DD271819A3 - METHOD OF OBTAINING HIGH-PURITY, HIGHLY-DEDICATED DISEKUNDAERER DIAMINE - Google Patents

Abstract

The invention relates to a process for obtaining high purity, high boiling disecond diamines 1 from a, v-dihalogen compounds and primary monoamines, RNHRNHR 1wobei for the purification of the diamines the complete removal of water by azeotropic distillation with an entrainer and the subsequent separation of the alkali metal salts by filtration essential Refurbishment operations are. Discundary diamines according to the invention can be used for the preparation of epoxide-amine addition polymers, polyamides, polyureas and as adhesives, laminates, composites and the like. v. a. m. be used.

Description

Field of application of the invention

The invention relates to a process for obtaining high-purity, high-boiling disecided polymers of the general formula R'-NH-R-NH-fV,

wherein R represents a difunctional araliphatic, cycloaliphatic or aliphatic radical and R 'represents a monofunctional aromatic, araliphatic, cycloaliphatic or aliphatic radical.

Di-secondary diamines according to the invention can be used for the preparation of epoxy-amine addition polymers, polyamides and polyureas, which in turn can be used in a wide variety of applications as adhesives, casting resins, laminates and composites.

Characteristic of the known technical solutions

Secondary amines have been widely prepared in the literature by numerous synthetic methods (see Houben-Weyl 3d.Xl), among which the two-axis diamines as components for polyaddition and polycondensation are of particular interest.

The preparation of individual disecondary diamines has recently been described repeatedly. Khim Zhur, 35 (1982) 721) was able to substantially simplify the complex synthesis processes which gave only relatively low yields of di-secondary diamines (Collect., Czech, Chem., Commun., 45 (1980), 1567, 1567) (DD 141677, DD 244749, J. prakt. Chem. 322 [1980] 445). However, there is the problem that the high-boiling disecondary diamines incurred as yellow to reddish colored products and due to the manufacturing process partly still contain salts by the described in DD 141677 and DD 244748 workup, addition of concentrated potassium hydroxide, separating the deposited amine phase (Rohamin), drainage of Rohsminphnse by solid KOH and subsequent fractional distillation, were not completely removed.

Due to the coloring, their use in optical precision instrument construction is not readily possible and the sometimes relatively high salt content is in turn limiting for applications of the amines as components for special polymers in the field of microelectronics.

Due to the impurities (salts) for the production of highly pure amines a multiple distillation is required, which is to be realized by the sometimes occurring decomposition of the amines in the presence of salts only in 50 to 100g scale.

As a result, these amine syntheses are very complicated and expensive.

ZIOS of the invention

The object of the invention consists in a simple technically feasible recovery of high purity, high-boiling disekundärer diamines that can be used as high-purity monomers for the production of polymers for precision equipment and electrical engineering / electronics (microelectronics).

Explanation of the essence of the invention

The object of the invention is to obtain high purity, high boiling disecondary diamines by removing the salts contained therein. The diamines disekundaren 2 are thereby get * :, that α, ω-dihalo compounds 1 with a 2- to 20-fold excess of primary monoamines between 20 to 200 C are converted ^0,

20-200 ° C

XRX + 2R - NH>R'-NH-R-NH-R ¹

_Λ ^d -2HX ₀

where R is a difunctional substituted or unsubstituted aliphatic, aliphatic or cycloaliphatic radical and R 'is a monofunctional aromatic, araliphatic, cycloaliphatic or aliphatic radical. Dihalogen compounds and primary amines are reacted in a solvent such as benzene, toluene or the like, preferably without a solvent for 2 to 20 hours at temperatures between 20 to 200 ° C, preferably between 100 to 190 ⁰ C. The Aufaroeitung of the amines takes place through the following operational stages:

1. Addition of concentrated potassium hydroxide solution

2. Separation of the separated amine phase (crude amine!

3. Drainage of Rohaminphace by solid KOH

4. Distillative separation of the monoamine and

5. Fractional Distillation Over Short Path Distillation Anlay,

according to the invention before or after desiillativen separation of the monoamine dehydration by oceotrope

Distillation with an entraining agent such as toluene or benzene and subsequent separation of the precipitated salts

he follows.

