DE2739917A1 - Poly:alkylene-poly:amine(s) prodn. - by contacting hydrogenated reaction prods. of ethylene di:amine and acrylonitrile with a Gp=VIII metal catalyst - Google Patents

Abstract

Mixed ethylene-propylene-polyamines with >=4 alkylene units/mol. and >=1 ethylene unit/mol. of formula H2N-(Prop-NH)k- Prop-NH-EtH-NH-(Prop-NH)m- n-(prop-NH)1-H (I) in which Prop and Eth are the alkylene residues from propylenediamine-1,3 and ethylene diamine; k and 1 are 0-3; m is 0 or 1; and n is 1 or more. (I) and cpds. H2N-(Prop-NH)pH, where p >=4, are made by reacting hydrogenated reaction products of ethylenediamine with acrylonitrile of formula H2N-Eth-NH-Prop-NH2 or H2N-Prop-NH-Eth-NH-Prop-NH2, and/or oligomers of propylenediamine with >=2 propylene units/mol. alone or with propylenediamine-1,3, with a catalyst of a gp. VIII metal at 50-250 degrees C with splitting off of ammonia. Pref. after the reaction polyalkylenepolyamines with =3 alkylene units/mol. are sepd. from the reaction mixt. and returned to the reaction. The process is relatively simple and required fewer process stages than prior art processes. Undesirable cyclisation of the prod. is reduced to a min. and compared with some previous processes, the amt. of effluent produced for disposal is very small. The prods. are useful e.g. in papermaking and as sedimentation aids. (I) have good solubility in water compared to uniform polyalkylenepolyamines.

Description

Process for the preparation of polyalkylene polyamines

Polyalkylenepolyamines, e.g. diethylenetriamine and triethylenetetramine, have so far been produced industrially by aminolysis of chlorine or hydroxyethanes.

For example, both connections are created next to each other in the technical Conversion of 1,2-dichloroethane with ammonia to ethylenediamine. The creation of the Ethylenediamine predominates, so that the desired products are dependent on it and must be viewed as by-products. Describes a similar procedure US Pat. No. 3,462,493 with the reaction of 1,2-dichloroethane and ethylenediamine.

Common to both processes is the splitting off of chlorine in the form of Amine hydrochloride. This must be converted into free amine and alkali chloride with strong lye be disassembled. The resulting mixtures contain amine, water, alkali and salt. The work-up by distillation is because of the progressive crystallization of the dissolved salt is cumbersome and requires additional work steps. aside from that is the removal of the accumulating salt load (it corresponds in quantity to approximately amine produced) expensive and environmentally unfriendly.

The implementation is aminolysis without exposure to salt formation of ethanolamine with ammonia in the presence of hydrogen on transition metal contacts. The resulting ethylenediamine is also accompanied by many by-products here. Among them are proportions of diethylenetriamine and triethylenetetramine, however also a variety of other products, such as aminoethylethanolamine, piperazine, Aminoethyl piperazine and viscous, high-boiling polyamines with hydroxyl groups in changing number. The separation of such mixtures is always expensive and with the high-boiling fractions impossible.

The specific production of diethylenetriamine and triethylenetetramine is described in DT-OS 24 39 275. Diethylenetriamine and triethylenetetramine are obtained by condensation of ethylenediamine with elimination of ammonia according to the equations: 2H2N - CH2 - CH2 - NR2 H2N - CH2 - CH2 - NH - CH2 - CH2 - NR2 + NH3 3H2N- CH2 - CH2 - NH2 H2N - CH2 - CH2 - NH - CH2 - CH2 H2N - CH2 - CH2 - NR + 2 NH3 This reaction does not produce any water that would have to be separated from the amine.

However, the method has the disadvantage that for restraining Ring closure reactions the conversion must be limited and only relatively low molecular weight Products are created. Obtaining higher molecular weight products (e.g. with 4 to 10 alkylene units per molecule) is desirable from an application point of view. Such higher molecular weight Products are currently only available as polymers of the dangerous ethyleneimine.

The chemistry of the condensation of alkylenediamines with ring closure is refer to the following publications: (1) Martin et al, J.A.C.S. 70 1817 (1948); (2) U.S. Patent 2,267,686; (3) DT-PS 870,416; (4) Nippon Kagaku Zasshi 82, 1700 (1961); (5) Kindler, dear. Ann. 644, 23 ff; (6) U.S. Patent 3,151,115; (7) DT-QS 25 32 871; (8) Poppelsdorf et al, J. Org. Chem., 26, 131 (1961).

