DE2116500C3 - - Google Patents

Description

The production of!, L'-peroxydicyclohexylamine by reacting cyclohexanone with hydrogen peroxide and ammonia is known. From British patent specification 1 IS) S 421 it is known to carry out this reaction in the presence of a nairium salt of ethylenediaminetetraacetic acid (EDTA). Furthermore, from the French patent specification I 54S ¹ J15, the use of the Magncsiumsalz.es from EDTA for this Zv.eck is known. In both cases, however, large quantities of the EDTA salt are required to obtain the best bumps on IJ'-Peroxydicacloh :: \ ykiMiin. It would be of great value if one were able to use an additive. which is effective in smaller amounts than the sodium and magnesium salts of EDTA.

According to the invention, it is a process / ur production of I.l'-Pernxydicydohe \ y! Amine by reacting cyclohexanone with hydrogen peroxide and ammonia in the presence of a metal derivative of ethy-diamine octraacetic acid, which is characterized by this. Since ¹ ) the reaction takes place in the presence of an aluminum or lanthanum derivative to ethylenediaminetelraacetic acid, which is used either alone or in conjunction with zinc, nickel (iile cadmium derivatives, on ethylenediamine tetraacetic acid).

While in the method of the French patent specification 154X915 with a Mugiicsiumioncnkoii / cntration \ on about 7 g liters, ie about 0.7 Ge v. ight percent. the peroxyamine content is only N7.5 "/" is obtained when using the method according to the invention at concentrations of only about 0.03 to 0.OS percent by weight, calculated on the total melalkkrival (whereby in most cases only half the amount the claimed metal derivative of EI) TA and the remainder consists of disodium I.DTA). Peroxvamiiiaushcutcn from S8 to ¹ Hi "". compared to only «S3 to 86% of a product that is furthermore impure when using the disodium EDTA alone. This increase in yield with a simultaneous considerable reduction in the use concentrate compared to the Magncsium-MiI / I DTA is surprising. In particular, the state of the art does not offer the laughter any indications that the observed bulging could be achieved with the claimed method.

The cyclohexanone, hydrogen peroxide and ammonia can be used over a moderately wide range of Conditions can be implemented with each other. The molar ratio of cyclohexanone to hydrogen peroxide is preferably about 2: 1, e.g. B. between 2.1: I and 1.9: 1, while the molar ratio of ammonia to hydrogen peroxide is at least 1: 1, preferably about 3: 1 matters.

ίο The reaction between the cyclohexanone, hydrogen peroxide and ammonia can be carried out over a moderately wide temperature range. z. Example in the range of 20 to 60 ^c C. especially 30 to 50 "C.

The amount of the metal derivative of ethylenediaminetraacetic acid in the reaction mixture can be over vary over a wide range, e.g. B. ve.i about 0.005 to about 1 weight percent, based on the total Reaction mixture, preferably from about 0.01 to

so about 0.2 percent by weight, based on the total Reaction mix.

The reaction can be carried out in the presence of a catalyst, e.g. B. in the presence of Ammonium nitrate, ammonium chloride or ammonium or metal salts of organic carboxylic acids, of the I. group of the periodic table, for example ammonium acetate.

The response time can widen over a moderate amount The range will vary and the optimal time will depend on the temperature and the applied Catalyst off. Examples of suitable times are 1 to 20 hours. So germinate with continuous conversions Total actions from 4 to 12 hours can be applied.

The implementation can be in any suitable · .. ·!] Way to run /. B. by mixing together the reactants in one or more Stirred tanks.

In the case of the metal deri-.aleii of the EI) TA does not occur in the time required for the reaction to form Ι, Γ-Pcroxydicyclohcxylamin noticeable hydrolysis.

The derivatives can e.g. B. be prepared by adding a salt of the metal and a nitrium salt of EDTA mixed together in solution. Examples of suitable salts are carbonate, nitrate and the Acetate.

The sodium salts of EDTA can e.g. B. Dinatrium-EDTA and Tetranalrium EDTA. The

sea salt made in this way. can be insulated as a solid material which may also contain sodium salts of the anion introduced by the metal salt.

It is preferred, however, to put the salt in Eon »one Solution to be used without isolating a solid. It may be desirable to have a (iberschul. 5 of EDIA's nutrient salt during production des lYlctall.snl / v.s / u. So it can It may be desirable to use an amount of the sodium salt of EDTA that is up to an overshoe

^6, "150 percent by weight relative to the amount stöchiomctrischcn, z. B. represents up to 100 "". The mechanical amount corresponds to 1 gram atom of metal to 1 gram molecule of the sodium salt of EDTA. The use of an excess of the sodium salt of EDTA can help to stabilize the metal salt against hydrolysis.

It may be desirable at the llcr.stelluiiu from solutions of metal salts to alkaline solutions

2 I 16

manufacture, either by preparing the metal salts in an alkaline medium or by makes the solution alkaline after preparation. the A solution of the metal salts can, for example, have a pH of 5 to 12. Therefore it is preferred at the Implementation of cyclohexanone, hydrogen peroxide and ammonia the Metnilsalz in the fed Add ammonia, although it will also be introduced into one of the other two reactants can. It is believed that the use of an> ° alkaline solution increases the stability of the metal salts increased, although the use of a very alkaline solution, e.g. B. with a pH greater than 9, im Case of some metal salts, ζ. B. in the case of the aluminum derivative, the extent of hydrolysis taking place can increase. Examples of suitable metal salts of EDTA used in the method of the invention additionally Zinc, cadmium and nickel derivatives can be used for aluminum or lanthanum derivatives. Mixtures of two or more such metal derivatives can also be used. The examples illustrate the invention.

