DE1933866A1 - Separation process - Google Patents

Description

concerning:
"Separation Process"

The priority of filing in Great Britain July 1968 is used.

The present invention relates to the separation of salts, which have an increased proportion of the salt of the trans-trans isomers have, from salts of mixtures of the isomers of 4,4'-diaminodieyclohexy! methane.

4, 'I'-Diaminodicy clohexy! Methane is a well-known compound which occurs in three geometrically isomeric forms, namely the cia-cie-, the cis-trans- and the trans-trans-Forra. It is often referred to under the abbreviation PACM cited and is used in the following description in the interests of convenience

ÖAD ORIGINAL

90988371735

Spelling: kissed in the same way.

PACM wii'd iibll & hsrweise duroh catalyvisohe hydrogenation of 4 _s 4 ^? -Difiimlnodiphsny lme than using a variety of τοη catalysts, κ.3. of ruthenium and its compounds, produced and obtained as a hall-proof mixture of the three gaometric isomers ". The mixture can approximately contain 50 % deo fcranstrans isomers; the rest usually consist of ciss-trana-13OBie-3cen together with a small proportion, usually not more than 10 %, of cis-cis isomers.

The trans-trans-Isomsra of PACM is a valuable intermediate product for the production of Polymsrsn and because of the geometrical configuration of this Laomsren especially in the production of polyamides, which are used for the Fabrication of synthetic fibers _a useful.

Ea were indeed baraits procedures £ ur separating the geometric Isomers of PACM, see B. by crystallization from solvents, suggested, but there is always a note * Licher proportion of the trans-trans isomers in the cis-cis, ice-tranB mixture.

It has now been found that when PACM is in the form of its salts with Dicarboxylic acids are subjected to a simple water wash,

"" ■ '"' ■■■ '^ BAD ORIGINAL

■. ■■ - ■ - ■■■■■: .. ■■ "- '■" - 3 -

909883/1735.

the insoluble sale remaining after the water treatment has an increased trane-trans-aehe.lt and either as such isolated or "by treatment with alkali to one PACM can be converted back from increased trans-trans content can.

So, therefore, according to the present invention, a method for the separation of salts which methanes an increased proportion of the salt of the trans-trans isomers have, of salts of a mixture of the stereoisomers of 4, ¹ J'-Diaminodicyclohery! With dicarboxylic acids Rait dera indicator created by subjecting the original string to a water wash and separating the solid salt, which has an increased proportion of salt of the transtrane isomer, from the liquid phase.

Mixtures of the geometric isomers of PACM for the salts, to which the present process can be applied, can be prepared in any way, for example by reducing 4.4. The proportions of the various isomers in a mixture thereof can be determined approximately from the melting point of the mixture or by using the nuclear magnetic resonance method. In this way it is possible to increase the proportion of the existing trans-trans isomers before and the separation process su determined by the application, and to determine how much of the _s availability

909883/1735

- Ij _

has been separated off trans-trans isomers. Such * Determinations are usually made on the free PACM and not carried out on its salts ο The free FACM can from the salt very easily by treatment with aqueous alkali and then Extraction can be regenerated with an organic solvent «

The salts of PACM employed in the present process can be salts of any dicarboxylic acid, although salts of dicarboxylic acids having an overall number of carbon atoms, including the carbon atoms in carboxyl groups _9, greater than 6 are preferred. The process is also preferably carried out with salts of aliphatic dicarboxylic acids.

Examples of dicarboxylic acids include βk & HDeeandioic acid, Of, <γ-dod8aandioic acid _? Succinic acid, azelaic acid _a sebacic acid, glutaric acid, adipic acid _p phthalic acid and isophthalic acid c.

A particularly preferred aliphatic dicarboxylic acid is fef-dedeandioic acid; ca has been found ₃ that it is possible with this acid, the. for the most part the trans-trans-18ome: s to be separated from an isomer mixture ₃ while the main part of the ois-sia and cis-trans isomers remains.

