DD150744A1 - METHOD FOR THE CONTINUOUS PREPARATION OF CYCLOALKYL HYDROPOXORS - Google Patents

Abstract

The invention relates to a process for the continuous preparation of mixtures of cycloaliphatic and / or alkyl-substituted cycloaliphatic ketone hydroperoxides with phlegmatizers, which are used as polymerization initiators for ungesettigte polyester resins. It is a safe method compared to previous methods significantly higher space-time yield indicated that the reaction takes place in certain pH ranges briefly within 1 to 10 minutes at temperatures above the exothermic decomposition point of the peroxides at temperatures of 333 to 358 K and Subsequently, the reaction mixture is cooled immediately to temperatures below the exothermic decomposition point. The reaction takes place in an equivalent 2 to 5-stage reaction vessel cascade with reliable degassing with temperature control with a continuous-flow temperature control agent and with an additional stabilization of the reaction mixture with dialkylmethanediphosphonic acid. The peroxide mixture formed is stabilized with Trialkylolammoniumdiakylaminomethandiphosphonat at aequimolekularemesüberschusz of trialkylolamine. A Stoffausbeuteherhoehung with respect to the hydrogen peroxide used is effected by the extraction of the mother liquor of the reaction mixture with the cycloaliphatic ketone, which is anschlieszend used for the reaction in the reaction vessel cascade.

Description

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Title of the invention

Process for the continuous production of cycloalkyl ketone hydroperoxides

field of use

The invention relates to a process for the continuous preparation of mixtures of cycloalkyl ketone hydroperoxides, which are formed by the reaction of hydrogen peroxide with cyclohexanone, and in which the "l-hydroxy-1'-hydroperoxi-dicyclohexyl peroxide as a main component in admixture with 1,1'-bis-hydroperoxi The process likewise relates to the preparation of mixtures of the substituted cycloalkyl ketone hydroperoxides which are formed by reaction of the positionally isomeric o-, m- and p-alkylcyclohexanones with hydrogen peroxide, mixtures of these with one another and with mixtures of these peroxides with phlegmatizers represent valuable polymerization initiators, are mainly used for the processing of unsaturated polyester resins on an industrial scale and therefore have great industrial importance in the arts st off Industrie. ι;

Characteristic of the known technical solutions

The known technical solutions for the preparation of Cycloalkylketonhydroperoxiden carried out according to the classical synthesis route of the addition of hydrogen peroxide

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to the carbonyl group of the cycloaliphatic ketone and the stepwise and partial substitution of the resulting hydroxide by hydrogen peroxide, as first described in US Pat. No. 2,298,404. In the course of using the cycloalkyl ketone hydroperoxides as commercial products for use in the plastics industry _For example, in order to initiate the polymerization of unsaturated polyester resins, several processes were protected in which mainly a discontinuous reaction of the reaction products followed by a batchwise work-up took place. An essential feature of the substitution reactions is the reaction in an acidic environment. Thus, the use of various proton suppliers and their concentration such as sulfuric acid in DE-PS 832 743, nitric acid in SU-PS 177 883, hydrochloric acid in the DE -PS 1 088 485 or protected by cation exchange resins in FR-PS 1 319 091. Other essential features are the molar ratios of the reaction components used hydrogen peroxide and cycloalkyl ketone and the temperature limits in which the reactions are carried out. Thus, for example, in SU-PS 177 883 in a temperature range from 283 to 303 ⁰ K, the 1,1'-bishydroperoxi-dicyclohexyl peroxide prepared, the method both by the molar ratios of hydrogen peroxide to cyclohexanone of 2 to 3 to 1 and characterized by the concentration of nitric acid in the solution of 0.8 to 1.6 g equivalent / liter. In DE-PS 1 060 857, the cyclohexanone peroxide is prepared in the temperature range from 308 to 333 ⁰ K and advantageously at temperatures between 313 to 323 ⁰ K. Due to the exothermic reaction reaction in these discontinuous processes for the safe control of Te raperaturregulierung using coolant, a reaction time is required, the between 20 minutes when working in the temperature range from 308 to 333 ⁰ K and 1.5 hours when working in the temperature range from 283 to 303 ⁰ K,

