transformation efficiency in the comparative example 2 the 6th hour of reaction the time is that 34.0%, two tertiary amine and monodentate tertiary amine are respectively 2.9%, 29.1% (amounting to 32.0%), the transformation efficiency height of embodiment 2 can obtain the highly selective to the target tertiary amine as can be known.In addition, if compare the speed of response in second step, compare with comparative example 2 as can be known, embodiment 2 reacts by the high speed of response more than 40 times.
Also have, comparative example 3 is compared with comparative example 2, though the ammoxidation speed in second step increases substantially, compares with embodiment 2 and shows that the colloid catalyst that contains calcium that uses among the present invention is at the coabsolute height of catalyst activity.
According to present embodiment, all can be with high speed of response acquisition as the amino alcohol of the resultant of reaction of the ammoxidation the first step with as the tertiary amine that reacts second resultant of reaction that goes on foot, thereby show the volume production that can carry out amino alcohol or tertiary amine with low cost, productivity is obviously excellent.
In addition, among the embodiment 3 and 4, the transformation efficiency during the 19th hour of reaction is that the total of 100%, two tertiary amine and monodentate tertiary amine is about 90% substantially, thereby shows the transformation efficiency height, can obtain the highly selective to the target tertiary amine.
In addition, according to embodiment 6, transformation efficiency, 12-hydroxyl-1-N when reacting 16 hours, N-dimethyl stearic amine (monodentate tertiary amine) and 12-N, N-dimethylamino-1-N ', the generation ratio of N '-dimethyl stearic amine (two tertiary amines) is respectively 94.7%, 61.6%, 33.1%, the ammoxidation speed (moleh of the first step
-1Mole
(Cu) -1[mole
(DMA) -1H
-1]
-1) be that 13, the second ammoxidation speed (unit is as previously discussed) that go on foot are 4.The above results shows, the colloid catalyst that contains calcium by use, not only can be by 12-hydroxyl stearyl alcohol preparation 12-hydroxyl-1-N, N-dimethyl stearic amine, and can carry out amination to stable 12-hydroxyl, thus preparation 12-N, N-dimethylamino-1-N ', N '-dimethyl stearic amine has demonstrated the high catalyst activity of the colloid catalyst that contains calcium that uses among the present invention.
In addition, in table 2, the embodiment and the comparative example of total less than 100% of ratio that has ratio, the low-boiling point material of ratio, the high boiling substance of ratio, the monodentate tertiary amine of ratio, two tertiary amines of polyvalent alcohol, this is considered to owing to the error brought of gas chromatographic analysis, produced influence from the ester of catalyzer raw material etc., and this is specifically studied.
In addition, for the embodiment 5 that in catalyst solution, supplies with polyvalent alcohol and dimethylamine continuously, not only do not observe inductive phase fully, and average retention time (reaction times) is 2.1 hours, transformation efficiency is that 99.5%, two tertiary amine and monodentate tertiary amine are respectively 85.9%, 11.8% (adding up to 97.7%), and high boiling substance and low-boiling point material are respectively 1.2%, 0.2%, this shows can realize high conversion and selectivity, can greatly reduce high boiling substance simultaneously.In addition, the anti-speed of amination is 305 in the first step, is 262 in second step, has demonstrated the maximum in these embodiment and the comparative example.
Also have, do not adopt continuous process (not using catalyst solution), carry out with embodiment 5 identical 1 but adopt to react with embodiment 1～4 identical intermittent, during the ammoxidation of 6-hexylene glycol, transformation efficiency when the reaction times is 5.5 hours is that the total yield of 20%, two tertiary amine and monodentate tertiary amine is 20%.
In addition, the continuous process that embodiment is carried out is applicable to 1 of embodiment 3 and 4, and 9-nonanediol and 1 is identical with the situation of embodiment 5 during the ammoxidation of 8-ethohexadiol, can make completely dissolve inductive phase.
Demonstrated the absolute superiority of the continuous process of carrying out among the embodiment 5 thus.
Also have, when the generation ratio of two tertiary amines of the generation ratio of two tertiary amines of embodiment 7,10 and monodentate tertiary amine, embodiment 8,9 and monodentate tertiary amine compared when reacting 1 hour, embodiment 7,10 had significantly than embodiment 8,9 and reduces.Can confirm by these embodiment, in catalyzer is formed, if when calcium exceeds 0.1～0.5 scope with respect to the ratio of copper with atomic ratio measuring, catalyst activity reduction.
