JPS60112743A - Production of tertiary amine - Google Patents

Abstract

PURPOSE:To obtain the titled compound tertiary amine useful as a corrosion inhibitor, etc. in high yield, purity and quality, by methylating a specific amine under specific conditions in the presence of a specific hydrogenation catalyst while adding hydrogen and formaldehyde continuously to the reaction system. CONSTITUTION:An amine of the formula (R<1> is 8-24C straight chain or branched chain alkyl or alkenyl; R<2> and R<3> are H, 8-24C straight chain or branched chain alkyl or alkeyl; m is 0 or an integer 1-5; n is 2 or 3; either one of R<2> and R<3> is H when m is 0) is methylated with H and formaldehyde to give a tertiary amine. In the process, a hydrogenation catalyst obtained by supporting 0.1- 10wt% Co, Ni, Rh, Pd or Pt on a powdery or granular carbon in an amount of 5-5,000ppm based on the amine of the formula expressed in terms of the catalyst metal concentration is added to the amine, and the reaction is carried out at 80-250 deg.C reaction temperature under >=2kg/cm<2> hydrogen pressure (gauge pressure) while adding formaldehyde continuously to the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing tertiary amines, and more particularly, the present invention relates to a method for producing tertiary amines, in which primary or secondary amines are maximally methylated using hydrogen and formaldehyde in the presence of a hydrogenation catalyst, thereby producing tertiary amines in high yields. The present invention relates to a method for producing tertiary amines of high purity and madder quality.

Aliphatic tertiary amines are used as corrosion inhibitors and fuel oil additives.
It is also useful as an intermediate raw material for quaternary ammonium fences and amphoteric surfactants such as irritant, fungicide, disinfectant, leveling agent, and anti-oxidant agent. As the use of tertiary amines has expanded in recent years, the quality required of tertiary amines has been increasing year by year, such as high quality as a reaction intermediate raw material, for example, the absence of impurities that cause coloration and odor in the final product.

As a method for methylating primary or secondary amines, (A
) using formic acid and formaldehyde (page 72a)
(B) Method of methylation using hydrogen and formaldehyde (Organic Reactior+s fr
(C) Reaction of higher alkyl halide and methylamine (U.S. Pat. No. 3,379,764 M
) and (D) Reduction and minization reaction of higher alcohol and methylamine (JP-A-52-19604, JP-B-Sho 57-8)
No. 49, Special Publication No. 57-55704), etc. are known.

As one of the tertiary amines produced in the present invention, higher alkyldimethylamines are mainly industrialized by method (C), but 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 natural alcohol and methylamine, and this method is also a reaction method different from the present invention. Method (A) cannot obtain a sufficient reaction rate unless a large excess of formic acid is used, and since formic acid is expensive, it should not be put into practical use except for the production of special tertiary amines.

Method (B) is the same reaction method as the present invention, but in the past, the reaction yield and product quality were considerably inferior to method (C), so it was generally considered to be unsuitable for λ14. . However, since this method has a wide range of applications and is cost-effective if the yield and quality are improved, improvements have been desired.

For example, as described in Organic Reactions, Volume 4, Pages 244 and 248, νζ, when primary or tertiary amino acids are reacted with hydrogen and formaldehyde using a Raney nickel or platinum catalyst, the yield is 90%.
less than or equal to Japanese Patent Publication No. 39-17905 describes a method for improving the yield by using a known-chain aliphatic-basic acid or a short-chain aliphatic hydroxyl-base acid as an additional catalyst for the reaction. Also includes alkyl groups with 8 or more carbon atoms:)
Even when a primary amine is reacted under a Raney nickel catalyst, the amount of tertiary amine produced is about 85%, resulting in a low yield.

The present inventors conducted a detailed study on the methylation reaction using primary or tertiary amino hydrogen and formaldehyde, and as a result, the following fact became clear.