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The causes of the limitation of the reaction temperatures up to 333 ⁰ K in the previous technical solutions for the preparation of Cycloalkylketonhydroperoxiden example, the cyclohexanone peroxide are obviously based on the prejudice of the art that the reaction reactions are safe to handle only below the exothermic decomposition point, higher temperatures but strong decomposition The resulting peroxides and lead to destruction of the equipment used at high gas load. For example, the exothermic decomposition point of the 1-hydroxy-1'-hydroperoxi-dicyclohexyl peroxide with 10 % water content is 329 ⁰ K and the mixture of about 10 % 1,1'-bishydroperoxydicyclohexyl peroxide with 40 % 1-hydroxy-1 ' hydroperoxy-dicyclohexyl and 50 <%> dibutyl about 338 ⁰ K * This limitation on the reaction temperatures result in long reaction times and therefore low space-time yields. This disadvantage has so far been compensated in the general technical reactions by increasing the reactor volume. Due to the tendency of Cycloalkylketonhydroperoxide for decomposition and the presence of relatively larger amounts of material and constant increased gas formation in the liquid means this method of increasing the reactor volume in the production of Cycloalkylketonhydroperoxiden an increasing risk of explosion and thus an increasing security risk.

A preparation of cycloalkyl ketone hydroperoxides in the form of commercial solutions or pastes according to the discontinuous processes mentioned requires further processing steps such as washing, drying and mixing with phlegmatizing agent, as described, for example, in Antonovsky et al. Chim. prom. 4 (1964) p. 496-499, so that these technical processes represent a time-consuming overall process.

Tn DD DD 118 608 it was known that the cyclohexanone peroxide can be prepared by a continuous countercurrent process by in a pulsation extraction column, the cyclohexanone with a. Sodium sulfate in his

A disadvantage of this process is that it requires an additional use of materials both by the necessary use of a higher percentage of hydrogen peroxide of at least 54% by mass and the addition of sodium sulfate Temperatures up to 333 ⁰ K is feasible, since at higher temperature, the decomposing hydrogen peroxide leads to high gas formation and thus due to the formation of gas cushions underneath the sieve bottom plates to disturb the flow of material, continue in this process, the throughput is limited by the low rate of rise of the organic peroxide phase , so that the interpretable for high extraction performance optimal conditions such as a high pulsation intensity can not be used.

Object of the invention

The object of the invention is to eliminate the said disadvantages and to develop a continuous process which involves the safe preparation of cycloaliphatic ketone hydroperoxides, in particular the blending of 1-hydroxy-1'-hydroperoxydicyclohexyl peroxide with 1,1'-bishydroperoxydicyclohexyl peroxide and phlegmatization and their alkyl-substituted derivatives on an industrial scale with high throughputs and substantially more favorable space-time yields at the same time high material yields and with high efficiency and safety allowed.

Features and features of the invention

The invention has for its object to ensure by a process, the technical production of cycloaliphatic ketone hydroperoxides with high speed and high security, in which the necessary for rapid reaction temperature range, which is above the previously known technical reaction temperature ranges, both by heat supply from the outside also by using the exothermic reaction

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amount of heat released is set. It has been found that by the reaction of hydrogen peroxide with cycloaliphatic ketones in aqueous acidic as well as aqueous-neutralized medium, the safe production of Cycloalkylketonhydroperoxiden at temperatures above its exothermic decomposition point in conjunction with short reaction times and immediate removal of gases produced by utilizing the Reaktionsenthalpien at the same time high yields is possible. This surprising behavior forms the basis of the method according to the invention. According to the invention the object is achieved by the method such that the continuous reaction at reaction temperatures of 333 ⁰ K to 358 ⁰ K, in particular 338 ⁰ K to 353 ⁰ K is carried out with reaction times of at least 1 to 10 minutes in combination with intensive dispersion of the reaction components and the resulting reaction product is immediately cooled to a temperature below 318 ⁰ K, wherein a mixture with a suitable phlegmatizer supports this rapid cooling.