In addition, in embodiment 1～5, as the catalyzer raw material, when using tetradecanoic acid copper, acetylacetone copper, dimethyl glyoxime copper, Nickel Dimethylglyoxime, n-nonanoic acid nickel, acetylacetonate nickel, calcium laurate place of magnesium stearate copper, nickel stearate and calcium stearate, also having obtained is 100% transformation efficiency substantially, and can confirm has identical trend.In addition, in embodiment 1～5, when using barium laurate, sodium stearate place of magnesium stearate barium, also having obtained is 100% transformation efficiency substantially, and can confirm has identical trend.But, can confirm to use barium laurate, sodium stearate to compare with the use barium stearate, speed of response is low slightly.This shows and is suppressing on the aggegation effect of copper/nickel metallic colloid, chain length than the long Metallic stearates of lauric acid than lauroleate excellence.Show also that in addition the stearate of barium suppresses the effect excellence in the aggegation that suppresses on the aggegation effect of copper/nickel metallic colloid than the stearate of sodium.
In addition, when using ammonia, methylamine, hexahydroaniline etc., also can confirm identically, can obtain corresponding tertiary amine with embodiment 1～5 as raw material amine.
The above shows, according to these embodiment, reacts as catalyzer that must composition by using with copper, nickel, calcium, basic metal or alkaline-earth metal (except the calcium), can obtain tertiary amine with high yield and good selectivity.In addition, even in the second step ammoxidation, also can finish reaction with high speed of response as the controlled step of speed of response.Also show in addition,, can make catalyzer demonstrate original activity, disappeared inductive phase, obtain high speed of response, can reach high selectivity simultaneously by in catalyst solution, supplying with polyvalent alcohol and diethylamine continuously.Can make diversified amine thereby can provide, this was considered to impossible in the past, and the preparation method of the aminocompound of the obvious excellence of applicability.
Industrial applicibility
The present invention relates to use polyalcohol or amino alcohol and ammonia or primary amine or secondary amine to react, thereby the amino-compound preparation method of the tertiary amine that preparation is corresponding or amino alcohol etc., following amino-compound preparation method can be provided, for the method, owing to do not use the noble metals such as palladium or ruthenium in the catalyst, therefore can the decrease running cost, ammoxidation of the present invention is the reaction that does not basically need hydrogen (except the reduction irrigation processing of catalyst raw material) simultaneously, and strengthened the effect of catalyst component with calcium, therefore can be with high yield and the good industrial useful amino-compounds such as tertiary amine of selective preparation under high reaction speed.
Claims (4)
1. the preparation method of aminocompound, it is characterized in that, with copper, nickel, calcium, basic metal or alkaline-earth metal (except the calcium) as the catalyzer of essential composition in the presence of, polyvalent alcohol and/or above-mentioned polyvalent alcohol amino alcohol and ammonia or primary amine or the secondary amine after amination is reacted.
2. the preparation method of the described aminocompound of claim 1, it is characterized in that above-mentioned catalyzer is to utilize hydrogen or other reductive agent that the mixture more than a kind or 2 kinds in the carboxylate salt of more than a kind or 2 kinds and (d) basic metal more than a kind or 2 kinds, in the complex compound of the carboxylate salt of (c) calcium or calcium more than a kind or 2 kinds, in the intramolecularly complex compound of the carboxylate salt of (b) nickel or nickel in the intramolecularly complex compound of the carboxylate salt of (a) copper or copper or alkaline-earth metal (except the calcium) is reduced to handle and form in above-mentioned polyvalent alcohol or above-mentioned amino alcohol or solvent.
3. the preparation method of the described aminocompound of claim 2, it is characterized in that, in the above-mentioned solvent lower than above-mentioned polyvalent alcohol or above-mentioned amino alcohol polarity, above-mentioned catalyzer is reduced processing, in the above-mentioned solvent that contains above-mentioned catalyzer, supply with above-mentioned polyvalent alcohol and/or above-mentioned amino alcohol continuously, reach above-mentioned ammonia or above-mentioned primary amine or above-mentioned secondary amine and make its reaction.
