JPS60258145A - Production of tertiary amine - Google Patents

Abstract

PURPOSE:To prevent the formation of by-products, and to improve the yield and purity of the titled compound, by reacting an olefin with carbon monoxide, hydrogen and a primary amine in the presence of a catalyst obtained by mixing a rhodium compound and a ruthenium compound at a specific ratio. CONSTITUTION:The objective compound can be produced by reacting an olefin with carbon monoxide, hydrogen and a primary amine (preferably monomethylamine or monoethylamine) in an inert solvent such as ethylene glycol, preferably at 100-200 deg.C and 60-200atm in the presence of a catalyst obtained by mixing 1mol of a rhodium compound with 0.2-5.0mol, preferably 0.4-3.0mol of a ruthenium compound. The mount of the primary amine is 0.4-1.0mol per 1mol of the olefin. The molar ratios of the rhodium compound of the catalyst to the olefin and the ruthenium compound are preferably 1:(2,000-2,500) and 1:(0.4-3.0), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing long-chain dialkyl tertiary amines in one step by reacting olefins, carbon oxides, hydrogen and primary amines in the presence of a catalyst. be.

BACKGROUND OF THE INVENTION Long-chain dialkyl-type tertiary amines having two long-chain alkyl groups in the molecule, such as di-octadecyl-methylamine, are quaternized with methyl chloride, etc.
It is a useful substance that is widely used in the form of a quaternary ammonium salt as the main component of fabric softeners and hair rinses. At present, most of these amines having a long-chain alkyl group are manufactured through complicated processes using natural oils and fats such as coconut oil and beef tallow as raw materials.

Synthesizing a tertiary amine having a long-chain alkyl group in the molecule via an aldehyde by reacting an olefin, carbon oxide, hydrogen, and a lower amine in the presence of a catalyst.
j is publicly known, and numerous documents and patents have been disclosed.

For example, a method for synthesizing a tertiary amine from an olefin, hydrogen, carbon oxide, and a secondary amine in the presence of a catalyst consisting of an organic tertiary phosphine and cobalt carbonyl (
(Japanese Patent Publication No. 41-9527), with an olefin or aldehyde using a rhodium or ruthenium compound catalyst,
Method for synthesizing higher tertiary amines from hydrogen, carbon oxide and lower amines (Japanese Patent Publication No. 52-38527, JP-A-55-102520, JP-A-56-140952, U.S. Pat. No. 4,250'115) etc.), platinum compounds, Group I VB metal halides such as tin chloride, and Group VB metal halides such as tin chloride.
A method of synthesizing an aldehyde by hydroformylating an olefin using a catalyst consisting of a group element-containing ligand compound, and then synthesizing the corresponding amine by amino hydrogenation in the presence of a hydrogenation catalyst -116307,
U.S. Pat. No. 4,299,985), olefins, -
Method for synthesizing higher alkyl amines from carbon oxide, water and lower amines (U.S. Pat. Nos. 6,947,458 and 4)
No. 317932, He1vetica Chi-mic
a Acta, Vol. 54, pp. 1440-1445, 19
In 1971, Journal of Organic (!
hemist-r V + Volume 47, 445-447
Page, 1982).

These methods of synthesizing amines from olefins produce long-chain alkyl tertiary amines in just one step, without going through many steps, compared to existing production methods that use natural oils and fats as raw materials. It has the advantages of being able to freely obtain amines having the carbon number of rice ears by selecting the raw material olefin.

Problems with the prior art Most of these prior technologies are based on olefins, -
By the combination of carbon oxide, hydrogen and secondary amine,
O 0 reason 0th - G ma・long chain 7 /l; # /L-5th
During the synthesis of class 7 z:', i), heavy substances are produced as a by-product due to the condensation reaction of the long-chain aldehyde as a reaction intermediate, but in the case of the synthesis of long-chain monoalkyl tertiary amines, such The amount of heavy by-products produced is relatively small, and even if they are produced, they can be relatively easily separated from the target long-chain monoalkyl tertiary amine by distillation or the like.

On the other hand, for the synthesis of long-chain dialkyl tertiary amines,
The amount of heavy by-products increases significantly, and in addition, many of these heavy substances have boiling points close to the long-chain dialkyl tertiary amine, which is the target product, and are difficult to separate. It is virtually impossible to obtain chain dialkyl tertiary amines.

The second reason is that a considerable portion of the raw material olefin remains in the production of the intermediate long-chain monoalkyl secondary amine, and does not reach the reaction up to the long-chain dialkyl tertiary amine. The selectivity is small. In this case, it is of course possible to recirculate the intermediate long-chain monoalkyl secondary amine to the reaction zone to finally convert it into the desired long-chain dialkyl tertiary amine; Reactor space-time yields are reduced and extensive recirculation causes increased utility costs.