According to a feature of the invention, the process is in a reactor cascade consisting of series-connected stirred reactors with internals of baffles to increase the degree of dispersion. carried out, which is provided with a Temperiermantel · and is given by their special structure, the removal of resulting decomposition gases. It is any reaction skesse lcascade used in compliance with the requirement described. Most excellently suitable for the stated purpose of the vertically assembled multi-chamber reactor according to DD-PS 211 097, which consists of a juxtaposition of several reaction vessel and in which centrally mounted Gasabführungseinbauten, small reaction volumes and devices for suitable temperature control of the reaction vessel are present.

Advantageously, according to a v / eiteren feature of the invention by interpretation of the procedural

Parameters of the reaction vessel cascade "bei'intensive Vex- mixture of the reactants in the individual reaction vessels to set the desired ratio of peroxide species the average Verv / eilzeit within the limits of 3 to 8 minutes, the breakthrough time of passing through the stirred tank cascade fastest reaction molecules of The setting of the average residence time by selecting the flow rate of the continuously metered raw materials in relation to the reactor filling volume in conjunction with the adjusted pH of the reaction medium and the choice of the relative molar ratios of the reaction components Hydrogen peroxide to Cycloalkylketon leads to the desired peroxide composition In compliance with the optimum residence time in conjunction with the optimum reaction temperature spectrum and the appropriate molar ratio of the reaction components is the implementation of the reaction components completed in a short time and the production of high quality and. According to a further feature of the invention it is zv / eckmäßig, while maintaining the other reaction and process conditions according to the invention to temper the reaction vessels by means of a tempering whose temperature is more than 343 ⁰ K and preferably in the range from 343 ⁰ K to 363 ⁰ K, wherein by direct current flow of the temperature medium to the flow of the reaction medium rapid heating of the reaction medium in the first reaction vessels and thus a rapid reaction already in the first reaction vessels begins, surprisingly, it has been found in this method that despite the reaction in the temperature range above the exothermic decomposition point of the resulting Cycloalkylketonhj'droperoxide and the hydrogen peroxide used no "going through the reaction"

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carried out by uncontrolled heating of the reaction medium. In contrast, the rapid reaction of the reactants in the first ReaktionskesseLn is supported by the resulting enthalpy of formation, while in the subsequent reaction boilers the forced temperature control by the outer shell only to maintain the temperature stability in the ongoing reaction of the substitution of a part of the hydroxy groups by hydrogen peroxide, for example, for implementation of 1- Hydroxicyclohexyl • 1'-hydroperoxi-dicyclohexyl peroxide to the 1,1'-Bishydroperoxidicyclohexylperoxid in the desired degree of conversion takes place v / o depending on the pH used and concentration of the peroxide used peroxide, this substitution is controllable.

According to a further feature of the invention after reaction at temperatures above the exothermic decomposition point of the resulting Cycloalkylketonhydroperoxides an immediate cooling to temperatures below the exothermic decomposition point, advantageously to be carried out at least 318 ⁰ K. This is to be possible with the known aggregates, such as an intensive cooler with intensive cooling coils and by constant mixing with phlegmatizer, which has a temperature of less than 293 K.

According to a further feature of the invention, it has proven to be advantageous that after reaction, mixing and separation of the organic phase from the aqueous phase, a countercurrent extraction of the aqueous phase is carried out. In this, the extraction of the residual proportions of peroxide of the aqueous phase by the ketone, which is then immediately used for reaction with the hydrogen peroxide in the reaction vessel cascade, whereby the rapid reaction is coupled with a high yield of hydrogen peroxide.