In other words, the first 71c is a reaction between tertiary amino and polyaldehyde, methylolamine in the s, IJj form, and imine' produced by intramolecular dehydration are highly reactive compounds, but the antipodal The hydrogenation reaction of methylolamine and imine to methylamine is difficult to occur in the case of methylolamine and imine, which has insufficient reducing action, and reacts with the primary or niamine present in the polyolefin. A compound is generated and attached to the hydrogenation catalyst, which impairs the dispersion of the hydrogenation catalyst 1 and also prevents hydrogen from diffusing to the surface of the hydrogenation catalyst. Furthermore, methylolamines and imines may react with primary or tertiary amino acids or with active methylene groups of the formed polymethylene polyamine. Formaldehyde also reacts with polymethylene polyamines and methylolamines to produce complex by-products, which not only reduce the yield of the desired tertiary amino acids, but also cause odor, coloration, and We have discovered that there are many causes of discoloration.

Based on these findings, the present inventors determined that the three factors of simultaneous K As a result of our efforts to find a suitable water bulking catalyst, we have arrived at the present invention.

That is, the present invention is based on the general formula (1) % formula % (1) (wherein R' is a straight chain or branched alkyl group having 8 to 24 carbon atoms or alkenyl 4, R'' and R3 are a hydrogen atom or A straight or branched alkyl group or alkenyl group having B to 24 carbon atoms, m is O or the number of strands from 1 to 5, n Fj', 2 and k represent 3, and when m = 0, HR'' and R3, at least one of which is a hydrogen atom.) When performing methylation using hydrogen and formaldehyde, the reaction IA degree is 80 to 250 ° C1.
Under hydrogen pressure (gauge pressure) 2kp/, 4 or more rows, CO1Ni, Rh%Pd-t in powder form or granularity Fu
A bottification catalyst carrying 0.1-10 PT or PT was applied to the amine represented by the general formula (1) at a force of 5 to 5000 p,) m as a 4-9 metal particle degree. 1. A method for producing a tertiary amine, which is characterized in that the reaction is carried out while continuously adding formaldehyde.

The amine of formula (1) includes octylamine, dobutylamine, tetradecylamine, hexadecylamine,
In addition to octadecylamine, tocodylamine, oleylamine, linoleamine, erucylamine, etc., mixtures of coconut oil alkylamine, tallow alkylamine, hardened tallow alkylamine, rapeseed oil alkylamine, chassis oil alkylamine, di-tallow alkylamine, di-hardened Beef tallow alkylamine, aminoethyl coconut oil alkylamine,
Aminoethyl tallow alkylamine, aminopropyl coconut oil alkylamine, aminopropyl tallow purkylamine, NINT-coco alkylethylenediamine, N
- Coconut oil alkyl-N'- Beef tallow alkylethylene diamine, N- Coconut oil alkyl diethylene triamine, N-
Beef tallow alkyl diethylene trinoamine, N-coco alkyl dipropylene triamine, N-coco alkyl dipropylene triamine, N-coco alkyl tripropylene tetramine, N-coco alkyl tripropylene tetramine, N-coco alkyl tetrapzololene pennomine,
N-Beef tallow alkyltetrapropylene pentamine, N-Coconut oil alkylpentapropylene hexamine, N-Beef tallow 7
#Kilpentapropylenehexamine etc., 11・■
Also! [94] Can be used as a mixture of the above.

As formaldehyde, in addition to an aqueous solution, a slurry liquid of formaldehyde can also be used. The amount of formaldehyde used is 1 to 1.5 times the mole, preferably 1 to 1.05 times the mole of active hydrogen of the amino group or imino group of the primary or tertiary amine. 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.

Any one of Ni5Co, Rb, Pd, and Pt is added to the hydrogenation catalyst rj powder bed or granular carbon used in the present invention.
It was prepared by supporting 1 to 10 layers. Hydrogenation catalysts can be prepared by known methods, such as those described in Aduancain. The amount of hydrogenated Gi used is 5~s as the amount of melting metal for the raw material amine.
Q Q ppm't'4ru. This hydration catalyst ideally disperses in the amine layer even in systems where the water layer and amine layer coexist.
There is almost no dispersion into the aqueous 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, which is undesirable. Also, Raney nickel, Raney cobalt,
Single metals and metal oxides such as platinum oxide, platinum black, and palladium black are known as highly active hydrogenation catalysts, but good results cannot be obtained in the case of non-reaction.