According to DT-OS 25 40 871, the procedure of DT-OS 24 39 275 use for the production of polymers of propylenediamine-1,2 or propylenediamine-1,3.

It has now been found that the production of polyalkylene polyamines, the mixed or uniform polymers of propylenediamine-1,3 and optionally Ethylenediamine and which are either represented by the general formula I H2N- (Prop-NH) k-LProp-NH-Eth-NH- (Prop-NH) m - (Prop-N) 1-H (I) or the general formula II H2N- (Prop-NH) pH (11) can be represented, with at least four alkylene units per molecule, with Prop and Eth each being the Alkylene radicals of 1,3-propylenediamine or ethylenediamine are k and 1, respectively Values from 0 to 3, m can assume the values 0 or 1, n can assume a value of 1 or more and p means a value of at least 4, in a simple and clear manner succeeds if you hydrogenated reaction products of ethylenediamine with acrylonitrile the general structure H2N-Eth-NH-Prop-NH2 (III) or

H2N-Prop-NH-Eth-NH-Prop-NH2 (IV) and / or oligomers of propylenediamine with at least 2 propylene units in the molecule by itself or with propylenediamine-1,3 with elimination of ammonia on a catalyst made of metals from group 8 of the periodic table the elements converts at a temperature of 50 to 2500C.

Preference is given to catalysts of the type mentioned in a fixed arrangement Shape used.

Polyalkylenepolyamines with a content of less are preferred separated as 4 alkylene residues from the resulting reaction mixture and the reaction fed back. The separation can be carried out by distillation, if appropriate under reduced Pressure, happen.

The idea on which the invention is based is that in the reaction mixture only a relatively low concentration of monomeric propylenediamine and an excess to maintain already preformed oligomers. In general, a molar ratio should be from monomeric propylenediamine, if used, to oligomeric polyamines of 1: 2 must not be exceeded. Analogously, it can refer to a chemically uninvolved Solvents are dispensed with. On the other hand, when implementing in subordinate Amounts based on 1,3-propylenediamine, still ethylenediamine and / or 1,2-propylenediamine can also be used. This modification of the procedure is only possible under special circumstances economic prerequisites may be necessary because especially ethylenediamine is a relatively expensive raw material.

The preferred operating temperature for the process is 150 to 220, in particular 160 to 2000C, a catalyst being expediently used, containing cobalt or nickel on a suitable carrier. With a certain chance of success Can also be a catalyst based on these metals in unsupported Use form.

The use of catalysts containing cobalt is particularly preferred and nickel in addition to a smaller amount of copper on an aluminum oxide carrier, the heavy metal content being about 10 to 40 percent by weight.

Catalysts of the type mentioned are already known per se; she are, for example, used industrially on a large scale for aminating hydrogenation; Manufacturing regulations for suitable catalytic converters are e.g. DT-PS 11 72 268, U.S. Patent 2,225,059 and Org. Synth. 26, 77 can be found. A summary presentation finds in Houben-Weyl, Methods of Organic Chemistry, 3rd Edition, Volume 4/2, p. 137 ff. It should be mentioned that the present reaction is not a hydrogenation reaction can be considered, but on a catalytically induced elimination of ammonia is based. If the ammonia content in the reaction mixture is increased by the addition of gases, e.g. Nitrogen, is decreased, the conversion to polyamine increases. A preferred one used Gas is hydrogen. It can both dilute or discharge the ammonia, as well as suppressing the formation of colored by-products through its hydrogenation effect. Gas pressures of up to 250 bar in the reaction medium are useful and practical, among other things.

The reaction can be carried out or until complete implementation be terminated beforehand without affecting the quality of the reaction products is recognizable; this means that, if appropriate, monomeric 1,3-propylenediamine is returned. In relation to the monomeric propylenediamine, calculated with a residence time of 1 to 4 hours at an average reaction temperature.

The for the production of mixed poly-ethylene-propylene-polyamines or Starting materials required for polypropylenepolyamines are obtained, for example, advantageously, if one mole of ethylenediamine or propylenediamine-1,3 with 1 to 2 moles of acrylonitrile converts and the reaction product, which has the structure NC-CH2-CH2-NH-CH2- (CH2) 1> 2-NH2 or NC-CH2-CH2-NH-CH2- (CH2) 1,2-NH-CH2-CH2-CN, in the usual way hydrogenated.