The workup of the raw batches is problematic because the target products such. B. OPC-81 as a strong complexing agent for Alkali and ammonium salts act as well as to hydrate formation.

0PC-C1

Simple washing out of the salts from the crude amine with water is therefore unsuccessful because the amines are water-soluble. Although the dehydration of the crude amine with solid KOH precipitates a large amount of the salt absorbed by the phase transfer effect, it is not possible to achieve complete freedom from salt in this way.

Also, the direct distillation of the crude amine does not lead to water- and salt-free products, because by the high-boiling amines water and a part of the salts are always carried along and carried by decomposition products contamination. It has been found that the workup can be significantly improved if azeotropic distillation with iichleppmitteln such as toluene or benzene in the raw amine persistently detained water is removed (destruction of the amine hydrates). Due to this total dehydration, the alkali salts contained precipitate out and can easily be separated by filtration. Thereafter, a problem-free fractional distillation of large quantities of high-boiling disekundärsn diamines is possible. The di-secondary diamines thus obtained (Examples 1-8) are high-purity colorless compounds, salt-saline, and are therefore suitable for use in microelectronics and precision adhesives

 Examples of amines prepared by this process are:

CiH ₅ -CHi-NH-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -NH-CH ₂ -CeH ₆ (1) CH ₂ = CH-CH ₂ -NH-CHiCH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -NH-CH ₂ -CH = CH ₂ (2) C ₆ Hg-NH-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -NH-CeH ₆ (3)

C ₆ H ₆ -CH ₂ -NH-CH ₂ CH ₂ CH ₂ CH ₁ OCH ₂ CH ₂ CH ₂ CH ₂ -NH-CHr-CeH ₆ (4) Similar complex effects for water and alkali salts also occur with other di-secondary diamines. as

CH ₂ = CH-CH ₂ -NH-CH ₂ CH ₂ -NH-CH ₂ -CH = CH ₂ (5) C ₆ H ₆ -CH ₂ -NH-C ₆ H ₁₀ -NH-CH ₂ -CeH ₅ (6) C ₆ H ₆ -NH-CH ₂ -CeH ₄ -CH ₂ -NH-C ₈ H ₆ (7) C ₆ H ₆ -CH ₂ -NH-CH ₂ CH ₂ -NH-CH ₂ -CeH ₆ ! 8)

The preparation process and the work-up according to the invention can also be used expediently for the purification of these amines. Will in individual cases z. For example, for the preparation of (5) and (2) using a primary monoamine boiling lower than the entrainer (toluene / water), distillation of the low boiling excess primary amine occurs prior to azeotropic dehydration.

For the production according to the invention of high-purity, high-boiling disecondary diamines, the known working technique of azeotropic distillation is applied in a special field and thus a decisive improvement of the product quality is achieved. The success of this method is surprising because the basic chemical knowledge speaks against the applicability of the method. In the case of the analog crown ethers, the complex is just being removed by removing the water. Ligand / metal ion stabilized.

Bsi of the solution found for the purification of the amines according to the invention is not the reduction of the solubility of salt by dehydration, so not an .Oussalz effect. "Rather, the method is based on the surprising effect that the complexing tendency of these amines for interfering alkali and alkaline earth ions is reduced by the removal of the hydrate shell, and the formed anhydrous complexes in a distillation in contrast to the hydrous complexes undergo a decomposition to form the metal salts and the free amines.

embodiments example 1

187.1 g (1 mol) of 1,8-dichloro-3,6-dioxaoctane and 1071.6 g (10 mol) of benzylamine are refluxed together for 2 hours.

After cooling, 25% aqueous potassium hydroxide solution is added, thoroughly stirred and the amine phase separated. The Amingemiach is dried for several hours over solid KOH and then separated from the separated water. Subsequently, 100 ml of toluene are added and distilled off again, until pure toluene passes. The after this operation

precipitating salts are separated by filtration. Subsequently, the N, N-dibenzyl-3,6-dioxaoctanediamine-1,8 is fractionally distilled after the benzylamine has been distilled off.