BAD OWGLAL

- 5 909883/1735

The sals; © this special acid, are therefore selective! · Usable than those of the other acids and can not only be separated from the isomars of increased trans-trans content, scmd & rn also sur manufacturing iron practically pure trane-trans-FACM © ingesetst warden »

Sals® of PACM for dis Ve.vwimclung in the irorliegendam ITER egg can the standard procedure ₉ sB reaction of PACM and of the appropriate dicarboxylic acids in a Lösimgsinit & iil vrie säoB by any one. Ethanol and Isolation of the Salt from && 1? LSaimg by cooling, filtering and drying _s stoves.

The Tsrfahren ä®a "Torliegenden invention, by simple Rüfesran © IN82 ^s tSuspensiion of salt, preferably in einam fei nen physical state in Wass' r bsi Raumi; ^ inperatui ^j j t warden by 3®rüfe'3 to give the firm? Material e.g. by FiI-.Nation. dull zesstrifugation is removed and the solid is dried, resulting in a salt that contains an increased proportion: M: 5 ßalsss the t ^ ans-trans isomer.

To.rsiig3 ¥ ei3is the SaIs in water to a temperature of mthr: than. Heated to 50 ° C, the suspension to room temperature. » cooled and the imgeldste solid separated and dried.

, BAD ORIGJNAi '. "" ■ "- 6 -

909883/173 5

The method of the present invention can also be used using sines 3aises made in situ in water was carried out, whereby you can accordingly mix PACM and the appropriate diacid in water, the suspension is heated to ensure the reaction of salt formation and then cooled, and the enriched trans-trans sals ^ on of the aqueous phase «isolated.

It was used for the preparation of a Sal333 for use in the present invention as found convenient, _p aquimolakulare proportions of dicarboxylic acid and -VkQVx au use can be although lower or higher levels of dicarboxylic acid desired enfalls used.

It is neither the temperature _a at which «:? which are not treated with water, necessarily decisive, nor the temperature at which the insoluble, trans-trans-enriched salt is removed from the aqueous pimaa _a bucket ed, however, it is difficult to see that this depends at least in part on which special dicarboxylic acid is used -Salt has been applied. It can be assumed that the present process depends on the lower solubility of the salts of the tranatrans-boaeren in comparison with the salsa of the cis-cis and cis-trans isomers, and that this ratio depends slightly on the salt of one acid dam someone else

6AD ORIGINAL

- 7 909883/173 5.

different temperatures can vary,

In the case of the above-mentioned Dodeessidioio-Salsee it was found convenient the trans »tr © si @ -Sals at indoor or room temperature remove·

the "desired" kaira that free PACM from an isolated SoIm with increased fcrans-tr & as content by treatment with a base "ie sB" an alkali metal hydrocyanic acid, followed by solvent extraction "be regenerated

The amount of seu vorwendandeis water may vary depending on the particular SaIs and d © i? Temperature at which the trans-trane-rich Sale to be separated from the aqueous phase varies will. The amount of wagons can also vary depending on whether you have a Sal «can be obtained with practically pure trane-fcrans-isomex-en wishes or whether only the enrichment of the trans ~ tr & ns coaponents to a certain degree, varies will.

The present process can be used either for the separation of a salsa dea practically pure trans-trans isomers from PACM or for the separation of a mixture of salts of the isomers which are enriched with regard to the fcrana-trans-Ieomer,

"8ADOfWGlNAL - 8 -

909883/1735

can be applied. After separation of the practically pure trans- ' trans-Salses or the enriched trans-trans material the water, the aqueous solutions can be treated further in order to regenerate a PAGM which has an increased cis-tranß content. When you get the salt of the practical has separated pure trans-trans isomers, it is through this Extension of the present process possible to obtain a further »product see below, which largely contains the cis-trans isomer is.

The trans-trans enriched salt produced by the process of the present invention can be used as an intermediate for the oil production of polyamides, i.e., öd can be converted into a polyamide by heating, which repeating 3 structural units of the formula

-OC-R-GO-NH-CH CH- GH ₉ - CH; CH -NH-

^N CH - CH ^X CH - CH ₂

contains, wherein R is the remainder of the dicarboxylic acid and the Diaminodicyclohexylmethsn-part mainly the trans-translEcmere is. At your choice, dae tr-aas-trans-enriched free area regenerated and for · the production of polyamides

BATH

90 988 3/173 5 ~ ⁹ "

through conversion with dicarboxylic acids or amide-forming derivatives the same has been used.