Manufacture of metal derivatives of LDTA

Nickel derivative ^2a

6.2 g of basic nickel carbonate (NiCO., · 2 Ni (OH) ₂ · 4ILO) and 7.2 g of disodium EDTA (100 ° excess) were added together to 300 ml of water and the concentration was 15 to 30 years old Heated at 40 ° C. for 3 minutes. A solution of the \ ickelderi \ alcs was obtained.

Ahiminiumdcihal

i9 g Aluminiiimnitrat (AI _(NO,)., · vH, (); about 5 S) "".. \] _{(NO,): l)} and 37 μ disodium EDTA "(100""excess) were added together to 400 ml of water (the complex appears to be more water-soluble than Na., -1 DlA / u) and the mixture was heated with occasional shaking for 5 to 30 minutes at 40 C. The solution was heated to a pli value of 8 brought to 9 (by about 20 ml of ammonia 0.880).

λ .ϊ zinc derivative

Il g zinc acetate (Zn (OAt-J ₂ ^ HX »and 37.2 g disodium EDTA UOO ¹ V _n excess) were added to 100 ml water and the solution was purified by means of ammonia (e.g. about 50 ml ammonia 0.880) made alkaline.

Lant'nanderivat

4.3 g of lanthanum nitrate (La (NO ₃ ) _a · 6 H ₂ O) and 6.7 g of disodium EDTA (100% excess) were added together to 100 ml of water and the solution was made alkaline with ammonia.

Cadmium derivative

5.4 g of cadmium acetate (Cd (OAc) ₂ · 2 H ₂ O) and 13.4 g DinatriuniEDTA (100 ° / ₀ excess) was added to 200 ml water and the solution was made alkaline by means of ammonia.

Effect of individual aluminum and lanthanum derivatives of EDTA on the yields of peroxyamine

Examples 1 to 8 c

Cyclohexanone (2.13 mol hour), aqueous ammonia solution (z. B. 0.880; 2.8 mol NIl ₁ hour) and hydrogen peroxide _{solution (39 "Z 0} wt. Vol .; 1.13 mol HoOj.hour) were by way of separate Feed lines are continuously pumped to a continuous two-stage, stirred, cascade reactor system.

The catalyst (16 "" wt. Vol. Based on the ammonia fed in) was introduced into the reaction system in the ammonia fed in. the Stabilizer was introduced in either the ammonia fed or the peroxide fed: different arias of stabilizers were applied at different concentration, η. the further details can be found in table 1.

Both reactors were kept at 30 C and the Levels were set so that "-I had a grave dwell." of 9 hours. The yields achieved are shown in Table I.

Table I.

Effect of individual derivatives of LDTA on the yields of 1.1 Peioxydicyclolie \\ l In all experiments, it was held at 30 ° C for 9 hours

Aluminum / Na ₂ - EDTA in pure l'rucuct. stabilizer no reac t hcrsehüU M en ye in
;: esaiiiler Yield to
IVio \.> Annn Cvd »- ispiel Aluminum / Na ₂ -Ii DTA H'it'll, t. ill, Γ gate supplied Ν; ι ^ -1.η ΐ A liiisfeeding hrvinni
"him/ Lanthanum / Na. ,, - EDTA Γν <l 1.11 \ SiI 11 ¹ I
ί Anmioniunisal /) in Γ, .. <"") (".,) No. Aluminum / Na ₂ -I. DTA NH ₁ OII 100 0.03 96 l "', i) 1 Aluminum / Na ₂ -E DTA nitrate ΝΙΙ, ΟΙΙ 100 0.07 93 99 Aluminum / Na ₂ -IiDl A nitrate ΝΙΙ, ΟΙΊ HK) 0.08 88 100 3 Na ₁ -LDIA nitrate ΝΙΙ, ΟΙΊ no 0.08 90 99.5 4th Na ₂ -LDTA nitrate ΝΙΙ, ΟΙΙ 100 0.08 90 98.7 S. Compare chloride NII ₁ OH 100 0.08 89 ^U 9 6th 1 very ι acetate ΝΙΙ, ΟΙΙ 100 0.08 83 *) 7 c acetate 11.0., 100 0.08 86 M. 8c acetate

Effect of mixed aluminum and inihanderiivals of EDTA on the yields of IJ'-peroxydicyelohexylamine

Examples 9 to II

How the examples work! to 8c was repeated, with a picture, that now a mixed metal derivative by EDTA was employed and the catalyst in all of these examples was ammonium nitrate. All details and the results of the tests are shown in Table H,

Table Il

example
No. Mixed metal derivative
from EDTA (fed into
Ammonia solution) a lot of
Complex in the
entire feed
sung (»/") Yield of I ¹
Base titration eroxyumin (%)
lodomclrisehe
analysis Cyclohexanone
Balance sheet
( ¹ Vo) 9
10
11th 1: 1 Al / Zn complex
1: 1 Al / Ni complex
1: 1 AI / Cd complex 0.08
0.08
0.08 89.1
91.7 89.1
91.2
89.3 99
98

Claims (1)

Claim: Process for the preparation of U'-peroxydicyclohexylamine by reacting cyclohexanone with hydrogen peroxide and ammonia in the presence of a metal derivative of ethylenediaminetetraacetic acid, characterized in that the reaction takes place in the presence of an aluminum or lanthanum derivative of ethylenediaminetetraacetic acid which is either alone or in conjunction with zinc, nickel or cadmium derivatives of ethylenediaminetetraacetic acid is used.