JPS59210051A - Production of tertiary amine - Google Patents

Abstract

PURPOSE:To obtain the titled compound economically, in an industrial scale, by reacting a long-chain olefin with carbon monoxide, hydrogen and an alkanolamine in the presence of a catalyst, using a specific polyhydric alcohol or its mixture with water as a solvent, and separating the catalyst layer from the product. CONSTITUTION:The objective tertiary amine can be produced in high yield, by (1) reacting a 8-30C long-chain olefin with carbon monoxide, hydrogen and a monoalkanolamine or dialkanolamine in the presence of a catalyst composed mainly of a compound containing rhodium and/or ruthenium (e.g. rhodium chloride), using a solvent comprising an alcohol selected from 2-3C dihydric alcohol, 3-6C trihydric alcohol, or an intermolecular dehydrative condensation product of 2-3C dihydric or trihydric alcohol or its mixture with water, (2) separating the reaction product into the amine layer containing the produced tertiary amine and the solvent layer containing the catalyst by phase separation, and (3) recycling the solvent layer containing the catalyst to the reaction zone.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for layer-terminating tertiary amines having long-chain alkyl groups and hydroxyalkyl groups in their molecules, and more specifically, to a method for layer-terminating tertiary amines having long-chain alkyl groups and hydroxyalkyl groups in their molecules. - Reacting carbon oxide, hydrogen and alkanolamines,
The present invention relates to a method for producing tertiary amines having a long-chain alkyl group (Iff + dialkyl group).

Higher amines and their derivatives having long-chain alkyl groups are useful substances that have a variety of uses depending on their structure, such as intermediates for detergents, anti-rust agents, and fabric softening agents, and currently the majority of them are Parts are commercially derived from natural fatty acids such as coconut oil, palm oil, and tallow.

In particular, the tertiary amines having long-chain alkyl groups and hydroxyalkyl groups obtained by the method of the present invention can be used in the form of quaternary ammonium salts for fabric softeners, antistatic agents, shampoo rinses, etc. The members are useful as nonionic surfactant ingredients for hair washing and the like after being induced into the form of amine oxide.

PRIOR ART Tertiary amines of this type have heretofore been obtained by addition of alkylene oxides to amines containing long-chain alkyl groups derived from fatty acids.

This method consists of: ■ Synthesizing fatty nitriles by high-temperature reaction of fatty acids and ammonia; ■ Conversion to primary or secondary amines by hydrogenation; ■ Oxidation of primary or secondary amines to secondary amines. It consists of the step of converting into a hydroxyalkyl group-containing tertiary amine by addition of alkylene, and requires many steps.

On the other hand, long-chain alkyldimethylamines and long-chain alkyldiethylamines are produced in good yields by reacting higher alcohols with lower secondary amines, such as dimethylamine and diethylamine, under hydrogen pressure in the presence of a hydrogenation catalyst. Tetrahedron Letters
triatEngineering Chemistry
yResearch and Development
, Vol. 16, pp. 261-266 (1977), details of this method are described.

However, this method cannot efficiently produce tertiary amines having a hydroxyl group in the molecule, such as the hydroxyalkyl group-containing tertiary amine which is the target substance of the present invention.

In order to produce such tertiary amines by this method, a higher alcohol must be subjected to a so-called amithrisis reaction with jetanolamine, etc. In this case, not only the hydroxyl group of the higher alcohol but also jetanolamine and the product are It also reacts with the hydroxyl group in the tertiary amine, making it impossible to obtain the desired product in good yield.

On the other hand, it is also known to synthesize tertiary amines from long-chain olefins, carbon oxide, hydrogen, and primary or secondary amines. Olefin using a catalyst containing a complex compound consisting of and cobalt carbonyl, -
A one-step method for the synthesis of tertiary amines from carbon oxide, hydrogen, and secondary amines is disclosed. However, this method produces a large amount of alcohol as a by-product and is not necessarily effective as a method for producing the desired tertiary amine.

Hetvetica Chimica Acta, 5
4 (1971), pp. 1440-1445 and US Pat. No. 3,947,458, amines are removed from olefins, carbon oxides, water and nitrogen-containing compounds by using a catalyst consisting of iron pentacarbonyl and a rhodium compound. ◎This method has a fairly good amine yield, but it does not use an inexpensive mixed gas of hydrogen and carbon monoxide as a raw material gas, and requires pure carbon monoxide. In addition, it is necessary to recover expensive rhodium compounds. Japanese Patent Publication No. 52-38527 discloses that the electron-donating atom is oxygen, nitrogen, or sulfur. discloses a method for producing a tertiary amine by reacting an olefin, carbon oxide, hydrogen, and a secondary amine.