According to a further feature of the invention, it is expedient to carry out the reaction of hydrogen peroxide and the cycloalkyl ketones, in particular in neutral medium after prior

Addition of effective stabilizers such as the Dime thylaminomethan-diphosphonsaure perform, wherein the neutralization of the hydrogen peroxide with proton f äng or Wa ₂ CO ^ J NaHCOo, NapHPO / or sodium acetate takes place. By the addition of dimethylaminomethane-diphosphonic acid in a concentration of up to 1 Ma. -% based on the hydrogen peroxide used, surprisingly occurs in both the neutralized hydrogen peroxide and the cycloalkyl ketone hydroperoxide produced no significant loss of active oxygen, so that the safe implementation is ensured even at high temperatures. Likewise, it is advantageous to use an addition of trialkylolammonium dialkylaminomethane diphosphonates with a low equimolar excess of the trialkylolamine as an effective stabilizer for the Cycloalkylketonhydroperoxide produced, whereby their active oxygen content and the applicability as an initiator for the polymerization of unsaturated, polymerizable compounds. In Fig. 1, the general process scheme for the continuous production of Cycloalkylketonhydroperoxidpaste is shown in admixture of the peroxide with phlegmatizer. The reaction is carried out in a reaction vessel cascade used as reactor a in the manner of a technical multi-chamber reactor, the ketone A and a 35 Ma.-fidge hydrogen peroxide B. according to the selected MoI ratio of hydrogen peroxide B to ketone A and the pH value of the set Hydrogen peroxide solution B and by the temperature of the flowing in the DC tempering of 343 ⁰ K to 363 ⁰ K is carried out at a short average residence time of the reaction media in the reaction vessel used as a cascade reactor a rapid reaction, the Reaktionsgeraisch the reactor a with a temperature of 338 ⁰ K. leaves until 358 ⁰ K. In the preparation of Peroxidabmischlingen with phlegmatizers C, which do not dissolve in the aqueous phase, after the exit of the Reaktionsgemi sehes from the reactor a is an immediate mixing and cooling in one

Run through mixer b and intensive cooler c. Wax transfer this Geraisches in das.Beruhigungsgefäß d is carried out therein due to the present difference in density of the organic phase and aqueous phase a separation of both phases, so that the below the aqueous phase accumulating organic phase v / Eiterer cooling to 301 ⁰ C to 293 ⁰ K obtained in the continuous crystallizer e as a thin paste, which is assembled after collecting in the collector f in the transport vessels g in which the residual crystallization is carried out to form a stable paste.

To increase the material yield with respect to the hydrogen peroxide used, the aqueous phase is extracted in a countercurrent pulsation extraction column h with the ketone A in question for the intended reaction as the solvent. Due to the low concentration of hydrogen peroxide in the Gegenstrornpulsationsextraktionskolonne h, the ketone A as a molar excess over the forming Cycloalkylketonhydroperoxid before, so that, for example, when using cyclohexanone as the ketone

.A at temperatures between 313 ⁰ K and 323 ⁰ K no crystallization and clogging occurs in h and a functionally safe operation of the Gegenstrompulsationsextraktionskolonce h in their optimal working range is possible, since there are no significant gas cushion below the sieve plate in this temperature range. The ketone A rising to the top of the column with its proportion of dissolved cycloalkyl ketone hydroperoxide is then transferred to the reaction vessel cascade used as reactor a, while the extracted aqueous phase as raffinate D with the reduced proportion of 1 to 2 Ma.-tigers hydrogen peroxide and äßxa slightly to 1 Ma .- $> dissolved extractant ketone A is discarded.

In Hg. 2, the general process scheme for the continuous production of Cycloalkylketonhydroperoxidlösungen is shown in Abmiscbung the peroxide with phthalnatisierungs- • means C, in which the phlegmatizer c partially or completely in the aqueous phase

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to solve. For this purpose, the reaction of the reactants ketone A and 35 Ma .- # iges hydrogen peroxide B in the reaction vessel cascade used as reactor a, which is used in particular in the manner of a multi-chamber technical reactor. The reaction mixture obtained therefrom is cooled in Inten sivkühler c and in the sedative vessel d below the aqueous phase collecting still liquid cycloalkylketone hydroperoxide is mixed after separation from the aqueous phase in the mixer b with the phlegmatizer C. After collection in the collector f, the resulting solution in the transport vessel g is made up.

