JPS59134754A - Preparation of bis(2-(n,n-dimethylamino)ethyl)ether - Google Patents

Abstract

PURPOSE:To prepare the titled substance useful as a catalyst, easily and safely, by reacting diethylene glycol or 2-[2-(N,N-dimethylamino)ethoxy]ethanol with dimethylamine in a closed vessel in the presence of a copper-based catalyst under specific condition. CONSTITUTION:The objective compound is prepared by reacting diethylene glycol or 2-[2-(N,N-dimethylamino)ethoxy]ethanol with dimethylamine in a closed vessel in the presence of hydrogen and a copper-based catalyst, e.g. Raney-Cu catalyst, copper chromium catalyst, etc. at about 150-300 deg.C, especially about 200-250 deg.C, and subjecting the partly by-produced secondary amino compound to the methylation reaction without separating from the reaction system. The amount of the dimethylamine is preferably about 3-4mol per 1mol of diethylene glycol and about 1.5-2mol per 1mol of the other raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a safe and economical improved method for producing bis(2-(N,N-dimethylamino)ethyl phether (hereinafter abbreviated as BDMEE J)).

BDMgE is a useful compound used as a catalyst in the production of polyurethane foam from organic incyanates and polyols, and therefore a number of production methods have been developed to date, as described below. That is, a method of producing bis[2-(chloroethyl)]ethyl and trimethylamine via methochloride of BDMEE (U.S. Pat. No. 3,400,157, U.S. Pat. No. 3,426)
No. 072), a method for producing from 2-(N,N-dimethylamino)ethyl chloride and sodium 2-(N,N-dimethylamino)nidoxide (No. 348)
No. 0675), a method for producing from sodium 2-(N,N-dimethylamino) nitoxide and s05 gas (
No. 4247482), and a method for producing from sodium 2-(N,N-dimethylamino)ethoxide and 2-(N,N-dimethylamino)ethanol in the presence of sulfur oxychloride (No. 4177212).
(No.) etc.

However, when chlorine compounds or sulfur compounds are used as raw materials, there is a risk of corrosion of the equipment, and there is also the disadvantage that large amounts of chlorides and sulfates are produced as by-products, which require troublesome disposal costs.

Also in the presence of nickel throughout the range 2-[2-(N.

N-dimethylamino)ethoxy]ethanol (rD
There is a method for producing trimethylamine (abbreviated as MEEJ) and trimethylamine (US Patent No. 3,957,875), but the catalyst is expensive, the reaction time is long, and it is necessary to use more than 3 moles of trimethylamine based on the DMEE raw material. It is difficult to say that this is an industrially satisfactory manufacturing method, as BDMEE cannot be obtained with sufficient convergence.

Therefore, a manufacturing method that is easier to operate, safer, and more economical has been desired.

As a result of extensive research, the present inventors have found that diethylene glycol or DMEE reacts easily with dimethylamine in good yield in the presence of a copper-based catalyst, and has thus created the present invention. The method of the present invention is a novel and economically valuable method.

A feature of the method of the present invention is that diethylene glycol or DMEE is produced at a temperature of about 150°C to 300°C in the presence of a copper-based catalyst and hydrogen during closed fatigue.
(i) Reaction with dimethylamine, and then methylation reaction of some of the secondary aminated products produced as by-products.

The method of the present invention typically involves liquid phase patch production, but depending on the equipment selection, continuous production is also possible.

Carrying out the method of the invention. The reaction can easily proceed by mixing the raw alcohol, amine, and catalyst in a suitable container and heating it in the presence of hydrogen gas, but a closed container is used to keep the raw amine in a liquid phase. do.

Suitable copper catalysts for use in the method of the invention include Raney copper catalysts, reduced copper catalysts, copper-chromium catalysts, and the like. The amount used is 0.2 to 20% by weight based on the raw material alcohol.
It is effective at a certain amount, and usually 1 to 5% by weight is used.

The reaction proceeds smoothly at a temperature of about 150 to 300°C,
In particular, a temperature of about 200 to 2,500 is preferable in view of economic efficiency.

As mentioned above, since the reaction takes place in a closed apparatus, an increase in internal pressure due to the amine is observed as the reaction temperature increases, but this can be adjusted as appropriate by adjusting the amount charged in the container. Generally, it is preferable to carry out the reaction at a pressure of about 50 to 130 kP/m2 from the viewpoint of operability and safety.

The method of the present invention is suitably carried out in an inert gas atmosphere that does not have an adverse effect on the reaction, such as a hydrogen gas atmosphere or a purple gas atmosphere in the presence of tree leaves. It is preferable to carry out in a hydrogen gas atmosphere applied from above.

The reaction of the process of the invention proceeds in stoichiometric amounts of starting compounds, usually diethylene glycol and D
The amount of dimethylamine used relative to MEE is an amount in excess of the respective reaction equivalent, that is, about 3 to 4 mol per mol of diethylene glycol, and about 1 mol per mol of DMEE.
．． Preference is given to using 5 to 2 mol.

The reaction conditions described above are preferable for suppressing side reactions and increasing the conversion rate.

In the method of the present invention, DMEE is recovered as an intermediate when diethylene glycol e is used as a raw material, which can be further used as a raw material for producing BDMEE.

When the method of the present invention is carried out, by-products that require troublesome disposal treatment as described above are not produced, and only a secondary aminated product having the formula % of N-methylmorpholine and a structure with an extremely high boiling point are produced. It only produces unspecified compounds as by-products. After the amination reaction is completed,
After filtering the reactants and recovering the catalyst, unreacted dimethylamine is recovered by distillation, followed by methylation of the secondary aminated product using a methylation reaction, for example, a formic acid-formalin method, followed by fractional distillation to obtain BDMEE. It will be done.

Since it is difficult to separate the secondary aminated product and BDMEE, it can be easily converted to the target product by further subjecting it to a methylation reaction in the reaction mixture, and BDMEg can be obtained in high yield.

Next, the method of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight."

Example 1 In a 10100O autoclave equipped with a stirrer, 2-
(2-(N,N-dimethylamino)ethoxy) 300 parts (2.25 mol) of ethanol (DMEE), 180 parts (3.99 mol) of dimethylamine, and a copper-chromium catalyst [manufactured by JGC Chemical Co., Ltd.] After charging with 115 parts of N-203 and purging with nitrogen, 10 kg/crIL2 of hydrogen was added under pressure and heated with stirring.

Temperature 225-235℃, pressure 60-67 kl? / 慕2
After reacting nearby for 10 hours, the reaction mixture is filtered to recover the catalyst. Gas chromatography analysis of liquid F revealed that residual DMEE was 64.0 parts (conversion rate 787%).
155.5 parts of bis(2-(N,N-dimethylamino)ethyl)ether (BDMEE) (selectivity 54.7%),
There were 25.0 parts of N-methylmorpholine as a by-product and a small amount of secondary aminated product. After recovering υdimethylamine by distillation, 10.2 parts of parafor-mualdehyde and 15.5 parts of formic acid were added, heated at 118°C for 2 hours to convert it to secondary aminated compound 'iiBDMEE, and then diluted with 50% sodium hydroxide. Neutralize with 5.2 parts of an aqueous solution, take the upper oily part separated into two layers, and fractionate it in a 15-stage rectification column to obtain blool.
150 parts of BDMEE having a temperature of 20.5°C (selectivity 52.8%) were obtained.

Example 2 In the same operation as in Example 1, 300 parts of DMEE (
225 mol), 200 parts (4.44 mol) of dimethylamine, and 15 parts of Raney copper catalyst at a temperature [230°C,
The reaction was carried out at a pressure of 60 to 70 J/cyn2 for 9 hours. Gas chromatography analysis of the reaction solution revealed that residual DMEE was 111 parts (conversion rate 63.0%), BDMEE 124 parts (selectivity 54.5%), and N-methylmorpholine 15 parts.

Example 3 In the same operation as in Example 1, 200 parts (1,89 mol) of diethylene glycol and 33 parts of dimethylamine
5 parts (7.43 mol) and 10 parts of copper-chromium catalyst were charged, and the temperature was 230°C and the pressure was 133-135°C.
．． The reaction was allowed to proceed for 5 hours. The chromatograph analysis results of the reaction solution showed residual diethylene glycol 1.5 parts (conversion rate 99.2%), BDMEE 117.7 parts (selectivity 89.3%),
The contents were 58.1 parts of DMEE (selectivity 23.3%) and 27.7 parts of N-methylmorpholine.

Example 4 In the same operation as in Example 1, 200 parts (1,89 mol) of diethylene glycol and basic copper carbonate [CuCo
3 ・Cu (OH) 2 ・H20) 20 @
Charge f, seal hydrogen, and reduce at 165°C for 2 hours to produce a metallic copper catalyst. After cooling, dimethylamine 200 parts (444
mol), and after nitrogen substitution, further hydrogen 10 kg/'C
nL2 was press-fitted at a temperature of 250℃ and a pressure of 80 to 97kg/C.
It was reacted with rIL2 for 10 hours. The results of gas chromatography analysis of the reaction solution showed that the remaining diethylene glycol was 6 parts (conversion rate 97%).
%), BDMEE 67 parts (selectivity 229%), N-methylmorpholine 80 parts, DIvIEE 39 parts (selectivity
16.0%).

Reference Example In the same operation as in Example 1, 200 parts (189 mol) of diethylene glycol and 240 parts (5 mol) of dimethylamine were added.
, 32 mol) and 10 parts of Raney nickel catalyst were charged at a temperature of 230°C and a pressure cuff of 8 to 80 kg/cnL.
Allowed time to react. Gas chromatography analysis results of the reaction solution showed residual diethylene glycol 40 parts (conversion rate 80%), BDM
EE was at a trace level.

Patent applicant: Nippon Nyūkazai Kaishiki Co., Ltd. Representative Patent Attorney Shoji Kashi

Claims (1)

[Claims] 150 in the presence of hydrogen using a copper-based catalyst in a closed apparatus.
Diethylene glycol or 2
- bis[2-(N, Method for producing N-dimethylamino)ethyl phether.