Although this method also has an extremely good yield of the target amine, the recovery and reuse of expensive Group I metals, such as rhodium and ruthenium, which are used in considerable amounts, is a problem in industrial use9. There is no mention of any point.

In other words, in the method of synthesizing higher amines having long-chain alkyl groups using long-chain olefins, the reaction selectivity is low when relatively inexpensive cobalt etc. among Group III metal compounds is used. Yield is low. On the other hand, when an expensive metal compound such as rhodium is used, a high yield can be obtained, but it is not necessarily industrially advantageous because the catalyst cost is high.

Therefore, in the one-step synthesis method of higher amines having long-chain alkyl groups from olefins, when expensive catalysts such as rhodium are used to obtain high yields, it is difficult to establish techniques for catalyst recovery and reuse. is necessary.

Conventionally, various methods have been proposed for recovering rhodium catalysts used in hydroformylation reactions, etc., such as (1) a method of separating the product and catalyst by evaporation or distillation (for example, Japanese Patent Application Laid-Open No. 125103/1983). 2) A method of separating the formed aldehyde by extracting it with a polar solvent such as water (e.g., JP-A No. 51-29412) (3) A method of separating the rhodium complex by adsorption (e.g., JP-A-50-62936) (4) ) Separation methods using membranes made of silicone rubber, cellulose, etc. (for example, Japanese Patent Publication No. 47-7365) are known. However, method (1) above is applicable when the product is a lower aldehyde with a low boiling point and the catalyst is a rhodium complex modified with triphenylphosphine etc., which has relatively high thermal stability. However, there are various problems in applying it to the production process of high boiling point higher amines, which is the object of the present invention. Further, the method (2) above cannot be applied to higher amines having low water solubility. (
The adsorption method described in 3) has been applied to industrial processes for producing higher aldehydes, but it cannot be said to be an effective method when the product is a nitrogen-containing compound such as an amine that may have a negative effect on the adsorbent. . Furthermore, membrane separation in (4) requires a large difference in molecular size between the product and the catalyst complex, and is not an effective method for higher amine products with relatively large molecules.

Summary of the Invention The present inventors previously proposed the invention in Japanese Patent Application No. 56-201986. Amines having a hydroxyalkyl group and a long-chain alkyl group in the molecule, which are the target substances of the present invention, have increased compatibility with polar solvents compared to corresponding amines without a hydroxyl group, and as a result, after the reaction phase separation becomes difficult. Even if phase separation becomes possible, it is expected that a long time will be required for the separation and that an increased amount of expensive noble metal complexes and solvents will be eluted into the generated amine layer.

However, by using a limited number of specific polyhydric alcohols as a solvent in this reaction, phase separation proceeds quickly even in such a reaction system, and there is little loss in the elution of precious metal catalysts such as rhodium, and the catalyst layer can be easily removed. The present invention was completed by discovering that it can be used for repeated reactions.

That is, the present invention provides long chain olefins having 8 to 30 carbon atoms, -
Tertiary amines having a hydroxyalkyl group in the molecule are produced by reacting carbon oxide, hydrogen and monoalkanolamines or dialkanolamines in the presence of a catalyst containing a compound containing taurodium and/or ruthenium as the main components. In the manufacturing method, as a solvent,
Polyhydric alcohols selected from the group consisting of dihydric alcohols having 2 to 3 carbon atoms, trihydric alcohols having 3 to 6 carbon atoms, and intermolecular dehydration products of dihydric or trihydric alcohols having 2 to 3 carbon atoms. A tertiary alcohol, which is characterized by reacting with a hydric alcohol or a mixture thereof and water, and causing the reaction product to undergo phase separation into an amine layer containing the produced tertiary amine and a solvent layer containing a catalyst. The purpose is to provide a method for producing amines.

By using the method of the present invention, hydroxyalkyl group-containing tertiary amines, which are produced by adding ethylene oxide or propylene oxide to higher primary or secondary amines derived from natural fatty acids, can be produced for long periods. It is now possible to produce it in one step from chain olefins.

(Catalyst) The catalyst used in the present invention is a compound of rhodium and/or ruthenium among group (I) noble metals, and is used in the form of a halide, nitrate, halocarbonyl, carbonyl complex, or the like.

Specifically, rhodium chloride, rhodium nitrate, rhodium bromide, rhodium iodide, chlorodicarbonyl rhodium dimer, rhodium carbonyl, ruthenium chloride, ruthenium nitrate, ruthenium bromide, ruthenium iodide, dichlorotricarbonyl ruthenium dimer. and ruthenium carbonyl.

