JPS6172734A - Preparation of tertiary amine - Google Patents

Abstract

PURPOSE:To obtain a tertiary amine of high purity and quality in high yield, by reductively alkylating a primary or secondary amine with hydrogen and a carbonyl compd. in the presence of a hydrogenation catalyst, i.e. Co, Ni, Pd etc. supported on carbon. CONSTITUTION:An amine expressed by formula I (R<1> is 8-24C alkyl or alkenyl, R<2> and R<3> are H, 8-24C alkyl or alkenyl, m is an integer 0-5, n is 2 or 3, in case of m=0 at least one of R<2> and R<3> is H) is alkylated with hydrogen and a carbonyl compd. expressed by formula ( (R<4> and R<5> are H, 1-24C aliphat ic, aromatic hydrocarbon group-substituted aliphatic or aromatic hydrocarbon group) in the presence of a hydrogenation catalyst, at 80-250 deg.C under <=2kg/cm<2> G hydrogen pressure to obtain a tertiary amine. The catalyst contains Co, Ni, Ru, Rh, Pd or Pt supported on powdery or granular carbon 0.1-10wt%, and it is used in amt. of 5-5,000ppm catalyst metal concentration based on the amine expressed by formula I. USE:Corrosion inhibitor and various intermediates.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a method for producing tertiary amines, and more specifically, the present invention relates to a method for producing tertiary amines. The present invention relates to a method for producing high-yield, high-purity, and high-quality tertiary amines by reductive alkylation.

(b) Conventional technology Aliphatic tertiary amines are used as corrosion inhibitors and fuel oil additives.
It is also useful as an intermediate raw material for quaternary ammonium salts and amphoteric surfactants for bactericides, fungicides, disinfectants, leveling agents, antistatic agents, etc. As the use of tertiary amines has expanded in recent years, the quality required for tertiary amines has been increasing year by year, such as high quality as a reaction intermediate raw material, for example, low impurities that cause coloration and odor in the final product.

As a method of methylating primary or secondary amines (Al
Organic methylation using formic acid and formaldehyde
Vol. 723, page 723) and Organic Reactions Vol. Reaction of higher alkyl halide and methylamine (US Pat. No. 3,379,764), (D+higher,...) Reductive amination reaction of alcohol and methylamine (JP-A No. 52-19604, JP-B No. 57-849,
Special Publication No. 57-55704) is known.

One of the products produced in the present invention is higher alkyl dimethylamines, which are mainly industrialized by the method (C).This method is a completely different reaction method from the present invention. Method (D) is a reaction between a higher aldehyde produced by dehydrogenation of a higher alcohol and methylamine.
Although the reaction is similar to the present invention, the reaction temperature is high and there are many by-products, so the quality of the tertiary amine obtained is extremely poor.

Method (A) does not require the use of a large excess of formic acid (and a sufficient reaction rate cannot be obtained, so formic acid is expensive, so it is not practical except in cases where special tertiary amines are being produced). Not completely transformed.

Method (B) is a reaction method similar to that of the present invention, but it has conventionally been considered industrially disadvantageous because the reaction yield and product quality are considerably inferior to method (C). However, this method has a wide range of applications, and if the yield and quality of the product are improved, it would be cost-effective, so improvements in this method have been desired. For example, Organic Reactions No. 4
Vol. 244, p. 248, when a primary or tertiary amine is reacted with hydrogen and formaldehyde using a Raney nickel or platinum catalyst, the yield is 9.
It is 0% or less. Japanese Patent Publication No. 39-17905 describes a method for improving the yield by using a short-chain aliphatic hydroquine-basic acid or a short-chain aliphatic hydroquine-basic acid as an additional catalyst for the reaction. Even when a primary amine having an alkyl group having 8 or more carbon atoms is reacted under a Raney nickel catalyst, the tertiary amine in the product is about 85%, resulting in a low yield.

(...) Means for Solving the Problems The present inventors have conducted detailed studies on alkylation reactions using hydrogen of primary or tertiary amines and carbonyl compounds, and as a result, the following facts have become clear: Ta.

That is, 1-hydroxyalkyl imine which is a reaction intermediate between primary or tertiary amine and carbonyl compound.
(-CH=N-) is a highly reactive compound, but hydrogenation reactions of l-hydroxyalkylamines and imines are difficult to occur under conditions where the reducing action of the reaction system is insufficient, and it is often present. It reacts with the first or minion amine to produce unstable polymers such as polyalkylene polyamines, which adhere to the hydrogenation catalyst and also hinder diffusion to the hydrogenation catalyst surface. Furthermore, Kl-hydroxyfurkylamine and imine can be used as the first or second 7-mer/, as well as the produced polyalkylene/
It is also possible to react with active methylene groups of polyamines. It is also possible that the carbonyl compound reacts with the polyalkyl//polymethyleno group. Carbonyl compounds also react with polyalkylenopolyamines and 1-hydroxyfurkylamine to produce complex by-products, which not only reduce the yield of the desired tertiary amine, but also cause odor generation and It has been found that this can cause coloring and discoloration over time.

Based on these findings, the present inventors have simultaneously satisfied three elements: good dispersion in the amine layer, which is the reaction phase, no deterioration of the dispersion due to the influence of moisture, and high hydrogenation ability. As a result of our earnest efforts to develop a hydrogenation catalyst, we have arrived at the present invention.

The present inventors have filed a patent application for the alkylation reaction using primary or secondary amino acids and formaldehyde (Japanese Patent Application No. 1982-218689), but a further development of the invention is This is the present invention.

That is, the present invention is based on the general formula (1) (wherein R1 is a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, and R2 and R3 are hydrogen atoms or 8 to 24 carbon atoms. a straight-chain or branched alkyl group or alkenyl group, m is 0 or an integer of 1 to 5, n is 2 or 3, and when m = O, at least one of R2 and R3 is a hydrogen atom. % formula (2) (where Kei and R5 are hydrogen atoms or saturated or unsaturated carbon atoms with 1 to 24 carbon atoms, linear or branched). A chain (・ is a cyclic aliphatic hydrocarbon group, an aromatic hydrocarbon group-substituted aliphatic hydrocarbon group, or an aromatic hydrocarbon group that may have a substituent, and R4 and Rs are hydrogen atoms at the same time) There isn't.

) When performing alkylation using a carbonyl compound represented by
Under conditions of i (gauge pressure) or higher, it is in powder form (・ is Co for granular carbon.

A hydrogenation catalyst on which Ni, Ru, Rh+Pd or pt is supported in an amount of 01 to 10% by weight is 5 to 5000 pp as a catalyst metal 6 degree relative to the amine represented by the general formula +11.
This is a method for producing a tertiary amine, which is characterized in that the reaction is carried out while adding m and a carbonyl compound continuously by IC.

The amines of formula (1) include octylamino, dodecylamine, tetradenylamine/, hexanalamine, octadecylamine, dophnorami/, oleylamino,
In addition to linolamine/, erucylamine, etc., mixtures such as coconut oil alkylamino, beef tallow furkylamine, hydrogenated beef tallow alkylamine, rapeseed oil alkylamino, coconut oil alkylamine, di-beef tallow alkylamine, hydrogenated beef tallow alkylamine, aminoethyl coconut oil alkylamine, aminoethyl tallow furkylamine, aminopropyl coconut oil furkylamine, aminopropyl tallow alkylamine,
N,N'-coconut oil furkylethylenediamine, N-coconut oil alkyl-N1-beef tallow alkylethylenediamine,
N-coco alkyl dipropylene triamine 7, N-coco alkyl dipropylene triamine, N-coco alkyl dipropylene triamine, N-coco alkyl dipropylene triamine, N-coco alkyl dipropylene triamine, N- Beef tallow alkyl tripropylenetetramine, N-
Coconut oil alkyltetrapropylene pentaS, N-beef tallow furkyltetrabrobylenepe/tamin, N-coconut oil alkylpentapropylene hexamine/, N'F fat 7
Roux? Examples include rube/tapropylene hexamine, which can be used alone or as a mixture of 21 I'ft or more.

The carbonyl compound of formula (2) is saturated or unsaturated, linear or branched, such as acetaldehyde, propionaldehyde, 1-hexanal, 2-ethylhexanal, l-hexenal, 2-7 nenal, cyclohexanal, etc. Chain or cyclic aliphatic aldehydes, aromatic group-substituted aliphatic ap-chlorobenozaldehydes such as α-tolualdehyde and phenylpropionaldehyde, aromatic aldehydes such as l-naphthylaldehyde, acetone, diethyl ketone, There are aliphatic ketones such as methyl octyl ketone, alicyclic ketones such as cyclobropanone and cyclohexano, and aromatic ketones such as acetopheno and benozopheno. If necessary, the carbonyl compound can be melted by heating and dissolved in water or an inert solvent.

The amount of carbonyl compound used is 7 of the primary or secondary amino acid.
The mole amount is 1 to 1.5 times, preferably 1 to 1.05 times, based on the active hydrogen of the mino group or imino group. If the amount is less than 1 mole, the primary or tertiary amine remains, and 1.5
Exceeding twice the molar amount is not only disadvantageous in terms of cost, but also requires a long reaction time to reduce and remove the remaining formaldehyde.

The hydrogenation catalyst used in the present invention is prepared by supporting powdered or granular carbon with 0.1 to 10% by weight of any of Ni, Co, Ru, Rh, Pd, and Pt.

Catalysis Vol. 20, p. 112 (1969)
It can be prepared by the method described in . The amount of hydrogenation catalyst used is 5 to 5 as the catalyst metal concentration relative to 7i7 of the raw material.
000 ppm. This hydrogenation catalyst is ideally dispersed in the amine 7 layer even in a system where water 1 and amine layers coexist, and is hardly dispersed in the water layer.

If alumina, silica, diatomaceous earth, etc. are used as a carrier for the hydrogenation catalyst, the dispersion state in the reaction system will be poor (unfavorable).
Single metals and metal oxides such as platinum oxide, platinum black, and radium black have extremely high activity (and are known as hydrogenation catalysts, but they do not give good results in this reaction.

In the method of the present invention, a pressure-resistant reactor is used, and the hydrogen pressure (gauge pressure) is 2Kz/c! Above, reaction temperature 80-250C1
Preferably, the reaction is carried out at a hydrogen pressure of 5 to 50 K9/c, r1 and a reaction temperature of 100 to 250C. Hydrogen pressure is 2 Ky
/ cd (reaction @ If the degree is less than 80C, the hydrogenation reaction will not proceed sufficiently, and by-products such as methylolamine derivatives, their polymers, and Ntuf base derivatives will increase, and the reaction temperature will exceed 250C. If this is exceeded, the amount of by-products such as poly long-chain fulkylamines and hydrocarbons derived from the dehydrogenation reaction of 7mino increases.

The method of adding the carbonyl compound is not particularly limited as long as it is added continuously, but usually a pressure pump is used to add the carbonyl compound little by little into the reactor.

If a large amount of water from the aqueous solution of the carbonyl compound or water generated from the reactor accumulates during the reaction, the reaction may be performed while releasing hydrogen or @ring to remove water from the system.

An example of a specific manufacturing method of the present invention will be shown below.

The raw material amine and hydrogenation catalyst are charged into a pressure-resistant reactor equipped with a stirrer, a pressure injection pump, and a gas circulation device with a cooling fundenosa if necessary, and the temperature is raised to the desired reaction temperature while stirring, and the atmosphere in the system is changed to hydrogen. After replacing the gas with hydrogen, add hydrogen to the specified pressure.

