DE1805411A1 - Process for the preparation of mono- (omega-aminoalkanoyl) -diamines - Google Patents

Description

Process for the production of mono - (^ - aminoalkanoyl) diamines.

It is known that lactams can be reacted with diamines to give the corresponding υ -aminoalkanoyl derivatives of diamines. According to a process which is already part of the state of the art, this reaction is carried out at temperatures of 150 ° -500 ° C. This gives within 7 hours at 250 ⁰ C diamines in yields of less than 50 %.

According to a further, already known process, caprolactam and at least Polyamines N, N'-Bis ~ (6-aminohexanoyl} derivatives containing 2 amino groups made of diamines, and then, if per Mole diamine one mole lactam is used.

- CO + H ₂ N - R - NH ₂ ^x '

The yield should be 90 #, i.e. about half of the one « Set diamine is not converted and has to be removed by distillation. This plague position could also apply to the homologues of the caprolactam with 6-11 ring carbon atoms. Monoid) aminoalkanoyl) derivatives of diamines are under the reaction conditions this known process is not available.

It has now been found that the mono- (4 / «aminoalkanoyl) derivatives of diamines are obtained in a targeted manner and within short reaction times if lactams are obtained together with diamines in the presence of acidic catalysts and / or water at temperatures of 100% «Preferably heated between 150 and 10000 q.

The invention therefore provides a process for the preparation of N-mono- (£ j «aminoalkanoyl) diamines of the following general terms Formula 1

H ₂ N - Jc _x H _2x ) -CO-NH-R-NH ₂

where R «aliphatic, cycloaliphatic or aromatic radical and χ β 3 «li mean

from / O-aminocarboxylic acids with 4-12 carbon atoms and diamines with 2 »

000826/2084

- d -.

Carbon atoms by heating mixtures of the corresponding lactams and diamines 100-350 ⁰ C, characterized in that mixtures are from lactams and diamines in the presence of acids and / or water is heated.

Mineral acids, e.g. phosphoric acid, are suitable as catalysts or sulfuric acid, acidic salts of polybasic mineral acids, such as monosodium phosphate or monosodium sulfate, organic Acids such as adipic acid, decanedicarboxylic acid, benzoic acid, Sulfonic acid, acidic salts of polybasic organic acids, e.g. Mono-sodium citrate or Mono-Na «adipate, acidic ion exchangers, e.g., polystyrene polysulfonic acid. All these acids and salts can also be on a finely dispersed or porous carrier, which itself does not need to have any catalytic activity, e.g. porous clay discs treated with sulfuric or phosphoric acid. Even water acts like an acid in these reactions.

The effectiveness of water and acidic compounds in polycondensation of lactams is known. However, one cannot conclude from this that the same catalysts cause the reaction of lactams need to speed up with diamines. Even less predictable and therefore surprising is the fact that the catalysts mentioned prefers the formation of the N-mono ~ (4? -aminoalkanoyl) compounds accelerate in the same reaction mixture that supplies the N, N'-bis (4? -aminoalkanoyl) compound without catalysts.

The latter only arise in the procedure according to the invention in small amount as a by-product. They can be avoided almost entirely by using an excess of amine.

The catalysts according to the invention - provided they are homogeneously miscible - are effective even in very small amounts. For mineral acids the preferred range is 0.005-5 % » for organic acids 0.1-10 % and for water 0.05 * · 10 %. For example, for phosphoric acid, an addition of 0.01% by weight is sufficient . . With an addition of 0.1 wt ^ 'the reaction proceeds, for example, in caprolactam so quickly that at 200 -. 230 ⁰ C of caprolactam in Reaktionsgemisoh within J50 min to less than 4% decrease. The acid catalysis can be further improved by using small amounts of water.

009826/2054

If water is used alone as a catalyst, a significant catalysis takes place within the meaning of this invention at a content of 0.25 ^c / o . Usable reaction rates with a conversion of almost 100% in a maximum of 2 hours are obtained with a water content of 1-2%.

The reaction can be carried out either in the gas phase or in the liquid phase. The reaction mixture can, for example, be heated in a stirred tank or in liquid or gaseous form through a tube with fixed contacts. If products of high purity are required, the reaction mixture can be purified by distillation in vacuo. This is necessary, for example, when the N contained as impurities, N'-bis (Lo -aminoalkanoyl) compounds in finely divided and sparingly excrete \ filterable form.

The yields of mono (& / -aminoalkanoyl) compounds are at least 85 ^c ß> ·

The process according to the invention can be used for the preparation of mono- (tU -aminoalkanoyl) compounds of aliphatic, cycloaliphatic and aromatic diamines with 2-58 carbon atoms in the molecule, for example ethylenediamine, 1,4-diaminobutane, 1,9-diaminononane , 1,2-diaminodecane, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, diethylenetriamine, 1,4-bis ~ (aminomethyl) -benzene, benzidine, 1,4-diaminediphenylmethsn, 1,4-diaminecyclohexane and 1 amino - ^ - aminomethyl-J5,5i5-trimethylcyclohexane. These are reacted with lactams of the formula OC - C _x Hd _x -NH, where x = 3-11, for example pyrrolidone, caprolactam, onanthlactam, capryllactam, laurolactam.