The amount of these catalysts used is 100 to 200% of the raw material olefin.
The range is 1 mole of the catalyst per 00 moles, particularly preferably 1 mole of the catalyst per 500 to 10,000 moles of the raw material olefin. It is an olefinically unsaturated compound having a hydrogen skeleton, and particularly suitable is one in which the hydrocarbon group is linear and has 8 to 30 carbon atoms.

Such linear olefins include ethylene oligomers obtained by low polymerization of ethylene, such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. are mentioned as suitable olefins.

In addition, molecular internals obtained by catalytic dehydrogenation of linear paraffins obtained from kerosene and gas oil fractions, or isomerization and disproportionation reactions of α-olefins having terminal double bonds such as the above-mentioned ethylene oligomers. Suitable olefins include linear olefins having a double bond, such as n-undecene, n-dodecene, n-tridecene, n-tetradecene, and n-pentadecene.

(Solvent) The conditions to be satisfied for the polyhydric alcohol used as a solvent in the present invention are as follows. (2) The rhodium and ruthenium complexes used as catalysts should be easily dissolved and have low elution into the formed amine layer, and the following polyhydric alcohols meet these requirements. .

That is, dihydric alcohols having 2 to 3 carbon atoms, and 3 to 6 carbon atoms.
or a mixture of these and water.

The compatibility between the product, a long-chain alkyl tertiary amine containing a hydroxyalkyl group, and the polyhydric alcohol used as a solvent changes depending on the carbon chain length of the long-chain alkyl group and the hydroxyalkyl group. That is, in general, as the length of these carbon chains becomes shorter, the compatibility with dihydric alcohols such as ethylene glycol increases and phase separation becomes impossible, or even if it is possible, a long standing separation time is required or the formation of This will increase the amount of loss due to elution of the noble metal complex catalyst into the amine layer. In such a case, such inconvenience can be eliminated by changing the solvent to a more polar polyhydric alcohol, such as glycerin or diglycerin, or by adding a certain amount of a polar medium such as water.

Specific examples of polyhydric alcohols used include ethylene glycol, fluoropylene gellicol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, polyethylene glycol with an average molecular weight of 2000 or less, polypropylene glycol, or ethylene oxide and propylene oxide. Examples include block or random copolymers of .

The amount of solvent used is not particularly limited, but using a larger amount of solvent than necessary will reduce the yield per reactor capacity and reduce the capacity of the high-pressure reactor required to obtain a certain amount of the desired tertiary amine. Disadvantages arise, such as the need to increase capacity. On the other hand, if the amount of solvent used is less than necessary, it may become difficult to phase separate the produced amine layer and the solvent layer, or the elution of the catalyst into the produced amine layer may increase.

In the past, the amount of solvent normally used was calculated by preparing it as a raw material.
! It is 20 to 70 parts by weight, especially 30 to 50 parts by weight, based on 100 parts by weight of the total amount of rv fins and alkanolamines.
It is preferable to use parts by weight in order to effectively carry out the present invention.

(Raw material alkanolamines) The alkanolamines used as one of the raw materials are not particularly limited, and are rather selected depending on the desired tertiary amine.

Suitable alkanolamines include monoalkanolamines and dialkanolamines obtained by the reaction of alkylene oxide and nitrogen-containing compounds, such as monoethanolamine, jetanolamine, monoisopropanolamine, and diisopropanolamine. Amine, mono-2-butanolamine, di-2-butanolamine, N-methylethanolamine, N-ethylethanolamine, N
Examples include hydroxyl group-containing primary or secondary amines such as -propylethanolamine, N-butylethanolamine, N-methylimpropanolamine, N-ethylisopropanolamine, and N-glopylinprobanolamine.

The molar ratio of olefin to dialkanolamine is in the range of 1:1 to 1:3, particularly preferably in the range of 1:1 to 1.5. If the amount is smaller than the above range, the concentration of intermediate aldehydes in the reaction zone tends to increase, and the amount of heavy by-products tends to increase. On the other hand, if it exceeds the above range, there will be disadvantages due to an increase in unreacted alkanolamine, such as difficulty in phase separation between the produced amine layer and the solvent layer, or an increase in the amount of catalyst eluted into the produced amine layer. .

In the case of monoalkanolamines, the reaction is carried out at an olefin:monoalkanolamine molar ratio of 1:0.3 to 0.7, particularly preferably 1:0.4 to 0.6. Outside this range, the yield of the tertiary amine, which is the target substance, decreases significantly in any case.