In the method of the present invention, pressure-resistant reaction-S is used, and hydrogen pressure (
Gauge pressure) 2KP/- or more, reaction temperature 80-300°C
1 Preferably a hydrogen pressure of 5 to 50 m/s. 5. Reaction temperature 100
The reaction is carried out at ~250"0.The external water pressure is 2K9/
If it is less than 6J or the reaction temperature is less than 80'C, the hydrogenation reaction will not proceed sufficiently, and 11 organisms such as methylolamine derivatives, their 11 compounds, and thick base derivatives will increase, and the reaction will be delayed. When the temperature exceeds 300°Qf, by-products such as poly long-chain alkyl amines and hydrocarbons derived from the dehydrogenation reaction of amines increase.

The formaldehyde addition method is not particularly limited as long as it is added to ki 4, but usually it is added to the reactor in small quantities using a pressure pump.

If a large amount of formaldehyde water 44 liquid or water produced by the reaction accumulates during the reaction, hydrogen can be released or circulated to remove water from the system and react from Δ.

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 pump, and a gas circulation device with a cooling condenser if necessary, and the desired reaction temperature i1 is maintained while stirring.
After raising the temperature and replacing the atmosphere in the system with hydrogen, hydrogen is added to the predetermined pressure.

Next, press injection of formaldehyde water solution was started, and
The reaction is carried out under a hydrogen pressure of t. When circulating water ≦5, condensed water is removed from the system using a cooling condenser.

After the injection of the formaldehyde aqueous solution is completed, the reaction is aged for a certain period of time while keeping the reaction temperature and hydrogen pressure constant.

When amines are methylated by the method of the present invention, the desired reaction proceeds almost quantitatively, and almost no by-products that cause quality deterioration are produced. That is, the crude tertiary amine obtained is almost colorless and has no off-odor. The methylation rate of the amine reaches 97 degrees or more regardless of the S@ of the primary amine or tertiary amine as the raw material. In addition, the distillation yield is 95% or higher, and the purity of the tertiary amine is 98% or higher.

The heat resistance and light resistance of the tertiary amine obtained by the method of the present invention are extremely excellent, and there was no change in color or odor even after a heat resistance test during storage in SO'C and a sunlight exposure test on 6 blades. No changes observed.

In addition, the amine oxide, quaternary ammonium oxide, and salt produced using the obtained tertiary amine are nearly colorless and odorless, and there are no problems in terms of appearance or quality.

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

Examples 1 to 9 800 Jl of primary or tertiary amine as a raw material and a hydrogenation catalyst were placed in a 2-volume autoclave equipped with a stirrer and a pressure pump, and the mixture was heated to a predetermined level while being stirred at 9° rpm by a flat-blade turbine. After the temperature was raised to a certain temperature and the atmosphere in the system was replaced with hydrogen, hydrogen was added to a predetermined pressure. Next, the reaction was carried out at a constant temperature and constant pressure while adding a formaldehyde water bath liquid at a predetermined time using a full-pressure pump, and after the addition was completed, the reaction was aged for 30 minutes. After the reaction was completed, the hydrogenation catalyst was separated from F, and then water was separated to obtain a crude tertiary amine. In addition, some tertiary amines were purified by vacuum distillation.

Table 1 shows the reaction conditions and the analytical values of the F↓) products.

As is clear from Table 1, the hue of the obtained coarse tertiary amine was below APHA3Q and was almost colorless.

Further, the distilled purified tertiary amine was completely colorless and transparent. Further, no odor other than the amine odor was observed in either the purified tertiary amine or the crude tertiary amine. The purity of each crude tertiary amine was 9B or higher, and the purity of each purified tertiary amine was 99 or higher. Furthermore, purified tertiary amine was stored at 50'C for 6 months and subjected to outdoor sunlight exposure test f: 6, but there was no change in appearance or odor.

Examples 1O to 23 The raw material amine 20 YK9 and hydrogenation catalyst were placed in a 50 mm capacity autoclave equipped with a hydrogen circulation device with a stirrer, a cooling condenser, and a pressure pump, and the temperature was raised to a predetermined temperature while stirring. , after replacing the atmosphere in the system with hydrogen,
Hydrogen was added to the specified 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 the furnace to remove the crude tertiary amine odor. In addition, some tertiary amines were purified by vacuum distillation.

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

From Table 2, the hue of the obtained Japanese tertiary amine is APHA3
0 or less, it was almost colorless, and the purified tertiary amine was also the same. Furthermore, no odor other than the amine odor was observed in either the crude tertiary amine or the lit IU m tertiary amine. In addition, the purity of the crude tertiary amine, sheath, and AM triamine were all 98% or higher.