Summary of the Invention In order to solve the above problems, the present inventors investigated the synthesis of IR dialkyl tertiary amines from olefins, -carbon oxide, hydrogen, and primary amines, and found that rhodium compounds, ruthenium compounds, and By using a catalyst mixed in a specific range of ratios, the production of heavy products due to the condensation reaction of the intermediate product aldehyde is substantially suppressed, and a highly pure long-chain dialkyl tertiary amine can be obtained. I found out what I got. The selection of long-chain dialkyl tertiary amines also increases the reaction rate to dialkyl amines by increasing the relative concentration of olefins in the reaction mixture, resulting in the suppression of heavy product formation.

The rate can be greatly improved.

That is, in the present invention, by reacting an olefin, carbon oxide, hydrogen, and a primary amine, the olefin has 1 carbon atom.
In a method for producing a long-chain dialkyl amine having two long-chain alkyl groups in the molecule, 0.2 to 5 ruthenium compounds are used per 1 mole of rhodium compound as a catalyst.
．． This is a method for producing a tertiary amine characterized by using a mixed catalyst in a proportion of 0 mole.

Rhodium compounds and ruthenium compounds used as catalysts in the present invention include halides such as rhodium chloride, ruthenium chloride, rhodium bromide, and ruthenium bromide;
Metal carbonyls such as rhodium carbonyl and ruthenium carbonyl, nitrates such as rhodium nitrate and ruthenium nitrate,
These include sulfates such as rhodium sulfate and ruthenium sulfate, or chelates of acetylacetonate such as tris(acetylacetonato)rhodium and tris(acetylacetonato)ruthenium. The amount of these catalysts used in the reaction zone is 1 mole of rhodium compound per 300 to 50,000 moles of olefin, preferably olefin:
, the ratio of 1 mol of the rhodium compound to 2,000 to 25,000 mol. On the other hand, the ruthenium compound is 0.2 to 5.0 mol, preferably 0.2 to 5.0 mol, preferably 0.2 to 5.0 mol, per 1 mol of the rhodium compound.
It ranges from 4 to 30 moles. When the ratio of ruthenium compounds is smaller than the above, an increase in heavy by-products is usually observed, while when the ratio of ruthenium compounds is increased, the catalyst activity not only decreases and the reaction rate decreases, but also the intermediate The amount of olefin retained on the chain monoalkyl secondary amine increases, resulting in a lower simple yield of the desired product and an increased amount of recycle.

The olefin used as a reaction raw material has 6 carbon atoms.
~30, having an olefinic double bond, and those having a linear hydrocarbon structure are particularly preferred. Examples of such raw material olefins include ethylene oligomers obtained by low polymerization of ethylene, or those obtained by thermal decomposition of wax or dehydrogenation of n-paraffin. An olefin having a linear hydrocarbon structure with a double bond at the molecular end is particularly preferred as the raw material olefin of the present invention.

The other raw material, the primary amine, is selected depending on the desired long-chain dialkyl tertiary amine, and is not particularly limited.
When obtaining long-chain dialkyl short-chain mo/alkyl tertiary amines used in textile softeners, hair conditioners, etc., primary amines with carbon numbers such as monomethylamine, monoethylamine, and monopropylamine are used. Lower amines having 1 to 4 alkyl groups are preferred, and monomethylamine and monoethylamine are particularly preferred as the secondary amines used in the present invention.

In the reaction of the present invention, the primary amine is used in an amount of 0.4 to 1.0 mol per mol of olefin. When the amount of primary amine used is high, the amount of long-chain dialkyl tertiary amine produced is small, and the amount of recycled long-chain monofulkyl secondary amine is increased; Condensation reactions between higher aldehydes, which are reaction intermediates, are likely to occur, and the amount of heavy products produced may increase. In addition, the primary amine in the reaction zone is also used for reaction with recycled long-chain monoalkyl secondary amines, so this must also be taken into account, and particularly preferred use of primary amines. The amount is 0.4 to 0.7 mol per mol of raw material olefin.

The reaction is usually carried out in the presence of a solvent inert to amine synthesis reactions. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, hexane,
Various types of aliphatic hydrocarbons such as heptane, monohydric alcohols such as methanol, ethanol, propyl alcohol, butanol, dihydric and polyhydric alcohols such as ethylene glycol, propylene dalycol, polyethylene glycol, polypropylene gelylcol, etc. However, among these solvent groups, especially dihydric and polyhydric alcohols such as ethylene glycol and polyethylene glycol, recovery of the catalyst from the product amine using the phase separation phenomenon previously proposed by the present inventors is possible. The method (JP-A-58-105945) can be applied and the invention can be carried out in a particularly advantageous manner.