(Reaction) This reaction is carried out in a temperature range of approximately 70 to 240°C, approximately 90 to 300°C.
Usually carried out under atmospheric pressure, sometimes 100-200°C,
Temperatures and pressures of 60 to 200 atmospheres are preferred.

The reaction pressure is essentially given by the partial pressure of hydrogen and carbon oxide used in the reaction, but in some cases nitrogen,
There is no problem even if inert gases such as helium and methane are mixed into the reaction.

Although the molar ratio of hydrogen to carbon oxide can vary over a wide range, it is often the case that the molar ratio of hydrogen to carbon oxide is 1.5.
~2.5: Good results have been obtained at 1.

Examples Example-1 RhCta・3H20: Polyethylene glycol with an average molecular weight of 600 containing 0.023 f: 32t, 1-hexadecene: 34 f, and jetanolamine: 2
32 was placed in a 200 d autoclave with electromagnetic induction stirring, and the reaction was carried out at 140° C. for 3 hours under a pressure of 1 aoKv/− of a mixed gas of hydrogen/carbon oxide molar ratio 1.7:1.0.

After the reaction was completed, the contents were cooled to near room temperature and taken out from the autoclave. When the contents were taken out of the autoclave, they were found to have phase-separated into a slightly pale yellow upper layer and a green lower layer. As a result of the analysis, the upper layer was a mixture mainly consisting of the product heptadecylbis(2-hydroxyethyl)amine and unreacted hexadecene, and the lower layer contained almost no amines or unreacted olefins. The main component was polyethylene glycol, which was used as a solvent.

Only 4 ppm of rhodium was detected in the produced amine layer, and most of it was contained in the lower solvent layer. Compositional analysis showed a hexadecene conversion rate of 91% and a yield of heptadecylbis(2-hydroxyethyl)amine of the desired substance of 72%.

Example-2 Solvent layer 28 containing most of the catalyst obtained in Example-1
The raw materials 1-hexadecene 342 and jetanolamine 23f were added to 2, and the reaction was carried out according to the method described in Example-1.

As in Example 1, the contents after the reaction were phase-separated into an almost colorless upper layer and a green lower layer.As a result of analyzing the composition of the upper layer, it was found that hexadecene conversion (tJss%, Heptadecyl bis(2-hydroxyethyl)amine yield 6
3%, and it was found that the catalyst-containing solvent layer obtained in Example-1 still had sufficient activity ◇ Example-3 Polyethylene glycol with an average molecular weight of 600 containing Rhcta 3HzO: 0.041 t: 322.1-dodecene: 34/and cyisogelobanolamine: 30f
Put 2 ooml into an autoclave with electromagnetic induction stirring,
The reaction was carried out at 150°C for 2.5 hours under a pressure of 150 Kf/- with a mixed gas of hydrogen/carbon oxide molar ratio 1.8:1.0. After the reaction, the contents were heated to 15-20°C. When cooled, the phase separates into a pale yellow upper layer and a green lower layer, and the upper layer is a mixture mainly composed of the product tridecylbis(2-hydroxypropyl)amine and unreacted dodecene, with a rhodium content of It was shown that most of the rhodium catalyst had migrated to the lower layer at 12 ppm.

As a result of analysis, the conversion rate of dodecene was 95%, and the yield of tridecylbis(2-hydroxypropyl)amine, the desired product, was 75%.

Example 4 Rhcta.3HzO: A reaction was carried out by the method described in Example 3 using diglycerin 301.1-dodecene: 321 and jetanolamine: 26f containing 0.031 S'.

After the reaction, when the contents were cooled, the contents phase-separated into an upper layer mainly containing the produced amine and a lower layer mainly containing diglycerin containing most of the catalyst. As a result of compositional analysis of the former, the conversion rate of dodecene was 96%, and the desired product tridecyl bis(2
-hydroxyethyl)amine yield was 75%.

Example-5 Rhcta・3Lo: 0.035 f, RuCta
・3 H20: Average molecular weight 80 including 0.0451
0 polyethylene glycol = 407.1-octene:
452, monoethanolamine 111 was charged into a 200 ml electromagnetic induction stirring autoclave, and 130 kg/m was mixed with a hydrogen/carbon oxide molar ratio of 1.7:1.0.
The reaction was carried out a/l over 4 hours.

After the reaction, the contents phase-separated into a pale yellow upper layer and a green lower layer, and the rhodium concentration in the upper layer was 2 ppm and the ruthenium concentration was 35 ppm, indicating that most of the catalyst was present in the lower layer. Ta.