Furthermore, when the ``ha'' tertiary amine was stored at 50°C for 6 months and subjected to 6 outdoor sunlight exposure tests, there was no change in appearance or odor.

Example 24 Add 500 ml of n-dodecylamine to a 2-volume Erlenmeyer flask!
The mixture was then heated to 70°C while stirring.

This was mixed with an aqueous formaldehyde solution at a concentration of 37% and stirred for 2X hours, and then the aqueous layer was separated.

The n-dodecylamine-formaldehyde condensate obtained in the autoclave used in Example 1 and a hydrogenation catalyst of 55 pa-c 0.5 F (0.1
weight i%) was added. 900 r using flat blade turbine
The system was heated to 160'C while stirring with prn, and the system was replaced with gold hydrogen, and then hydrogen was added until the gauge pressure reached 10 KP/-. Hydrogen absorption started immediately, but the hydrogen pressure was always kept the same. After 2 hours have passed and hydrogen absorption has stopped, formaldehyde aqueous solution with a concentration of 37 zllP
(05 mole times the active hydrogen of n-dodecylamine)
Pressure was introduced over 12 hours, and the hydrogen pressure was maintained at 10 to 9/- at this tlI+gauge pressure. 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 almost colorless below API (Aao), there is almost no odor other than amine fan, and the purity is 97.
It was 44. Tertiary amines purified by vacuum distillation are
Distillation yield 95.2%, pure T9&1T, hue is APRA
It was completely colorless and transparent at less than IO.

In addition, purified tertiary amines were stored in SO'C for 6 months, and all 6 sunlight exposure tests were conducted outdoors, but there was no change in appearance or odor in either case.

This experiment shows that high yields and good quality tertiary amines can be obtained even if the reaction is carried out by adding part of the formaldehyde first and then adding the rest continuously.

Comparative Examples 1 to 8 In Comparative Examples 1 to 5, reactions were carried out in accordance with Example 1. The catalysts used were Raney nickel in Comparative Example 1, palladium black in Comparative Example 2, platinum supported on silica in Comparative Example 3, palladium supported on limestone in Comparative Example 4, and platinum oxide in Comparative Example 5.

In Comparative Examples 6 and 7, the reaction was carried out according to Example 1o, and Raney nickel was used as the catalyst.

Comparative Example 8 The reaction was carried out by adding the entire amount of formaldehyde from the beginning, and the catalyst used was carbon-supported palladium used in the present invention. The reaction was carried out according to Example 1, but formaldehyde was not added during the reaction.

The raw material amine used was n-octadecylamine in Comparative Example 7, and n-dodecylamine in the others.

The obtained crude tertiary amine was purified by distillation under reduced pressure after removing the hydrogenation catalyst with F and separating the aqueous layer in the same manner as in each Example.

Table 3 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. Further, the hue of the purified tertiary amine was colorless and transparent immediately after distillation, but it was 5Lξ-colored. Furthermore, even immediately after distillation, the unpleasant odor became stronger than the amine odor.

Comparative Examples 1 to 5 show that catalysts other than those used in the present invention are not preferred, and Comparative Examples 6 to 7 show that there is no effect even if water is removed by circulating hydrogen during the reaction. Furthermore, Comparative Example 8 shows that formaldehyde must be added continuously during the reaction.

Patent applicant: NOF Corporation

Claims (1)

[Claims] 1 General formula (1) % formula % () (in the formula % R' is a straight or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, R2 and R3 are hydrogen atoms or A linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, m is O or an integer of 1 to 5, n is 2-1:F1a, and when m=o, R
At least one of 2 and R3 is a hydrogen atom. ) When methylating an amine represented by hydrogen and formaldehyde, Co, Ni, RhPd is added to powdered or granular carbon under conditions of a reaction temperature of 80 to 250° C., hydrogen pressure of 2 KIJ/4 (gauge pressure) or more. Alternatively, a hydrogenation catalyst carrying 01 to 10% by weight of Pt is added to the amine represented by the general formula (1) at a tactile metal concentration of 5 to 5000 PPm, and the reaction is carried out while continuously adding formaldehyde. A method for producing a tertiary amine, characterized by: