DE1130809B - Process for the preparation of polyamines or polyaminoamides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY KL. 12o 27

INTERNAT.KL. C 07 C

GERMAN

PATENT OFFICE

EXPLAINING EDITORIAL 1130 809

Sch27331IVb / 12o

REGISTRATION DAY! July 19, 1958

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL: JUNE 7, 1962

Basic derivatives of natural fatty acids, such as fatty amines, z. B. stearylamine and oleylamine, as well as polyaminoamides, these are basic condensation products from fatty acids and polyamines, have found a wide range of applications in technology. The known Connections of these classes have some disadvantages for technical application, some of which are due to this are based on the fact that they are solid at room temperature, partly on the fact that the alkyl radical of these products is not basic groups. The invention now relates to the extraction of basic substances at room temperature liquid derivatives of oleic acid which have an amino group in the alkyl radical.

There has now been a process for the preparation of polyamines or polyaminoamides of the general formula

Method of manufacture
of polyamines or polyaminoamides

Applicant:

Schering Aktiengesellschaft,
Berlin N 65, Müllerstr. 170-172

Dipl.-Chem. Dr. Eugen Griebsch, Berlin-Britz,

and Dipl.-Chem. Dr. Martin Wallis, Berlin-Tegel,

have been named as inventors

(CH ₂ ) _7oleS - CH - - - (CH ₂ ) _raerT - X

CH ₃

where X is a - CH ₂ - NH ₂ group or a substituted acid amide group in which the substituent on the amido group still contains primary and / or secondary amino groups, and where Y is either hydrogen or the atomic grouping

CH ₃

represents, found, which is characterized in that oleic acid or its ester or oleylamine in the presence of concentrated sulfuric acid, hydrocyanic acid accumulates, the primary formylamine compound saponified and, if one started with oleic acid or its esters, the resulting Aminostearic acid

a) either reacts with polyamines to give the corresponding aminoamides or

b) ^{treated si em in the} presence of acid-binding agents with phosgene and then reacted with polyamines to polyaminoamides.

This method can be used, for example make the following connections:

CH

NH ₂
CH ₃ - - (CH ₂ J ₇ -SKg-CH -

NH ₂
CH ₃ (CH ₂ ) _7W8 - CH

CH ₂ NH ₂

η CO NH CH ₂ CH ₂ NH ₂

IsodeFT CO NH CH ₂ CH ₂ - NH - CH ₂ CH ₂ NH ₂

NH ₂ (3)

or higher homologues of the ethylene and propylene series

H ₂ N CH ₂ CH ₂ HN CO (CH ₂ ) _815r7 - CH NH CO

Ws-CH ₃

- NH CH

sr, - CO - NH CH ₂ CH ₂ NH ₂

"8" ~ CH ₃ 209 608/367

It was not foreseeable that the breaking of the double bond would e.g. B. in oleylamine and also, for example, in oleic acid leads to amine products which are liquid at room temperature and have a low viscosity. Usually arise - such as B. in the hydrogenation to stearylamine or stearic acid - compounds which are solid at room temperature. So z. B. stearylamine has a melting point of 53 ° C; However, 1,9-1,10-diaminooctadecane is liquid at room temperature, its viscosity is 0.42 poise; Stearic acid methyl ester, however, has a melting point of 38 ° C, 9- and 10-Oxystearinsäuremethylester such of 31 ⁰ C ₃ 9- and 10-Aminostearinsäuremethylester is liquid at room temperature, its viscosity is 0.46 poise. The reaction product of stearic acid and diethylenetriamine is solid, the analogous product of 9-10-aminostearic acid, on the other hand, is liquid, and its viscosity is 8.8 poise.

When reacted with epoxy resins, the new compounds produce plastics with very good properties. In addition, the compounds which can be prepared according to the invention can be used industrially in many ways. They result in advantageous combinations with phenolic resins, isocyanates or urethanes. Furthermore can use them as plasticizers or intermediates for other find organic syntheses use.

example 1

1 kg of oleylamine with the amine number 82, dissolved in 1500 ecm of ethylene chloride, were ^{cooled to 0} ° C. in a 4-1 flask with stirring and 200 g of anhydrous hydrocyanic acid were added. In the course of 2 hours, 2 kg of concentrated sulfuric acid was added dropwise while the temperature was kept below 4O ⁰ C. After 31 ice water had been added, the reaction product was then refluxed for 2 hours for saponification and the ethylene chloride was first distilled off. After making the solution alkaline, the crude diamine was separated and dried. The crude yield was 990 g. The amine number of the product obtained was determined to be 345. For purification, the crude product was subjected to vacuum distillation, where pure diaminooctadecane with an amine number of 394 passed over at a boiling point of 190 to 195 ° C. at 1 mm pressure. D ₂₀ = 0.847, n% ° = 1.4630, η = 0.42 poise.

Example 2

175 g of raw methyl 9- and 10-aminostearate, obtained by amination of oleic acid analogously to Example 1 and subsequent esterification heated to 200 ° C. for 3 hours with 420 g of diethylenetriamine. The excess diethylenetriamine was im Distilled off under vacuum. The resulting aminostearic acid aminoamide had an acid number of 0.9 and one Amine number of 405, the viscosity was 8.8 poise.

Example 3

Phosgene was introduced into a soda-alkaline solution of 200 g of aminostearic acid, prepared according to Example 2, at room temperature with stirring until no more amino groups could be detected. After acidification, the deposited carbonyldi (aminostearic acid) was separated off and dried.

190 g of the carbonyldi (aminostearic acid) were mixed with 150 g of diethylenetriamine with stirring for 3 hours heated to 200 ° C and then distilled off the excess diethylenetriamine in vacuo.

Example 4

275 parts of methyl aminostearate, obtained according to Example 2, were mixed with 190 parts of tetraethylene pentamine Heated for 3 hours with stirring to 180 ° C. in the nitrogen atom. A liquid product is created with the viscosity 20 poise, the amine number 557 and the saponification number 0.

Claims (1)

PATENT CLAIM: Process for the preparation of polyamines or Polyaminoamides of the general formula CH ₃ H- NY in which X is a —CH ₂ —NH ₂ group or a substituted acid amide group in which the substituent on the amido group still contains primary and / or secondary amino groups, and Y either hydrogen or the atomic grouping - CO NH CH (CHJiöüsr- ^x (CH ₂ ) rssifs ~ " CH ₃ represents, characterized in that hydrocyanic acid is added to oleic acid or its esters or to oleylamine in the presence of concentrated sulfuric acid, the formylamine compound formed is saponified and, if oleic acid or its esters are used, the aminostearic acid formed a) either reacts with polyamines to give the corresponding aminoamides or b) treated with phosgene in the presence of acid-binding agents and then with polyamines converts to polyaminoamides. © 209 608/367 5.62