DE1020347B - Process for the production of fully oxyalkylated, symmetrical alkylenediamines - Google Patents

Description

The invention relates to a process for the preparation of completely oxypropylated, symmetrical alkylenediamines.

It is known to oxyalkylate alkylamines with alkylene oxides by adding tertiary monoamines in the presence of weak acids can be reacted with alkylene oxides.

It is also known to use aminohydroxyalkyl ethers by the action of ethylene oxide on ethylene diamine in one To produce a molar ratio of 6: 1. Here, however preferably obtained higher oxyalkyl derivatives.

It has now been found that by reacting propylene oxide with alkylenediamines having 2 to 6 carbon atoms in the presence of water in a molar ratio of 4: 1 at a temperature of 40 to 200 ° completely oxypropylated, symmetrical alkylenediamines of the formula below.

CH,

CH,

HO-CH-CH ₂ , CH ₂ -CHOH

/ Ν - RN (^
HO-CH-CH ₂ XH ₂ -CHOH

CH,

CH ₃

R represents an alkylene radical having 2 to 6 carbon atoms.

These compounds represent a new interesting class with a double chemical character, in that they are both polyhydric alcohols and high-boiling bases.

They are, and still are, valuable moisturizers for use on items such as cellulose glass valuable absorbent for removal because of their high boiling points and mildly basic properties of acidic compounds such as carbon dioxide and hydrogen sulfide from hydrogen and other gases.

A special feature of the procedure is the convenience and ease with which the completely oxypropylated alkylenediamines without concomitant formation of undesirable higher oxypropylated Derivatives are obtained. The compounds are obtained practically with quantitative yields, where 1 mole of propylene oxide is required for each amino hydrogen atom of the diamine. It will therefore 4 moles of propylene oxide applied to 1 mole of alkylenediamine; but even if you accidentally initiate one An excess of propylene oxide results in essentially no oxypropylation of the desired product. For example, in a laboratory test at about 80 ° and ordinary pressure, an excess of pro-method was used for the production

of fully oxyalkylated,

symmetrical alkylenediamines

Applicant:

Wyandotte Chemicals Corporation,
Wyandotte, me. (V. St. A.)

Representative: Dr. K. Griesing, patent attorney,
Hönebach near Bebra, Bahnhofstr. 9

Claimed priority:
V. St. v. America July 28, 1953

Lester Gordon Lundsted and Walter Franz Schulz,

Wyandotte, me. (V. St. A.),
have been named as inventors

initiated pylene oxide, which, however, did not react and was recovered by distillation. The reaction is carried out by introducing the calculated amount of propylene oxide into the alkylenediamine, preferably with stirring. Either at least a small amount of water of about 0.5 to 1% or an alcohol must be present as a catalyst for the reaction. The alkylene diamines are commercially available as concentrated aqueous solutions, that is, from 65 to 80 ⁰ J _0, available, and there are therefore preferably used solutions of this concentration, although very dilute aqueous solutions of diamines, that is, 10 to 20 ⁰ I _0, more suitable are. If it should be desired, you can work with the exclusion of water. In this case, however, an alcohol must be present as a conversion catalyst.

The reaction can take place at temperatures from about 40 to about 200 °, preferably in the range of about 50 to about 120 °. Either ordinary pressure or overpressure, i. H. from 1 to 5 atmospheres of propylene oxide can be used, with a faster course of the reaction being achieved under higher pressures.

Typical starting materials for the process are ethylenediamine, propylenediamine, butylenediamine and hexamethylenediamine.

709 808/291

The subject matter of the invention is to be explained in more detail using the following examples:

example 1

In a three-necked round-bottomed flask equipped with a mechanical stirrer, re-nut condenser, thermometer and gas inlet tube 94.1 g (1.57 mol) of ethylenediamine and 15.6 g of water are added. Nitrogen is used to remove the air passed through and heated to 90 ° with stirring. Propylene oxide is then converted into the ethylenediamine, as quickly as it is taken up, initiated until about 367 g (6.33 mol) of propylene oxide have reacted. The water is then removed from the reaction product by means of vacuum. The N, N, N ', N'-tetra- (2-oxypropyl) -ethylenediamine obtained is a viscous, amber-colored liquid. It can be without at 184 ° and 0.5 mm Hg Distill decomposition.