A material yield increase with respect to the hydrogen peroxide used is analogous to the process scheme Fig. Possible. For this purpose, after continuous separation of the aqueous phase from the cycloalkyl ketone hydroperoxide in the settling vessel d, the aqueous phase is metered continuously into the head of a countercurrent extraction column h, into which the metering of the ketone A used as extraction agent takes place simultaneously in the bottom of the countercurrent pulsating column h. After countercurrent extraction, the resulting mixture of ketone A and formed Cycloalkylketonhydroperoxid is fed into the reaction vessel cascade used as reactor a, while the extracted aqueous phase as Raffinate D with the reduced portion of 1 to 2 Ma .- per cent hydrogen peroxide and that in the raffinate D slightly to 1 Ma .- # dissolved extractant ketone A discarded v / ird. In Fig. 3, the general Verfahrenssehema for the preparation of mixed peroxide solution is shown in which after the implementation of the ketone A ₃ which consists of a mixture of different ketones and the 35 Ma .- # iger Wasserstoffper- Ox B in the reaction vessel cascade used as reactor a a mixture is formed which, after cooling in the intensive cooler c after phase separation in the settling vessel d and mixing the cycloalkyl ketone hydroperoxide mixture present above the aqueous phase with the phlegmatizer C in the mixer b, is still adherent or

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dissolved aqueous phase by drying with the usual TrockenmitteIn E as sodium sulfate in the dryer i must be dried. After separating the desiccant E from the resulting mixed peroxide solution using known continuously working illtrier j after collection in the collector f the solution in Tran sports vessel g to assemble. To increase the yield with respect to the hydrogen peroxide used, as in Hg. 1, use the countercurrent extraction. For this purpose, the aqueous phase resulting from the settling vessel d is extracted with the ketone A in the countercurrent pulsation extraction column h. The resulting mixture of ketone A and peroxide is then fed to the reactor a, while the raffinate D is discarded as 1 to 2 Ma .- per cent hydrogen peroxide solution with a small proportion of up to 1 $ dissolved extractant ketone A.

example 1

This process corresponds to process example Hg. 1. In a used as reactor a multi-chamber technical reactor with the nominal content of about 10 liters, consisting of 5 superposed reaction vessels with centrally mounted gas-discharging Domen be in the lowest

Reaction vessel · simultaneously and continuously 0.6 1 min

-1"" -

Cyclohexanone and 0.69 1 min 35 Ma .- # iges and 10gl HpSO, containing hydrogen peroxide dosed. In the tempering jacket of the multi-chamber reactor hot water of 353 ⁰ K is conducted in direct current to the product stream. The metered reaction mixture, with intensive stirring and mixing, passes through the 5 reaction vessels continuously and successively with an average residence time of 3 to 8 minutes at a mean residence time of 7 * 8 minutes and exits from the uppermost reaction vessel at a temperature of predominantly 348 ^° K off. The escaping mixture is immediately removed in the downstream

-1 shear b continuously with 0.7 1 min dibutyl phthalate as phlegmatizer C abgesaischt and cooled in an intensive cooler c to temperatures below 318 ⁰ K. To

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Transfer into the settling vessel d is the lowest phase in which the Cycloalkylketonhydroperoxid still present dissolved, cooled continuously in the following continuous crystallizer e to 298 ⁰ K, from this is obtained in a yield of 1.3 kg min a thin liquid paste whose peroxide predominantly consists of 1-hydroxy-1'-hydroperoxi-dicyclohexyl peroxide and a content of 6.3 to 6.6 <%> akt-. 0- has. The low-viscosity paste is collected in the collector f as a large batch and made up in the transport vessels g, in these transport vessels g, the residual crystallization, so that a stable Cyclohexanonperoxidpaste formed.