Yield: 269.4 g (82% of theory) Kp.207-210T / 0.1 Torr, ng ⁰ = 1.5406, D = 1.0475 ¹⁰ CmH ₂₈ N ₂ O ₂ 328.5 Ber. C 73.13 H 8.59 N 8.53

Gef. C 73.14 H 8.72 N 8.40 Cl 0.0

The amine prepared according to DD 141677 (without azeotropic dewatering and salt separation) still has a relatively high Cl content of 0.72%.

Example 2

99.6 g (0.5 mol) of 1,9-dichloro-S-oxanonan and 535, Cg (Smol) benzylamine are heated together for 2 hours at reflux. After cooling, 25% aqueous potassium hydroxide solution is added, and the amine phase is separated off and dried over solid KOH.

Then, after addition of 100 ml benzene, the remaining water is azeotropically distilled off, and the precipitated salts are filtered off

and distilled off excess benzylamine.

The amount of crude di-secondary diamine obtained from four of these approaches (about BoQg) _w j _{r (m} jj oil pump vacuum

fractionated and colorless N, N'-Uir> anzyl-5-oxanonandiamin-1,9.

Yield: 560 g (82.2% of theory), bp. 195-8 / 0.18 torr C ₂₂ H ₃₂ N ₂ O 340.5 Ber. C 77.60 H 9.47 N 8.23

Gef. C 77.59 H 9.61 N 8.11 Cl 0.0

In contrast, the amine prepared according to DD 244768 still contains 0.47% chlorine. Example 3

571.0 g of dmol) of allylamine are heated together with 99.0 g (1.0 mol) of dichloroethane stuncone on a water bath. After this

Cooling is shaken with 25% potassium hydroxide solution, the amine phase separated and dried over solid KOH. Subsequently, will

distilled off the excess allylamine and 100ml benzene added to the remaining crude amine to distill off residual water azeotrope. Thereafter, the NN'-diallylethylenediamine is filtered and fractionated in vacuo.

Yield: 76.3 g (54.4% of theory), bp.73-5X / 10 Torr A chlorine content of this amine is not detectable, while the analog prepared according to DD 141677 or DD 244 748 amine still

Contains 0.76% chlorine.

Example 4

285.5 g (5.0 mol) of allylamine are refluxed together with 93.6 g (0.5 mol) of 1,8-dichloro-3,6-dioxaoctun for 10 hours.

After cooling, it is poured with 25% aqueous potassium hydroxide solution (from 60 g KOH), the amine phase separated and solid KOH dried. Subsequently, the excess allylamine is distilled off, 100 ml of benzene added to the crude amine to

Distill off remaining water azeotropically and the amine freed by filtration of precipitating salts. After that it will be

N, N'-Diallyl -3,6-dioxaoctari-diamine-1,8 fractionally distilled. Yield: 60.8 g (53.3% of theory), bp. 108-9 ° C / 0.2 Torr The amine thus prepared contains no residual chlorine content, while the chlorine content a ', according to DD 141677 or DD 244748

analogously prepared amine still Cl = 0.34%.

Claims (3)

Claim: 1. A process for the recovery of high purity, high-boiling disekundörer diamines obtained by reacting α, ω-dihalogeno with primary monoamines and their workup by shaking with concentrated potassium hydroxide, Abtrerien ien of the oily amine phase, dehydration of the amine phase with solid potassium hydroxide, distillative separation the monoamine and subsequent fractionation in vacuo, characterized in that before or after the removal by distillation of the monoamine, a dehydration by azeotropic distillation with an entraining agent and a subsequent separation of the precipitated salts. 2. The method according to claim 1, characterized in that when using lower than the entrainer boiling monoamines, the azeotropic dewatering takes place after the separation by distillation of the monoamine. 3. The method according to claim 1 and 2, characterized in that benzene or toluene is used as the entrainer.