4. the preparation method of claim 2 or 3 described aminocompounds is characterized in that, the boiling point of above-mentioned solvent is than the boiling point height of resultant of reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JPPCT/JP2006/315937 | 2006-08-11 | ||
| PCT/JP2006/315937 WO2008018148A1 (en) | 2006-08-11 | 2006-08-11 | Process for producing amino compound |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101391964B (en) * | 2008-11-07 | 2011-06-01 | 天津大学 | Method for preparing 2-amido-1-alkyl alcohol and catalyst preparation method |
| CN102614886A (en) * | 2012-02-27 | 2012-08-01 | 上海应用技术学院 | Catalyst used in preparation of chiral amino alcohol, preparation method and application |
| CN103288722A (en) * | 2013-05-08 | 2013-09-11 | 温州大学 | High-selectivity synthesis method of secondary amine |
| CN105384706A (en) * | 2015-10-27 | 2016-03-09 | 中国科学院兰州化学物理研究所 | Preparation method of N-acetonyl amine compound |
| CN105622436A (en) * | 2016-03-01 | 2016-06-01 | 苏州艾缇克药物化学有限公司 | Preparation method of 6-amino-1-hexanol by taking calcium carbonate as catalyst |
| CN106546067A (en) * | 2015-09-18 | 2017-03-29 | 海南椰国食品有限公司 | Bacterial cellulose gel film replaces low temperature integrated dry drying system |
| CN109395743A (en) * | 2018-12-18 | 2019-03-01 | 浙江工业大学 | A kind of metalNicatalyst of solvay-type and its preparation method and application |
| CN114874100A (en) * | 2022-06-07 | 2022-08-09 | 中国日用化学研究院有限公司 | Preparation method of N, N, N' -tetramethyl alkyl diamine |
| CN116099537A (en) * | 2022-12-08 | 2023-05-12 | 东南大学 | Ni-NiO multiphase magnetic catalyst, preparation method and application thereof |
| CN116716031A (en) * | 2023-08-08 | 2023-09-08 | 广州市交通运输职业学校(广州市交通运输高级职业技术学校、广州市交通运输中等专业学校) | Paint-spraying-free quick-drying vehicle body repair material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011020B2 (en) * | 1979-09-17 | 1985-03-22 | 花王株式会社 | Production method of tertiary amine |
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2006
- 2006-08-11 WO PCT/JP2006/315937 patent/WO2008018148A1/en active Application Filing
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- 2007-07-17 CN CNA2007101368025A patent/CN101121666A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101391964B (en) * | 2008-11-07 | 2011-06-01 | 天津大学 | Method for preparing 2-amido-1-alkyl alcohol and catalyst preparation method |
| CN102614886A (en) * | 2012-02-27 | 2012-08-01 | 上海应用技术学院 | Catalyst used in preparation of chiral amino alcohol, preparation method and application |
| CN103288722A (en) * | 2013-05-08 | 2013-09-11 | 温州大学 | High-selectivity synthesis method of secondary amine |
| CN106546067A (en) * | 2015-09-18 | 2017-03-29 | 海南椰国食品有限公司 | Bacterial cellulose gel film replaces low temperature integrated dry drying system |
| CN106546067B (en) * | 2015-09-18 | 2022-08-19 | 海南椰国食品有限公司 | Low-temperature integrated drying method for replacing bacterial cellulose gel film |
| CN105384706A (en) * | 2015-10-27 | 2016-03-09 | 中国科学院兰州化学物理研究所 | Preparation method of N-acetonyl amine compound |
| CN105622436A (en) * | 2016-03-01 | 2016-06-01 | 苏州艾缇克药物化学有限公司 | Preparation method of 6-amino-1-hexanol by taking calcium carbonate as catalyst |
| CN109395743A (en) * | 2018-12-18 | 2019-03-01 | 浙江工业大学 | A kind of metalNicatalyst of solvay-type and its preparation method and application |
| CN114874100A (en) * | 2022-06-07 | 2022-08-09 | 中国日用化学研究院有限公司 | Preparation method of N, N, N' -tetramethyl alkyl diamine |
| CN114874100B (en) * | 2022-06-07 | 2023-12-22 | 中国日用化学研究院有限公司 | Preparation method of N, N, N' -tetramethyl alkyl diamine |
| CN116099537A (en) * | 2022-12-08 | 2023-05-12 | 东南大学 | Ni-NiO multiphase magnetic catalyst, preparation method and application thereof |
| CN116716031A (en) * | 2023-08-08 | 2023-09-08 | 广州市交通运输职业学校(广州市交通运输高级职业技术学校、广州市交通运输中等专业学校) | Paint-spraying-free quick-drying vehicle body repair material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| WO2008018148A1 (en) | 2008-02-14 |
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