Example 2.

2. Following reaction of 0.6 l of cyclohexanone as ketone A with 0.69 l of " ¹ 35% methanol, 10 g of" ¹ H ₂ SO ₄ and 1% of dimethylaminoethane diphosphonic acid containing hydrogen peroxide B in the reactor a, which is designed as in Example 1 as Mehrkarnmerreaktor at reaction temperatures of 343 ⁰ K to 353 ⁰ K and the average residence time of 3 to 8 minutes, the reaction mixture after leaving the reactor a immediately with an intensive cooler c cooled to 318 ⁰ K and transferred to the settling vessel D. The still liquid cyclohexanone peroxide which separates out at the bottom is continuously added to the connected mixer b with 0.69 l of a mixture of about 60% by volume of ethylene glycol, about 27% by volume Ethyl acetate, about 12% by volume of acetone, about 0.15% of dimethylaminomethanediphosphonic acid and about 0.3% of triethanolamine, and the resulting solution with the main portion of 1-hydroxy-1'-methylene chloride. hydroperoxidicyclohexyl peroxide is used with a

act. Op content of 5.8 % in an amount of 1.7 kg min. It is transferred after collecting a large batch in the collector f in transport containers g.

Example 3

It will initially the reaction according to Example 1

ei r: r'i ο

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* -i

and Example 2 0.6 1 min cyclohexanone as ketone Λ with

-1 0.69 1 min. 35% by mass hydrogen peroxide B in the reactor a

reacted at temperatures of predominantly 348 ⁰ K. »After passing through the mixer b. or the bypass of the mixer b, the cooling of the reaction mixture in the intensive cooler c and the separation of the aqueous phase of the

organic phase after settling in the sedative vessel d. * "* -Λ

It is obtained as an aqueous phase, an amount of about 0.3 1 min, which still contains about 10 Ma .- # hydrogen peroxide. This aqueous phase is metered into the upper part of a countercurrent pulsation extraction column h and molar therein with a hydrogen peroxide present

- 1

Excess of cyclohexanone extracted as ketone A from 0.6 1 min. At the beginning of the extraction, the cyclohexanone which collects in the top of the column as ketone A has a peroxide content of about 20 to> 35 ° h and is immediately metered from this directly into the lowest reaction vessel of the technical multi-chamber reactor used as reactor a. With the beginning of the feeding of the ketone A from the column h into the reactor a, the metered addition of the cyclohexanone as ketone A takes place exclusively in the counter-current extraction extraction column h. Likewise, at the same time the metered amount of 35 Ma .- # hydrogen peroxide B in the reactor a on

-1

reduced from 0.52 to 0.55 1 min. After workup of the resulting Cycloalkylketonhydroperoxidgemische according to Example 1 or Example 2, the peroxide or the peroxide solution at the same yield wie.bei these examples, but at e'inem by 0.17 to 0.14 1 min reduced expenditure of 35 Ma .- ^ hydrogen peroxide solution B obtained.

Example 4 '

In the bottom of the first reaction vessel of the reactor a are simultaneously and continuously 0.69 1 min of a mixture of technical o-, m- and p-methylcyclohexanone as ketone A with a ketone content of $ 85 with 0.62

-1 -1

min. 35% and 10% PIpSO, containing

Hydrogen peroxide B is metered. In the reactor a, the tempering medium 348 ⁰ K to v / ei st, the reaction takes place with intensive mixing and reaction at an average residence time of 3 to 8 minutes and a mean residence time of 7.2 minutes. After subsequent immediate cooling in the intensive cooler c to temperatures of less than 318 ⁰ K, the organic phase collecting it in the mixer b is mixed with 0.415 1 min "dibutyl phthalate as phlegmatizer C after transfer of the mixture into the settling vessel d and with about 0 Dried sodium sulfate as drying agent E in the drier i After separating the desiccant E from the resulting mixed peroxide solution over the drum-type filter used as a continuous filtration apparatus j, the peroxide solution in an amount of 1.1 kg min "with an act , Obtained Op-content of 6.6 <$> and transferred after collecting in the collector f in the Tran sport vessels g.