Propylenediamine-1,3 is produced by aminating hydrogenation of acrylonitrile easily accessible.

The work-up of the reaction products obtained during the implementation happens in many cases by distillation. Unreacted propylenediamine is optionally obtained as a low-boiling component and can be added to the process can be fed back in without any additional cleaning operation. The procedure can Consequently in combination with a reaction tube and a distillation plant carried out particularly advantageously in a closed, continuous cycle will. A thin-film evaporator is particularly advantageous as the distillation device to use.

But it must be said that the method of the invention is very pure Can supply products; so you can in cases where relatively high molecular weight products of a broader molecular weight range can be readily produced refrain from distillation because these products are colorless. The polyamines obtained are important substances that are used, for example, in paper production and as sedimentation aids to be needed.

The mixed ethylene-propylene-polyamines obtainable according to the above formula (I) are particularly valuable products.

Due to their irregular structure, they tend less than the pure ones Ethylene or propylene polyamines cause disruptions in production or processing. Above all, the good solubility in water should be emphasized while uniform Polyalkylenepolyamines form poorly soluble, sometimes rock-hard hydrates with water.

Example 1 1,2-ethylene diamine is placed in a stirred tank at 500 ° C and at this temperature acrylonitrile is added until a molar ratio of 1: 1 is reached is. The hydrogenation in the presence of ammonia with subsequent distillation In addition to unreacted ethylenediamine (10%), N-aminopropyl-ethylenediamine-1,2 (70 %; Sp. 78-810/3 mbar) and N, N'-bis-aminopropyl-ethandiainine-1,2 (20%; Sp. 137 ° / 0.4 mbar).

For the production of polyamine, 800 ml of a contact made of 3 mm strong extruded strands of aluminum oxide, which are soaked with 25% cobalt salt and put in the oxidic form are converted into one Pressure reactor at 250 bar hydrogen and a temperature rising to 250 0C into the reactive form brought. The pressure is then set to 50 bar and the temperature to 170.degree and a continuous flow of 100 ml / hour. N-aminopropyl-ethanediamine-1,2 over directed the contact. In addition to the liquid reaction products, 150 ml / hour. a hydrogen-ammonia gas mixture is discharged.

The liquid-viscous discharge is carried out on a thin-film evaporator 1800/5 mbar in a distillate (30%; main proportion aminopropylethane diamine) and a separated non-boiling, colorless-viscous portion.

According to elemental analysis, this contains 32% nitrogen; the titration with aqueous hydrochloric acid shows that all nitrogen is strongly basic. The salary on primary amino groups is reacted with 2,4-pentanedione (Critchfield and Johnson; Analytical Chemistry, Vol. 29, 1957, 1174 ff.) Determined to be 12.9%.

There is no tertiary bound nitrogen (reaction with excess Acetic anhydride and titration against perchloric acid). The total basic difference Nitrogen minus primary nitrogen "provides N (sec) = 19.3%; the ratio N (prime) N (sec) is 2: 3, corresponding to a linear connection of 5 N atoms. The relationship the athenane and propane bridge members are found to be 1: 1 by mass spectroscopy.

In contrast to that after the same reaction from N-aminopropyl-propanediamine-1,3 The polyamine obtained, which forms a rock-hard hydrate with water, is the after The polyamine obtained in the example is miscible with water in any ratio.

Example 2 Cobalt oxide in strand form is tempered in a muffle furnace and converted into metallic form at 2500 and a hydrogen pressure of 250 bar.

A high-pressure reactor in tubular form contains 800 ml of the pretreated in this way Contact. At a temperature of 1800C and one set with hydrogen At a pressure of 60 bar, 200 ml of bis-aminopropyl-ethanediamine are passed through the contact every hour directed.

200 Nl of a gas mixture hydrogen / ammonia are emitted every hour relaxed the reactor; The liquid discharge is evaporation in a thin film 1800/1 mbar subjected, with 20% of a distillate consisting of used Bisaminopropyl-ethanediamine and 80% of a non-boiling under these conditions light brown, viscous oil of the composition C 61 los H 12%, N 27% will. All nitrogen is strongly basic. According to that described in Example 1 Analysis method accounts for 5 to 6 secondary nitrogen atoms for 2 primary nitrogen atoms, i.e.

the mean chain length of the polyamine is 7 to 8. The content of tertiary bound nitrogen is less than 1%. That determined by mass spectroscopy The ethylene / propylene ratio is 1: 2.