The reaction conditions are a temperature of 70-240°C, a temperature of 30-300°C.
Atmospheric pressure, preferably 100-2oO°C, 6
C1 to 200 atm. - The H2/CO molar ratio of the mixed gas of carbon oxide and hydrogen can be varied over a wide range, but in most cases a value of 1.0 to JO gives good results in both olefin conversion and heavy amine yield. obtain.

The reaction solution usually consists of unreacted olefin, long-chain monoalkyl secondary amine as an intermediate, and long-chain dialkyl tertiary amine as the target substance. It can be recycled into the reaction zone depending on the requirements. In particular, nearly all of the recycled long-chain monoalkyl secondary amine can be converted into the long-chain dialkyl tertiary amine, which is the target substance, and as a result, the selectivity to the target substance is significantly improved. becomes.

Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited thereto unless it goes beyond the gist. In addition, in the following examples and comparative examples, the conversion rate and yield are all mol%, and the olefin conversion rate does not include conversion to internal olefin.

Comparative Example 1 40 g of methanol containing only 7 mg of Rh CZ 3.3 H2039 and 5 og (o, +5 mol) of 1-octene were charged into a 200 ml autoclave equipped with an electromagnetic induction stirrer, and after purging the inside of the autoclave with N2 gas, 9-tylamine was added. 7 g (o, 23 mol) was injected.

Next, while stirring, add synthesis gas (H/CO molar ratio 1.8) to 80 Yu/c++! The temperature was raised to 150°C. Is the autoclave pressure 95 kl? /c+J a
However, after adding more syngas, the total amount was 110kl? /c
++! (), the reaction was continued at 150°C for 3 hours.

%, but hardly any di-nonylmethylamine, which is the desired tertiary amine, was obtained, and a large amount of heavy substances caused by condensation of nonanal, which is an intermediate of this reaction, was detected.

Comparative Example 2 40 g of polyethylene glycol with an average molecular weight of -600 containing only R'u C13.3 N2039.9 mg,
Comparative Example 1 using 50 g (0.45 mol) of l-octene
It reacted in the same way as in the case of The analysis result of the product is 11i
.

The -octene conversion rate was 53.1%, the nonylmethylamine yield was 21.5%, and the yield of the desired tertiary amine was 18.5%.

Unlike the case of Comparative Example 1, almost no heavy by-products due to the condensation of nonanal were observed, but the yield of the desired amine was low and the results were not satisfactory.

Example 1 Rh C133N2018, 9 mg and Ru 013
3 N2019. Omg of 35 g of ethylene glycol, 50 g of 1-octene (o, 45 mol),
The mixture was placed in a 200 ml autoclave with electromagnetic induction stirring, and after purging the system with N2 gas, 7.5 g (0.24 mol) of monomethylamine was injected as a primary amine.

Pressurize the system with synthesis gas (H2/CO molar ratio 169),
The reaction was continued with stirring at 145°C and 100 klJ/ci G for 5 hours. After the reaction was completed, the upper and lower layers of the contents separated into two layers were analyzed and the results showed that the conversion of 1-octene was 81%, the yield of nonylmethylamine was 1o, 5%, and the desired tertiary amine, di-nonyl. Methylamine yield is 6
It was 9.9%.

The di/nylmethylamine fraction isolated by distillation has an amine value of 3.51 mmol/g (theoretical value 3j 3
mmol/g), and the infrared spectrum also ranges from 1600 to
ν (c = c) + ν (0
=N), and almost no peaks due to condensation products of aldehydes were observed, indicating that isolation can be achieved with high purity.

Example 2 42 g of bo-12 ethylene glycol with an average molecular weight of 400 containing 1 g of Rh (No. Using 5.5 g (0.18 mol) of monomethylamine as a class amine,
When the reaction was carried out according to the method described in Example 1,
The conversion rate of 1-dodecene was 74.7%, the yield of tridecylmethylamine was 6.0%, and the yield of di-tridecylmethylamine, the desired tertiary amine, was 67.6%.

The amine value of the portion obtained by distilling off unreacted olefin and tridecylmethylamine was 2.42 mmol 7g, and the theoretical value of di-tridecylmethylamine was 2.53 m
The value was very close to mol/g.

Example 6 Rh'013-3 N203, 8 mg and Ru cz
All examples except that 40 g of ethylene glycol containing 3.012.5 mg of 3.H, 50 g (0.45 mol) of 'l-oc,ten, and 7.3 & (24 mol) of monomethylamine were used. When the reaction was carried out according to 1, the conversion of 1-octene was 69.3%, the yield of nonylmethylamine was 19.3%, and the yield of di-nonylmethylamine, the desired tertiary amine, was 49.1%. .

Example 4 Ru C13-3N2032.5 mg and Ru 0
13-3 Average molecular weight 600 containing 1.8 mg of N202
30g of polyethylene glycol, 7g of 1-hexadecene
0 g (0,31 mol) and monomethylamine 5.8
The reaction was carried out according to the method described in Example 1 using g (0.19 mol).

The analysis result of the product shows that the conversion rate of 1-hexadecene is 78.5.
%, the yield of heptadecylmethylamine was 6.9%, and the yield of di-heptadecylmethylamine, the desired tertiary amine, was 69.3%.

The amine value of the residue obtained by distilling off hexadecene and heptadecylmethylamine, a long-chain monoalkyl secondary amine, was 1.79 mmol/g, which was close to the theoretical value (1.97rnm01/g). The values were close. Also,
In the infrared spectrum, almost no peak attributable to heavy substances caused by self-condensation of aldehydes near 1600 to 1800□-1 was detected.

Comparative Example 6 The reaction was carried out according to the method described in Example 1 except that the amount of monomethylamine used was increased to 32 g (1.03 mol) and the reaction was carried out at 155°C and 110 kl/CJG for 3 hours. carried out.

The analysis result of the reaction product shows that the 1-octene conversion rate is 89.
However, the yield of di-7ylmethylamine, which is the desired tertiary amine, decreased significantly to 15.2%, and nonylmethylamine was produced as a by-product by 47.2%.
In addition, a considerable amount of N-/N-methylformamide, which was hardly produced in the previous examples, was also obtained.

)4 Example 5 Tris(acetylacetonato)rhodium 14.0 mg
and tris(acetylacetonato)ruthenium19.
41 g of ethylene glycol and 55 g (0.39 mol) of l-decene containing Omg were charged into a 200 ml autoclave with electromagnetic induction stirring, and after purging the reaction system with N2 gas, 1 g of monoethylamine was added as a primary amine.
' (o. 224 mol) and synthesized gas (H2/CO
Molar ratio='J:l) was press-fitted, 155°C, 20kg/
cn! The reaction was continued for 4 hours at G. As a result, the conversion rate of l-decene was 80.1%, and the yield of undecylmethylamine was 1%.
The desired tertiary amine, diundecylmethylamine, had a yield of 65.3%.

After distilling off unreacted decene and undecylmethylamine,
The amine value of the obtained dipentacylmethylamine fraction is J
It is 93 mmol / g, which is the theoretical value (2゜95 mm
ol/g).

The infrared spectrum of the sample was also 1600-180.
The peak attributed to the product resulting from the condensation reaction of decanal, which should be seen in 0G-1, was not observed.

Example 6 Rh CjZ 3.3 H2015, 4mg and R
u 013・, N2018. Average molecular weight including Omg 6
00 polyethylene glycol, 25 g of l-tetradecene, and 30 g of pentadecylmethylamine corresponding to the intermediate product of this reaction instead of the lower primary amine were charged into a 200 m1 autoclave equipped with electromagnetic induction stirring, and the inside of the reactor was heated with N2 gas. Replaced with. Next, synthesis gas (H2
/CO ratio 1.8) was injected and heated to 150'C, 90K.
g/c++! The reaction was continued for 4 hours under the conditions of G.

As a result of analyzing the contents after the reaction, the conversion rate of 1-tetradecene was 93.5%, and the yield of dipentadecylmethylamine, the desired tertiary amine, was 90.3%. Almost the entire amount of a certain pentadecylmethylamine was converted to the target substance.

Applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent attorney Katsura Atsuta

Claims (3)

[Claims] (1) A method for producing a long-chain dialkyl-type amine having two long-chain alkyl groups in the molecule with one more carbon number than the olefin by reacting an olefin, carbon oxide, hydrogen, and a primary amine. A method for producing a tertiary amine, characterized in that a mixed catalyst containing a ruthenium compound in a ratio of J2 to 5.0 moles per 1 mole of a rhodium compound is used as a catalyst. (2) 0.0% primary amine per mole of olefin.
The method according to claim 1, wherein 4 to 1.0 mol is used. (3) The method according to claim (1) or (2), wherein the long-chain monoalkyl secondary amine is separated from the reaction product and recycled to the reaction zone.