It has also been found that the content of N, N ″ - bis (to -aminoalkanoyl) compounds in the reaction of branched "aliphatic and cycloaliphatic diamines" is lower than that in the corresponding unbranched compounds. In the case of the particularly advantageous trimethylhexamethylene diamines and trimethylaminomethylcyclohexylamines, the content of N, N ^f -bis (i ^ -aminoalkanoyl) compounds is so low that no distillation is necessary after the reaction.

009826/2064

th diamines which have J5 or more alkyl groups as substituents on Carrying a C-framework therefore represents a particularly favorable embodiment of the method according to the invention.

The compounds prepared according to the present invention are excellent Hardener for epoxy resins.

example 1

a). 226 parts by weight (2 mol) of caprolactam and 206 parts by weight (2 mol) of diethylenefriamine were heated to 215 ° C. in a pressure vessel and stirred for 24 hours. The excess amine was then distilled off by vacuum distillation and approx. 110 parts by weight were added. The yield of bis (6-aminohexanoyl) compound was 306 parts by weight (95 % de * ¹ stoichiometrically calculated yield). According to the material balance, mono- (6-aminohexanoyl) compounds can only be present in very small amounts.

b). 226 parts by weight of caprolactam, 206 parts by weight of diethylenetriamine and 8 parts by weight were heated to 215 ° C. for > h in a pressure vessel and stirred. The water was distilled off by letting down the pressure. About 15 parts by weight of amine were then recovered by distillation in vacuo. The residue of 415 parts by weight consisted of 567 parts by weight of mono- (6-aminohexanoyl) compound and 48 parts by weight of bis- (6-aminohexanoyl) compound

Example 2

a). 257 parts by weight (1.5 mol) of a mixture of approximately equal parts of 2,2,4- and 2,4,4-trimethylethylenediamine and 15 parts by weight (1 mol) of caprolactam became 160 parts by weight of unreacted amine distilled off in vacuo. The residue contained 175 parts by weight of bis (6-aminohexanoyl) compound (91 % of the stoichiometrically calculated amount)

b). 237 parts by weight of a mixture of approximately equal parts of 2,2,4- and 2,4,4-trimethyl! Hexamethylene diamine, 115 parts by weight of caprolactam and 0.1 parts by weight of phosphoric acid was 1/2 h at 240 ⁰ C heated . Then 87 parts by weight of excess amine were distilled off in vacuo The residue contained 258 parts by weight of mono- (6-aminohexanoyl) compound (95 % of the stoichimetrically calculated amount) and 12 parts by weight of bis- (6-aminohexanoyl) - Link.

009826/2054

example 3

1 kg of clay with a grain size of less than 5 mm was treated with 20% sulfuric acid and dried after washing with water. This contact mass was filled into a heatable glass tube. A mixture of 255 parts by weight of 1-amino-3-aminomethyl -3 * 5,5-trimethylcyclohexane and MJ parts by weight of caprolactam was passed through the catalyst tube at 240 ° C. The residence time was minutes. The outlet was cooled and the excess diamine was distilled off in vacuo. 95% of the residue consists of mono- (6-aminohexanoyl) compounds.

Example 4

197 parts by weight (1.5 mol) of 2,2,4-Trimethylhexa-methylenediamine, 197 parts by weight ä (1 mole) of lauryl lactam and 0.4 parts by weight of phosphoric acid was in a! Pressure vessel for 2 hours under stirring to 270 ⁰ C heated. 95 parts by weight of trimethylhexamethylene diamine were then distilled off in vacuo. The highly viscous liquid that remained consisted of the mono- (12-aminododecanoyl) compound of triraethylhexamethylandiamine.

/ ine ι

Claims (6)

1, process for the preparation of N-mono- (0-.aminoalkanoyl) -diamirien of the following general formula HgN- (C Hg _x ) -CO-MHuR-NHg, where R = aliphatic cycloaliphatic ^ or aromatic radical and χ = J5 - H mean from O-aminocarboxylic acids with 4 - 12 C atoms and diamines with 2 - J58 C atoms by heating mixtures of the corresponding lactams and diamines to 100 - J55O C, characterized in that mixtures of lactams and diamines in the presence of acids and / or Water can be heated. 2. The method according to claim 1, characterized in that preferably 0.005-5 % mineral acids are used. 3. Process according to Claims 1 and 2, characterized in that 0.05-10 % water is preferably used. ² I ^- * Process according to claims 1-3, characterized in that 0.1 to 10 % organic acids are preferably used. 5 · Method according to claims 1-4, characterized in that fixed or liquid acids which are not soluble in the reaction mixture can be used. 6. The method according to claim 1-5, characterized in that all-phase or cycloaliphatic diamines with at least 3 C-alkyl groups are used.