The trans-trana-enriched, free, regenerated from the salt Aain can also be converted into the corresponding diisocyanate by phosgenation, and the diisocyanate can then be used in the production of polyurethanes Find.

Both, including the polyamides and polyurethanes mentioned above bsaitsGß valuable fiber-forming properties, which result from the hearing of the trans-trans isomer in the diaminodicyelohexylmethane portion can be increased.

The invention is illustrated, but not limited, by the following examples, in which all parts are parts by weight and all percentages are percentages by weight, unless ₁ , something else is expressly mentioned.

Example 1 {salt made in aitu in water)

A® mixture of PACM (containing about 34 % trans-trans isom «res) (21 parts),«, (O-dodaoandioic acid (23 parts) and water (480 parts) was heated to 90 to 95 ° C. with stirring and Maintained at this temperature for 2 hours.

SAO ORfStNAL

- to -909883/1735

- Io -

Amount of solids remained in suspension. The mix was cooled, filtered and the filter cake dried

Weight of the dried, purified salt = 15 _S 2 parts, ie 3 ^; 4.5 % of the total solids introduced. A sample of the dried product was suspended in water and made alkaline, and the liberated PAGH was extracted with chloroform. The chloroform solution was dried, filtered and checked by means of nuclear magnetic nucleation spectroscopy. The PACM was found to be 97 % trans-trane isomer.

Example 2

A sample of the o & w-dodocandiolesic acid salses from PAGH wnrfii by dissolving FACH (34 % trans ~ fcra?>. 3) (21 part a) and ^ Ö-dodeandioic acid (23 parts) in hot ethanol (22 * 1 part K cooling, filtration and drying produced and yielded

37.6 parts = 86 % of the total solids introduced "20 parts of this PACM salt were suspended in wa33er (300 parts)," heated to boiling, cooled and filtered. Dex fluorescence was dried and gave 8 _S ? Share some solid matter. This was made alkaline and extracted with chloroform as in Example 1. According to the nuclear magnetic resonance investigation, the PAOM obtained contained at least 97 % of trans-trans isomers.

BAD LOCAL ■ '■ -....-....... -Ii-

909883/1735 '.

Example 3

A sample of the Dodecandioicsäure-Salées of PACM was "% trans trans isomer ο s prepared from PACM containing 3 ¹ and as isolated in 86-f yield from ethanol in Example 2. Fig. 13 parts of this salt were stirred with 80 parts of water at room temperature for 2 hours, filtered, washed with 80 parts of water and, after drying, gave 8 parts of purified salsa.

This was made alkaline and extracted with chloroform as in Example 1. The check by nuclear magnetic resonance showed that the PACM obtained contains at least 65 % of trans-trana isomers.

Example * J

A mixture of isophthalic acid (16.6 parts), PACM (with a content of approximately * \ 8% of trans-trans isomer) (21.0 parts) and Wasβer (230 parts) were heated with stirring to 90 ⁰ C and 1 Maintained at this temperature for one hour. It was then cooled down to below 20 ° C. and the suspended solid was filtered off. This was washed on the filter twice with 50 parts of cold water and dried in an oven at 70 ⁰ C. There were 12 _s l parts PACM Tsophthalat, equivalent to 32.1% of the total filled solids obtained.

6AD ORIGINAL

- .12 -

909883/1 735

A sample of this PACM isophthalate was heated with an aqueous solution of sodium hydroxide to decompose the salt. The mixture was cooled and the liberated FACM extracted with chloroform. The chloroform solution was dried and subjected to nuclear magnetic resonance analysis. Eb it was found that the lusted PACH contained 95 % of trans-trans-xsomers.

Game 5

A mixture of phthalic acid (16.6 parts), PACM (with a content of approximately 48 % of trans-trans isomers) (21.0 parts) and Wasner (230 parts) were heated to 90 to 95 ° C. with stirring and Maintained at this temperature for 1 hour. Ea was then cooled down to 10.degree. C. and the suspended solid was filtered off, washed twice with 50 parts of cold water and dried in an oven at 70.degree. There was obtained 13.3 parts of PACM phthalate equivalent to 35.3 percent of total solids fed.