Example 5

A mixing of 25 parts by volume of a mixture of technical o.-, m.- and p.-methylcyclohexanone having a ketone content of 85 % and 20 parts by volume of cyclohexanone as ketone A in the reactor a is continuous reacted with a 35 Ma per cent hydrogen peroxide B, wherein the hydrogen peroxide was previously stabilized with 1 $> Dimethylaminomethandiphosphonsäure and adjusted by addition of i ^ CO-j to a pH of 6 to 6.5. The conversion takes place after simultaneous

-1 -1

Dosage of 0.69 1 min of ketone A and 0.69 1 min of the stabilized and neutralized hydrogen peroxide B in the reactor a at an average residence time of the reaction mixture in this reactor a of about 7.2 minutes. The temperature of the reactor a is carried out with a tempering agent in direct current to the product stream at an average temperature of about 343 ⁰ K. The leaving the reactor a gera geraisch is then immediately cooled in the intensive cooler c to less than 318 ⁰ K and in

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Pacifier d separated into 2 layers. After conversion of the upper phase, which contains the methyl-substituted Cycloalkylketonhydroperoxidgemisch in the mixer b in this mixing with 0.4-6 first

Dibutyl phthalate, which is used as phlegmatizer C. After drying with the sodium sulfate used as the desiccant E in the dryer i and separating the desiccant E by means of the continuous filtration apparatus j is in an amount of

-1 1.4 kg min a mixed peroxide solution with an act. O ₂ ^-

Obtained content of 4.5 % , the peroxidic portion mainly from the mixture of 1-hydroxy-1'-hydroperoxicyclohexan with the 1-hydroxy-1'-hydroperoxide of o-, m.- and p.-l ^ e thy! cyclohexane exists.

Claims (3)

-fi- 2 2 oil 6 invention claim 1. A process for the continuous production of Geraischen from Cycloalkylketonhydroperoxiden and / or'alkylsubstituierten Cycloalkylketonhydroperoxiden by reacting cyclohexanone and / or alkyl-substituted cyclohexanone with hydrogen peroxide in aqueous-acidic or aqueous-neutral medium in conjunction with intensive dispersion of the reaction components characterized in that the implementation of Reaction components continuously at temperatures of 333 ⁰ K to 358 ⁰ K, in particular 338 ⁰ K to 353 ⁰ K and with reaction times of 1 to 10 minutes, in particular 3 to 8 ivünuten carried out, and the reaction product thus obtained immediately to a temperature below 318 ⁰ K. is cooled. Zt process according to item 1, characterized in that the reaction takes place in a reactor of the type Rührkesselkaskade with an equivalent number of stirrers from 2 to 5, in which the removal of resulting decomposition gases is guaranteed. 3. proceed according to point 1. and 2. ». characterized in that the temperature control is carried out with a flowing in the DC tempering, the temperature in the range of 343 ⁰ K to 363 ⁰ K. -47- 22OU The method according to 1 st to 3 <- characterized in that used as an additional stabilizer for the hydrogen peroxide in the preparation and implementation of the reaction Dialkylaminomethandiphosphonsäure, and for stabilizing the resulting peroxide mixtures Triallcylolammoniumdialkylaminomethandiphosphonate be used in equimolar excess of the trialkylolamine. 5 · Procedure according to items 1 to 4 ·. characterized in that, while maintaining the short optimum residence time in the reactor, the reaction to the desired Peroxidtnodifikation is substantially determined by the previously set pH of the reaction medium, in particular the hydrogen peroxide. 6. The method according to item 1 to 5, characterized in that after reaction of the reactants and separation of the resulting peroxide from the aqueous phase, this aqueous phase is extracted by the cycloalkyl ketone and / or alkyl-substituted cycloalkyl ketone, which then immediately to the reaction 'with the hydrogen peroxide is used in the reactor. For this 3. pages drawings