As a result of compositional analysis of the upper layer, the octene conversion rate was 76%, and the desired dinonyl(2-hydroxyethyl)amine yield was 52%.
Met.

Example-6 RhCl3.3) (20: A mixture of polypropylene glycol with an average molecular weight of 800 containing 0.028 t: 30? and water: 52, 1-hexadecene: 349. jetanolamine: 24 t was mixed with 200 ml of electromagnetic induction. The mixture was charged into a stirring autoclave, and a reaction was carried out under the conditions described in Example-1.

After the reaction, the contents were phase-separated into a pale yellow upper layer and a green lower layer. Compositional analysis of the former revealed that the conversion of 1-hexadecene was 78% and the desired yield of heptadecylbis(2-hydroxyethyl)amine. It showed 58%.

Example-7 Rh(NOa)s・3H20: Ethylene glycol containing 0.085 t: 40f, 1-octadecene:
352, jetanolamine: 15? 200 ml was charged into an electromagnetic induction stirring autoclave, and a mixed gas of hydrogen and carbon oxide in a molar ratio of 1.8:1.0 was mixed with 1zoKii/
The reaction was carried out at 150° C. for 4 hours under a pressure of d.

When the contents were removed from the autoclave after the reaction was completed, they were found to have phase separated into an almost colorless upper layer containing the produced amine and unreacted olefin as main components, and a lower layer containing most of the catalyst.

Although 12 ppm of rhodium was detected in the produced amine layer, it was shown that most of it was present in the lower layer mainly composed of ethylene glycol.

Analysis of the composition of the produced amine layer showed that the conversion rate of 1-octadecene was 89% and the yield of the desired nonadecylbis(2-hydroxyethyl)amine was 61%.

In the lower layer 292 with most of the catalyst, 1-octadecene:
When 20t and jetanolamine:9f were added and the reaction was carried out again under the same conditions, the conversion rate of 1-octadecene was 82%,
The desired amine yield was 46%, indicating that it still had sufficient activity as a catalyst. 1-
Tetradecene: 36 F, jetanolamine: 20
1 was placed in a 200 rnl electromagnetic induction stirring autoclave, pressurized to 140-/- with a mixed gas of hydrogen/carbon oxide in a molar ratio of 1.9:1.0, and the reaction was carried out at 150° C. over 6 hours.

After the reaction, the contents phase-separate into a pale yellow upper layer and a reddish brown lower layer, and the former is a mixture mainly composed of pentadecylbis(2-hydroxyethyl)amine, the desired product, and unreacted tetradecene. The latter was a mixture whose main component was polyethylene glycol, which was used as a solvent. As a result of the former analysis, the conversion rate of tetradecene was 53%, and the yield based on the desired pentadecylbis(2-hydroxyethyl)amine was 44%.

Ruthenium contained in the generated amine layer was 18 ppm.
It was shown that the majority was present in the solvent polyethylene glycol layer.

Solvent layer thus obtained: 321 and 1-tetradecene:
When 28 t, jetanolamine: 161 was added and the reaction was carried out under the same conditions, 38% of the tetradecene was converted and the desired amine was formed in 33% yield, indicating that the catalyst was still active. Patent applicant Mitsubishi Yuka Co., Ltd. Agent: Patent attorney Hidetoshi Furukawa Agent: Masahisa Hase

Claims (3)

[Claims] (1) Long chain olefin with 8 to 30 carbon atoms, -carbon oxide,
Tertiary amines having a hydroxyalkyl group in the molecule are produced by reacting hydrogen and monoalkanolamines or dialkanolamines in the presence of a catalyst whose main components are compounds containing rhodium and ruthenium. In the method of manufacturing, the solvent is a carbon number of 2
- Polyhydric alcohol selected from the group consisting of dihydric alcohols having 3 to 6 carbon atoms, trihydric alcohols having 3 to 6 carbon atoms, and intermolecular dehydration condensates of dihydric or trihydric alcohols having 2 to 3 carbon atoms @ or a mixture of tertiary amines and water, and the reaction product is phase-separated into an amine layer containing the produced secondary amine and a solvent layer containing the catalyst. Manufacturing dice. (2) A method according to claim 1, wherein the solvent layer containing the catalyst is recycled to the reaction zone. (3) The intermolecular dehydration condensate of dihydric and trihydric alcohols having 2 to 3 carbon atoms is polyethylene glycol, polypropylene glycol, or a block or random copolymer of ethylene oxide and propylene oxide with an average molecular weight of 2000 or less. , Katsutake diglycerin.