A sample of this PACM phthalate was replaced by aqueous sodium hydroxide and the PACM which had been released was extracted with chloroform. The chloroform solution was dried and subjected to nuclear magnetic resonance analysis. The dissolved PACM was found to have 96 % of trans-trans isomers.

ORIGINAL 909883/1735 '

Example 6

A mixture of sebacic acid (20.2 toils) PACM (with an 8 © halt τοπ approximately 34% of trans-trasas isomers) (21 part) and water (125 parts) was Rühi'sn at 90 to 95 ⁰ C. heated and kept lasig at this temperature for 2 hours. Ice was then cooled down to 15 ⁰ C, the suspended solid filtered, washed with cold water 50 Teiisn washed imü in © INEM Of © n at 70 ⁰ C dried. 30 parts of PACM-Sefaacat j equivalent were obtained as 73 % of the total solids introduced.

A sample of this PACM sebacate was extracted with aqueous nitrate hydroxide and the PACM released with chloroform. The ChlorofoEro solution would not

miu. the magnetic resonance analysis. It hurdle g © fundan _s that the dissolved PACM had a content of trans-% trana-Isomeran.

BATH ORIGINAL

909883/1735

Claims (11)

- in »claims 1. Process for the separation of salts, which have an increased proportion of the salt of the trans-trans isomer, from salts of a mixture of the stereoisomers of ¹ J, 4 · - -Oi aminodieyclohexylmathßns with dicarboxylic acids, thereby f indicates that the original salts are subjected to a x ^% water milling and the solid sals, which has a substantial proportion of the trana-trans isomer, -mn $.? £ ■ the liquid phase is separated off. 2. The method according to claim 1 "characterized in that _ä dia Anaahl the Kohlimefeoffatome the Dicarbonsäurs, including represents the carbon atoms in the carboxyl groups, gpftter 3. The method according to any one of claims 1 and 2, characterized in that the dicarboxylic acid is an aliphatic © Is dicarboxylic acid. 4. The method according to any one of claims 1 to 3, characterized in 'that the dicarboxylic acid, ω-Dodecandioicsäure is a'. BATH ORIGINAL 009883/173 5 * ■ '. " ¹⁵ " 5. The method according to any one of claims i to Ί, characterized in that the salts of a mixture of the stereoisomers of 4,4 '~ diaminodioyclohexylmethane with a dicarbanic acid in water to a temperature of 50 ⁰ C, cooled to room temperature and the undissolved solid separates and dries. 6. The method according to any one of claims 1 to 5, characterized characterized in that the salts of the stereoisomers of 4,4'-diaminodicyclohexylmethane produces in situ in water. 7 · The method according to any one of claims 1 to 6, characterized characterized in that the dicarboxylic acid Οΐ, ω-dodecanedioic acid and the solid salt, which contains an increased proportion of the salxes of the trans-trans isomer, is separated off from the liquid phase at room temperature. 8. The method according to any one of claims 1 to 7, characterized characterized in that the free I ^ '- diaminodicyolohexylmethane is regenerated from the separated salt with the increased transtrans content by treatment with a base and subsequent solvent extraction « 9. Process for the preparation of dicarboxylic acid salts of k ₉ 4'-diaminodicyclohexylmethane with an increased trans- - 16 -909883/1735 ■ BATH ORIGINAL tr & ns-xsomer content according to claim 1 as described above with reference to the examples. 10. Oicarboxylic acid salts of lJ, V-diarainodicyclohexylmethane with an increased trans-trans content, as far as this according to a method according to any one of the preceding claims from salts of a stereoisomer mixture of this diamine have been severed " 11. A process for the preparation of polyamides containing structural units of the formula -OC- (CH ₂ ) ^ -CO-NH-CH \ jH-CH ₂ -CH CH-NH- H \
^N CH ₂ -CH ₂ in which the dicyclohexylmethane part is mainly trans-trans isomer, characterized in that a dodecanedioic acid salt of H ₃ H »-diaminodicyclohexyl methane with an increased trans-trans isomer content is heated. PATENTANWÄLTE 9R.-IN · H-FINCKt Din. · «« «, A» OHR BATH ORIGINAL
909883/173 5