DE1215373B - Process for the preparation of linear or branched polypropylene glycol ethers with amino groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN JmVml · PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C08g

German class: 39 c-30

1215 373
F37297IVd / 39c
July 12, 1962
April 28, 1966

It is known that alcohols with primary or secondary hydroxyl groups can be converted into amines with ammonia or amines in the presence of a hydrogenation catalyst ("Methods of Organic Chemistry", Houben-Weyl, 1957, 4th edition, Vol. 11/1, p. 126 to 134). Triethylene glycol has also been treated in this way with ammonia and amines. However, it was already shown that the reaction no longer proceeds as completely and only some of the hydroxyl groups are converted into amino groups. If polyethylene glycol is used, then the replacement of the OH groups by NH ₂ groups by means of ammonia only takes place with a very inadequate reaction rate and unsatisfactory yield.

From US Pat. No. 2,522,155, polyethylene glycols with predominantly primary hydroxyl groups are known in the presence of a dehydration catalyst such as sulfuric acid, phosphoric acid, hydriodic acid, preferably in the presence of a solvent with ammonia or amines with elimination of water to form polyether glycols with amino end groups to implement. A disadvantage of this process is the incomplete implementation.

The invention now relates to a process for the production of linear or branched polypropylene glycol ethers with primary or secondary amino groups, which is characterized in that one has linear, predominantly secondary terminal hydroxyl groups containing polypropylene glycol ethers or predominantly secondary terminal hydroxyl groups having adducts of propylene oxide, optionally together with minor Shares of other alkylene oxides, of compounds with several reactive hydrogen atoms as starter molecules, with ammonia or a primary amine in the presence of a hydrogen-transferring one Reacts catalyst at elevated temperatures.

It was not to be expected that this process can be carried out in a simple manner with very good yield and with good quality, both on a small scale and on an industrial scale, when one considers that in the reaction of triethylene glycol with ammonia after 31 hours only 18 "vol In addition, the polypropylene glycol ethers contain essentially secondary hydroxyl groups, which are known to react more slowly than primary aliphatic hydroxyl groups, so that the reaction of polyhydroxyl compounds with amines even by processes for the production of linear or
branched polypropylene glycol ethers with
Amino groups

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Dr. H. c. Dr. e. H. Otto Bayer, Burscheid;

Dr. Rudolf Schröter, Neuenkirchen;

Dr. Friedrich Möller, Leverkusen-Bayerwerk

it is feasible that the primary hydroxyl group reacts almost exclusively. Furthermore, it was to be assumed that the accumulation of the quite reactive ether groups gives rise to side reactions such as splitting and aminolysis could give.

Suitable starting materials for the process are all polypropylene glycol ethers, be they linear or branched, the chains of which consist of three or more propylene oxide residues. You can click on the received in various ways. The process is particularly suitable for polypropylene glycol ethers with a molecular weight of about 1000 to 4000. This includes both the polymerization products of propylene oxide itself and its addition products to compounds with two or more reactive hydrogen atoms. The polypropylene glycol ethers can also be constructed asymmetrically, such that at the addition start component z. B. only one hydroxyl group is etherified with a polypropylene residue. To the polypropylene glycol ether in the sense of the present Invention also include those that, in addition to the polypropylene glycol residues, proportions of ethylene glycol or contain butylene glycol residues. The polypropylene glycol ethers contain essentially secondary ones Hydroxyl groups, but some primary hydroxyl groups can also be present.

Ammonia and amines, for example aniline, cyclohexylamine, propylamine, are used for the reaction, Butylamine or toluidine.

The general guidelines for carrying out the reaction can be found e.g. B. in »Methods of organic Chemie ", Houben-Weyl, 1957, 4th edition, Vol. 11/1, pp. 126 to 134. Examples of hydrogenation catalysts include Raney nickel, Raney cobalt activated with precious metals

609 560/531

can, copper chromite, palladium, platinum in question. In general, 1 to 10% of the catalyst is used, based on the polypropylene glycol ether to be converted.

You use the ammonia or the amine in excess, which is also quite large - about up to 30 moles - can be. The reaction temperatures are generally 150 to 250 ° C, but can also be exceeded or fallen below, depending on the reaction components. In the case of volatile compounds, especially with ammonia, you will work under pressure, which is easily up to 300 atm and can be more.

In general, the use of solvents is not necessary. If solvent is used they should be inert, e.g. B. hydrocarbons, tetrahydrofuran or tert-butyl alcohol.

With sufficient exposure to the ammonia or the amine, all of the hydroxyl groups of the polyhydroxyl ether become converted into amino groups, which in the case of ammonia are of primary nature. Depending on the reaction time, reaction temperature, type and Quantity ratio of the components can also be obtained products, which in addition to the formed Amino groups still contain hydroxyl groups in the molecule.

The polypropylene glycol ethers obtained, which either only have amino groups instead of the OH groups or contain amino groups in addition to hydroxyl groups and which also, depending on the reaction procedure Accumulated in a mixture and can be used as such are versatile products. They are polyadduct formers for epoxy resins and can also be converted into polyureas, which are suitable as plasticizers, or they serve as containing formaldehyde or methylol groups Resins to be crosslinked molding compounds, binders or textile finishing agents.

example 1

1000 g of polypropylene glycol ether, obtained by polymerizing propylene oxide in the presence, are poured in of aqueous sodium hydroxide as starter and catalyst (molecular weight 1870; OH number 62.4), 220 g of liquid ammonia and 80 g of dehydrated Raney nickel in a 5-1 stirred autoclave, added the pressure with hydrogen to 20 atü and heats in 2 hours to 220 ° C. The pressure rises to 127 atmospheres and falls to 120 atmospheres in the course of about 3 hours. The reaction is carried out for a total of 8 hours by. It is allowed to cool, relaxed at about 60 ° C. and the contents of the autoclave are pressed through a pressure filter. The light-colored filtrate is removed from the water of reaction under reduced pressure at 100 ° C. until the weight is constant freed. 922 g of a diamine with a content of 95% are obtained. Due to the ίο analytical examination, the remainder consists of a polyamine with secondary nitrogen. Tertiary Amine nitrogen is absent.

Example 2

A mixture of 250 parts by weight of polypropylene glycol (adduct of propylene oxide with Trimethylolpropane with sodium alcoholate as a catalyst; Molecular weight 3000; OH number 59), 80 parts by weight -liquid ammonia and 16 weight-

ao share Raney nickel is under an initial hydrogen pressure of 30 atm. Stir to 220 ° C heated. The pressure falls from 166 to 160 atmospheres over the course of 9 hours. Allow to cool, filter and work the crude product, as described in Example 1, on.

This leaves 242 parts by weight of a weakly colored triamine which, according to its analysis, has a purity of 93% has.

Claims (1)

Claim: Process for the preparation of linear or branched polypropylene glycol ethers with primary or secondary amino groups, characterized in that linear, predominantly polypropylene glycol ethers containing secondary terminal hydroxyl groups or predominantly addition products of propylene oxide containing secondary terminal hydroxyl groups, optionally together with small amounts of other alkylene oxides, of compounds with several reactive hydrogen atoms as starting molecules, with ammonia or a primary amine in the presence of a hydrogen transfer catalyst at elevated levels Temperatures. Considered publications:
U.S. Patent No. 2522 155. 609 560/531 4.66 © Bundesdruckerei Berlin