Example 2

There are a total of 499 g (4.3 mol) of hexamethylenediamine in 72.4% aqueous solution in the apparatus according to Example 1. A total of 983 g Propylene oxide (17 moles) is released over a period of 7 hours at an average temperature of 90 ° added under normal pressure. The water is removed by vacuum and the Ν, Ν, Ν ', Ν'-tetra- (2-oxypropyl) -hexamethylenediamine distilled at 214 to 215 ° and at 0.5 mm Hg. The resulting product is a waxy, white solid mass that melts at 50 to 56 °.

Example 3

321 g (5.7 mol) of ethylenediamine in 76% aqueous solution are placed in a 4.5-1 stainless steel autoclave Steel, which is equipped with a stirrer, thermocouple, pressure gauge and a gas inlet pipe with an outlet opening is provided below the stirrer, given. Over the course of 2.3 hours, a total of 1341 g (23.1 mol) Propylene oxide at an average temperature of 68 ° and an average working pressure of 0.85 at added to the reaction mixture. After removing the water by means of vacuum, the Ν, Ν, Ν ', Ν'-tetra- (2-oxypropyl) -ethylenediamine obtained in practically quantitative yield.

: The fully oxypropylated alkylenediamines are shown is characterized by a remarkable heat resistance.

This heat resistance is surprising because a ■ homolog of tetra- (2-oxypropyl) ethylenediamine, namely Tetra (oxyethyl) ethylenediamine, decomposes when heated and cannot be distilled (see Sect. Sherlin et al, Chemical Abstracts 35, 5858 [1941]).

When comparing the chemical structure of tetra (2-oxypropyl) ethylenediamine and the tetra (oxyethyl) ethylenediamine can be found that the tetraoxyethyl compound primary, while the tetraoxypropyl compound contains secondary hydroxyl groups. It is in It is well known in organic chemistry that primary hydroxyl groups tend to be more resistant to thermal decomposition are called secondary hydroxyl groups. Accordingly, it was to be expected that actually the Tetra- (oxyethyl) -alkylenediamines should be much more heat-resistant than the tetra- (2-oxypropyl) -alkylenediamines. The heat resistance of the completely oxypropylated alkylenediamines is therefore of particular importance, because it allows the manufacture of a colorless product which has many uses for such Products is very much desired.

With the continuation of the investigations on the thermal resistance of these compounds was continued found that their esters, the production of which is not claimed here, are more heat-resistant than that of their oxyethylated homologues. So z. B. the tetraacetyl ester of tetra (2-oxypropyl) ethylenediamine Distill at 178 to 179 ° and 0.3 mm Hg with the result of a colorless distillate, during the Tetraacetyl ester of tetra (oxyäthyl) ethylenediamine distilled at 0.3 mm Hg, a black distillate yielded, which occurred in a wide temperature range.

The symmetrical structure of the fully oxypropylated alkylenediamines along with their reactive ones Hydroxyl groups make them z. B. on valuable intermediate products in the manufacture of pharmaceuticals, Emulsifiers, surfactants, polyester resins, agricultural chemicals, plasticizers, Vulcanization accelerators.

Claims (4)

Patent claims: 1. Process for the preparation of fully oxyalkylated, symmetrical alkylenediamines by Reaction of alkylenediamines with alkylene oxides, characterized in that alkylenediamines with 2 up to 6 carbon atoms in the presence of water or an alcohol with propylene oxide at one temperature from 40 to 200 ° in a molar ratio of 1: 4. 2. The method according to claim 1, characterized in that the reaction at a temperature from 40 to 120 °. 3. The method according to claim 1 and 2, characterized in that the alkylenediamine is ethylene diamine is used. 4. The method according to claim 1 and 2, characterized in that the alkylenediamine is hexamethylenediamine is used. Considered publications:
German patent specifications No. 642 744, 844 449. © 709 808/291 11:57