Next, the injection of the carbonyl compound solution is started, and the reaction is carried out under a predetermined hydrogen pressure. When circulating hydrogen, condensed water is removed from the system using a cooling co/de/cooler. After the injection of the carbonyl compound solution is completed, the reaction is aged for a certain period of time while keeping the reaction temperature and hydrogen pressure constant.

(Effects of the Invention) When amines are alkylated by the method of the present invention, the desired reaction proceeds almost quantitatively, and almost no by-products that cause quality deterioration are produced. The amine is almost colorless and has no off-odor.The alkylation rate of the amine reaches over 97% regardless of the type of raw material, the primary or secondary amine.Also, the distillation yield is over 95%. and the purity of the tertiary amine reaches more than 98%.

The heat resistance and light resistance of the tertiary amine obtained by the method of the present invention are extremely excellent, and even after a heat resistance test of storage at 50C and a sunlight exposure test for 6 months, there was no change in hue, odor, temperature, etc. Not recognized.

Furthermore, the amine oxides and quaternary ammonium salts produced using the obtained tertiary amines are nearly colorless and odorless, and there are no problems in terms of appearance or quality.

(e) Examples The present invention will be explained below with reference to Examples and Comparative Examples.

Examples 1 to 8 Autoclave K for 2 units equipped with a stirrer and a pressure pump
, take the first or second aluminum/8ooy raw material and hydrogenation catalyst, raise the temperature to a specified temperature while stirring at 9° Orpm with a flat blade turbine, replace the atmosphere in the system with hydrogen, and then heat to the specified temperature. Hydrogen was added to the pressure.

Next, a solution of the carbonyl compound was added at a predetermined time using a pressure injection pump, and the reaction was carried out at a constant temperature and pressure, and after the addition was completed, the reaction was aged for 30 minutes. After the reaction is completed, the hydrogenation catalyst is separated from each other, and the aqueous layer is separated.
! ! In addition, some tertiary amines were purified by vacuum distillation.

Table 1 shows the reaction conditions and analytical values of the obtained products.

As is clear from Table 1, the hue of the obtained crude tertiary amine was APHA 30 or less, and was almost colorless.

Further, the distilled purified tertiary amine was completely colorless and transparent. Furthermore, neither the purified Kōsan amine nor the crude Kōsan amine had any odor other than the amine odor. The purity of the crude tertiary amines was all 98 or higher, and the purity was 4! ! ! The purity of all tertiary amines was 99% or higher. In addition, Seisei Kosan Amine was stored at 50C for 6 months and exposed to sunlight on 6 occasions, but there was no change in appearance or odor.

Examples 9 to 17 In a 50° capacity autoclave equipped with a hydrogen circulation system with a stirrer, a cooling condenser, and a pressure pump, 20° to 20° raw material amine and a hydrogenation catalyst were heated to a predetermined temperature while stirring.
The temperature was raised to 100°C, the atmosphere in the system was filled with hydrogen, and then hydrogen was added to a predetermined pressure. Next, the reaction was carried out while adding formaldehyde aqueous solution at a predetermined time using a pressure injection pump, and the reaction was aged for 30 minutes after the addition was completed. During the reaction, the reaction was continued at a constant temperature and pressure while circulating hydrogen and removing condensed water from the system.

After the reaction was completed, the hydrogenation catalyst was separated from each other to obtain a crude tertiary amide. In addition, some tertiary amino acids were purified by vacuum distillation.

Table 2 shows the reaction conditions and analytical values of the obtained products.

From Table 2, the hue of the obtained tita tertiary amine is A
It is almost colorless with a PHA of 30 or less, and is
The same was true. Further, no odor other than the amine odor was observed in either the crude tertiary amine or the purified tertiary amine. Also,
The purity of both the blocked tertiary amine and purified tertiary amine is 98.
% or more.

Furthermore, the purified tertiary amino acid was stored at 50C for 6 months and subjected to a 7% sunlight test (6) outdoors, but there was no change in appearance or odor.

Example 18 500y of dodecylamine was placed in an Erlenmeyer flask with a volume of 2, and heated to 70K without stirring. To this, 198 ml of acetaldehyde aqueous solution with a concentration of 60% (0.5 times the mole of active hydrogen of dodecylamine) was added dropwise over 30 minutes.
After the dropwise addition was completed, the mixture was stirred at 90C for 1 hour, and then the aqueous layer was separated.

Dodecylamine-acetaldehyde condensate obtained in the autoclave used in Example 1 and 5% as a hydrogenation catalyst
Pd-CO, 57 (0.1 weight 1% based on raw material amine)
added. After heating to 160C while stirring at 900 rpm using a flat-blade turbine and purging the system with hydrogen, the gauge pressure was 10KP/f:〃! Hydrogen was added until Hydrogen absorption started immediately, but the hydrogen pressure was always kept the same. After 2 hours have passed and hydrogen absorption has stopped, an acetaldehyde aqueous solution with a concentration of 60% 19
8y (05 mole times the active hydrogen of dodecylamine)
was injected for 2 hours, and the hydrogen pressure was maintained at IO at gauge pressure during this period.
Kri/cnl was maintained. The reaction was then aged for 1 hour under the same conditions. After the reaction was completed, the hydrogenation catalyst was filtered off, and the aqueous layer was separated to obtain a crude tertiary amine. The hue of the crude tertiary amine is below APHA30 and is almost colorless.
There is almost no odor other than amine odor, and the purity is 97.7%.
Met. The tertiary amine purified by vacuum distillation had a distillation yield of 96.1%, a purity of 98.4%, and a hue of APRAI.
It was completely colorless and transparent below 0.

In addition, purified tertiary amines were stored at 50C for 6 months,
I also conducted 6 sun exposure trials outside, but there was no change in external vision or smell.

This experiment shows that a tertiary amine of high quality can be obtained in high yield even if the reaction is carried out by adding a portion of the carbonyl compound first and then adding the remaining portion in succession.

Comparative Examples 1 to 8 In Comparative Examples 1 to 4, reactions were carried out in accordance with Actual Example IK. However, as catalysts, Raney nickel was used in Comparative Example 1, palladium black was used in Comparative Example 2, platinum supported on silica was used in Comparative Example 3, and palladium supported on silica was used in Comparative Example 4.

In Comparative Examples 5 to 7, reactions were carried out according to Example 9, and Raney nickel was used as a catalyst in Comparative Examples 5 and 7, and platinum oxide was used in Comparative Example 6.

In Comparative Example 18, the reaction was carried out by adding a total amount of acetaldehyde from the beginning, and the catalyst was the carbon-supported palladium used in the present invention. The reaction was carried out according to Example 1, but acetaldehyde was not added during the reaction.

The obtained crude tertiary amines were purified by distillation under reduced pressure after removing the hydrogenation catalyst and separating water 11 in the same manner as in each example.

Table 5 shows the reaction conditions and analytical values of the obtained product.

From Table 3, the distillation yield and the purity of the tertiary amine in the comparative example are both lower than in the example. In addition, although the purified tertiary amine was colorless and transparent immediately after distillation, it became considerably colored when stored at room temperature for one month, and became even more strongly colored when subjected to a storage test at 50 UK or a sunlight exposure test. Further, even immediately after distillation, there was a carbonyl compound odor and other unpleasant odors in addition to the amine odor, and the unpleasant odor became even more pronounced when a storage test at 50C and a sunlight exposure test were performed.

Comparative Examples 1 to 4 show that catalysts other than those used in the present invention are not preferred, and Comparative Examples 5 to 7 also show that removing water by ring-closing hydrogen during the reaction has no effect. Furthermore, it can be seen from Comparison 19118 that it is necessary to add the carbonyl compound quickly during the reaction.

Patent applicant Nippon Oil & Fats Co., Ltd. Procedural amendment 1t (voluntary) October 16, 1980 Commissioner of the Patent Office Mr. Manabu Shiga (Examiner of the Patent Office) 1 Indication of the case 1980 Patent Application No. 194758 2, Invention Name: Method for producing tertiary amine 3 Relationship with the case of the person making the amendment Patent applicant: IO No. 1-4, 1-chome Yurakucho, Chiyoda-ku, Tokyo, subject of amendment EA #l (Detailed explanation of the invention column #)吋≠轡手5, Contents of amendment (1) Page 6 of the specification, lines 9-11 “Also...
····Conceivable. ” to the following sentence.

"It is also possible that carbonyl compounds react with this active methylene group."
Corrected to "Hexanal".

(3) 1-hexenal, line 2 of page io, 12-
Corrected to hexenal j.

(→ ``Correct cyclohexanal j to cyclohexylaldehyde j'' on page 10, line 3 of the same 0(5), line 11 of the same
In lines 3 and 4 of the page, "formaldehyde" is corrected to "carbonyl compound."

(6) On page 12, lines 8-9, "methylolamine derivative" is corrected to "1-hydroxyalkylamine."

・1(7) Same page 12, line 9 “Ship base derivative” is changed to “
Correct it to ``Imi/''.

(8) On page 13, line 6, "solution of carbonyl compound" is corrected to "rcarbonyl compound".

(9) Page 13, line 9 “Carbonyl compound solution”
“Correct it to carbonyl compound j.

α1 Same page 14 line 15 rsoor” r400fJ
K Correct.

α, page 14, line 20 “Solution of carbonyl compound”
Correct r carbonyl compound JK.

(2) On page 16, line 5 from the bottom, [(2) Molar ratio of raw material amine to active hydrogen] was corrected to "(2) Molar ratio of raw material amine to active hydrogen. For acetaldehyde, use a 60% aqueous solution." do.

(To) On page 17, line 7, "formaldehyde aqueous solution" is corrected to "carbonyl compound."

α rod Page 19, line 6 from the bottom, "(2) Molar ratio of raw material amine to active hydrogen" is changed to "(2) Molar ratio of raw material amine to active hydrogen. A 60% aqueous solution of acetaldehyde is used. JK corrects.

αe 2nd line from the bottom of page 19 “(6) Examples 10-1
6 stands for "distilled purified product" (6) Examples 9 to 12 are distilled purified products. Examples 13 to 17 are crude products. ” is corrected.

α→ Correct “Table 5” on page 22, line 13 to “Table 31.”

(17) Line 4 from the bottom of page 23 [(2) Molar ratio of raw material amine to active hydrogen] is r (2) Molar ratio of raw material amine to active hydrogen. Acetaldehyde is 60%
Uses an aqueous solution. ” is corrected.

that's all

Claims (1)

[Claims] 1. General formula (1) R^1R^2N[(CH_2)_nNH]_mR^3(
1)………………(1) (In the formula, R^1 is a carbon number of 8 to 24
A straight chain or branched alkyl group or alkenyl group, R^2 and R^3 are a hydrogen atom or a straight chain or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, m is 0 or 1 to The integer of 5, n represents 2 or 3, and when m=0, at least one of R^2 and R^3 is a hydrogen atom. ) The amine represented by hydrogen and the general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………(
2) (In the formula, R^4 and R^5 are hydrogen atoms or have 1 to 2 carbon atoms
4 saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon group, aromatic hydrocarbon group-substituted aliphatic hydrocarbon group, or aromatic hydrocarbon group that may have a substituent, R^4 and R^5 are never hydrogen atoms at the same time. ) When performing alkylation using a carbonyl compound represented by
Under conditions of Kg/cm^2 (gauge pressure) or more, a hydrogenation catalyst in which 0.1 to 10% by weight of Co, Ni, Ru, Rh, Pd, or Pt is supported on powdered or granular carbon is heated according to the general formula A method for producing a tertiary amine, which comprises adding a catalytic metal concentration of 5 to 5000 ppm to the amine represented by (1), and carrying out the reaction while continuously adding a carbonyl compound.