The polyamine is miscible with water.

Example 3 The mixture of 20% nickel hydroxide and 80% alumina hydrate is dried, pressed to 3 mm strands, tempered and the molded bodies obtained cut into pieces of 4 - 5 mm in length.

A tubular reactor is filled with 800 ml of these shaped bodies and these at a temperature rising to 2500 in the course of several hours with hydrogen treated under a pressure of 250 bar. A temperature is then established in the reactor of 1800C and a pressure of 25 bar with hydrogen. Become hourly 200 ml of a mixture of equal parts by weight of 1,3-propanediamine and 1,2-N-aminopropyl-ethanediamine directed via the contact. Gases in the vicinity of 300 Nl are used in the same period relaxed from the reactor.

A part of the resulting liquid-viscous reaction mixture becomes from a flask out on a 30 cm long packed column fractionated distilled. At 137 - 1400/1000 mbar, propanediamine is initially transferred (10%), then up to 1100/20 mbar N-aminopropylethane diamine (15%), both starting materials. the The next fraction (8%) boils at 110 - 1200/20 mbar, has 32 w basic nitrogen and, according to gas chromatographic analysis, consists of dipropylenetriamine. The next one Fraction (22%) boils from 140 to 1800/1 mbar 'has 32% basic nitrogen and According to gas chromatographic analysis, contains 80% N, N'-bis-aminopropyläthandiamin-1,2 besides 20% tripropylenetetramine. The higher-boiling parts are at room temperature a viscous, pale yellowish colored polyamine with 28% basic nitrogen. The levels of primary to secondary nitrogen are like 2: 6.5. The polyamine is completely soluble in equal parts of water.

The proportion of polypropylene polyamine in the resulting polyamine is found thus as subordinate. Comparative admixtures (15%) of polypropylene polyamine to polyamines of Examples 1 and 2 solidify on addition of water.

Example 4 Equal parts by weight of N-aminopropyl-ethanediamine and N-aminopropyl-propanediamine-1, are reacted at 1800/50 bar hydrogen, as described in Example 3. 82 % of the reaction mixture obtained boil over 1800/1 mbar. It contains 27.5% basic Nitrogen; the molecule contains 8 nitrogen on average.

The polyamine is completely soluble in water.

Claims (4)

Claims Mixed ethylene-propylene-polyamines with 4 or more Alkylene units per molecule which contain at least one ethylene unit per molecule, of the general formula H2N- (Prop-NH) k- [Prop-NH-Eth-NH- (Prop-NH) m in ~ (Prop-NH) l-H (I) with at least four alkylene units per molecule, with prop and eth respectively denote the alkylene radicals of 1,3-propylenediamine and xthylenediamine, k and 1, respectively Values from 0 to 3, m the values 0 or 1 and n a value of 1 or more can. 2. Process for the preparation of polyalkylenepolyamines of the general Formula H2N- (Prop-NH i Prop-NH-Eth-NH- (Prop-NH) m-, n- (Prop-NH) 1-H (I) or H2N- (Prop-NH) pH (II), with at least four alkylene units per molecule, with prop and eth respectively the alkylene radicals of propylenediamine-1,3 or Xthylenediamine, k and 1 each have values from 0 to 3, m the Values 0 or 1, n can have a value of 1 or more, and p a value of means at least 4, characterized in that one hydrogenated reaction products of ethylene diamine with acrylonitrile of the general structure H2N-Eth-NH-Prop-NH2 (III) or H2N-Prop-NH-Eth-NH-Prop-NH2 (IV) and / or oligomers of propylenediamine with at least 2 propylene units in the molecule by itself or with propylenediamine-1,3 with elimination of ammonia on a catalyst made of metals from group 8 of the periodic table the elements converts at a temperature of 50 to 2500C. 3. The method according to claim 2, characterized in that one Maintains a temperature of 150 to 2200C. 4. The method according to claim 2, characterized in that from separating polyalkylenepolyamines from the reaction mixture obtained in the reaction, which contain 3 or fewer alkylene units per molecule and the reaction again feeds.