DE102008041138A1 - Process and plant for the preparation of glycidyl (meth) acrylate - Google Patents

Abstract

The present invention relates to a continuous process for the preparation of glycidyl (meth) acrylate comprising the reaction of allyl (meth) acrylate with H2O2 in at least one reactor in the presence of a catalyst, wherein unreacted allyl (meth) acrylate separated from the product mixture and in at least a reactor is recycled, which is characterized in that unreacted H2O2 is separated from the product mixture and recycled to at least one reactor.

Description

The The present invention relates to a process for the preparation of Glycidyl (meth) acrylate. In addition, the present describes Invention an installation for carrying out this method.

Glycidyl (meth) acrylate is often used as a comonomer, for example for the production of used reactive polymers. Accordingly, there are many Methods known to obtain this compound.

For example, this compound can be obtained by reacting epichlorohydrin with methyl (meth) acrylate. Methods of this kind are used, for example, in DE-A-25 25 026 described. However, epichlorohydrin is toxic and carcinogenic, so that plants in which epichlorohydrin is used, must meet very high safety standards.

Therefore, methods have been developed, according to which glycidyl (meth) acrylate can be obtained by partial epoxidation of allyl (meth) acrylate with hydrogen peroxide (H ₂ O ₂ ). Such methods are used inter alia in EP-A-190609 . EP-A-638,362 . JP-A-09059269 . JP-A-10158198 . JP-A-08188575 . JP-A-09132571 . JP-A-10168072 , JP-A-11165074 . JP-A-09235439 . JP-A-09301966 . CA-A-2033047 . EP-B-434 546 . EP-B-468 840 ( DE 69125540 ) US 5,283,360 and WO-A-98/28287 shown.

The publication EP-A-190609 describes the preparation of glycidyl (meth) acrylate by the reaction of allyl (meth) acrylate with H ₂ O ₂ in the presence of a TS-1 catalyst. In this case, for example, allyl (meth) acrylate can be initially charged with a catalyst, after which H ₂ O _{2 is} added. The reaction temperatures indicated in the document are in the range of 0 to 150 ° C. A disadvantage of the example in EP-A-190609 among other things, that the production costs are relatively high. Furthermore, the control of the product quality is often expensive, since influencing the reaction can only be carried out batchwise. Similar methods are also set forth in the other of the aforementioned references.

In addition, in JP-A-08188575 also describes continuous processes in which first of all reactants with one or more solvents, for example methanol, mixed and then reacted in the presence of a catalyst.

A disadvantage of the method described above is the low yield, which is due in particular to irreversible side reactions. Thus, in particular, the presence of H ₂ O ₂ in the purification of the mixture obtained is critical, since this compound can react with the double bond contained in the product. As a solution for this is inter alia in the document JP-A-09132571 proposed to catalytically decompose excess H ₂ O ₂ .

In In view of the prior art, it was now the task of the present Invention, a process for the preparation of glycidyl (meth) acrylate to provide, in which the product is very inexpensive can be obtained. In addition, the preserved Glycidyl (meth) acrylate only very small amounts of by-products contain.

A Another object of the invention was to provide a method in which glycidyl (meth) acrylate can be obtained very selectively. Farther the process should be as consistent as possible product quality provide.

About that It was another object of the present invention to provide methods for Preparation of glycidyl (meth) acrylate available that can be performed easily and safely. in this connection The product should preferably be in high yields and, overall seen to be obtained with low energy consumption.

Solved These and other not explicitly mentioned tasks that are however, from the contexts discussed hereinbefore are readily derivable or accessible by process with all features of claim 1. Expedient Modifications of the method according to the invention are in the dependent on claim 1 dependent Claims under protection. Regarding a plant for carrying out the inventive Method provides claim 25, a solution based lying tasks.

The present invention accordingly provides a continuous process for the preparation of glycidyl (meth) acrylate comprising the reaction of allyl (meth) acrylate with H ₂ O ₂ in at least one reactor in the presence of a catalyst, wherein unreacted in the reactor allyl (meth) acrylate separated from the product mixture and recycled to at least one reactor, which is characterized in that unreacted H ₂ O _{2 is separated} from the product mixture and recycled to at least one reactor.

This makes it possible to provide a method for the production of glycidyl (meth) acrylate in an unpredictable manner, in which the product is obtained very inexpensively. Surprisingly, the product obtained contains only very ge rings of byproducts, with generally very consistent product quality.

Of Further allows the inventive Process a particularly selective production of glycidyl (meth) acrylate.

Farther the process of the invention can be simple and be carried out safely, taking the product in high Yields and, overall, with low energy consumption can be obtained.

According to the invention Glycidyl (meth) acrylate, wherein the term glycidyl (meth) acrylate for glycidyl methacylate (CAS number 106-91-2), glycidyl acrylate (CAS number 106-90-1) and mixtures of glycidyl methacylate and Glycidyl acrylate stands.

For the preparation of glycidyl (meth) acrylate according to the invention allyl methacrylate (CAS number 96-05-9), allyl acrylate (CAS number 999-55-3) or mixtures of these compounds are used, hereinafter referred to as allyl (meth) acrylate. These compounds are reacted singly or as a mixture with hydrogen peroxide (H ₂ O ₂ ; CAS number 7722-84-1).

The hydrogen peroxide used can have more or less high amounts of water (H ₂ O), without this leading to problems with regard to the reaction procedure. A disadvantage of high amounts of water, however, is that they must be separated from the product mixture in the purification of the glycidyl (meth) acrylate. On the other hand, the production and use of highly concentrated hydrogen peroxide are complicated. Therefore, the molar ratio of hydrogen peroxide to water is expediently in the range from 20: 1 to 1:20, preferably in the range from 10: 1 to 1:10 and very particularly preferably in the range from 5: 1 to 1: 5, based on the reactants.

The molar ratio of allyl (meth) acrylate to H ₂ O ₂ is preferably greater than 1. Particular advantages with regard to the efficiency of the process can be achieved in particular in that the molar ratio of allyl (meth) acrylate to H ₂ O _{2 is} preferably in the Range from 20: 1 to 1: 5, more preferably in the range of 10: 1 to 1: 1 and most preferably in the range of 5: 1 to 2: 1.

The process according to the invention takes place in the presence of a catalyst. Catalysts that lower the activation energy of epoxidation are known per se. In this context, among other things, the pamphlets EP-A-190609 submitted on 22.01.86 to the European Patent Office with the application number EP 86100825.8 . EP-A-638,362 submitted on 10.08.94 to the European Patent Office with the application number EP 94112508.0 . JP-A-09059269 . JP-A-10158198 . JP-A-08188575 . JP-A-09132571 . JP-A-10168072 . JP-A-11165074 . JP-A-09235439 . JP-A-09301966 . CA-2033047-A . EP-B-434 546 submitted on 18.12.90 to the European Patent Office with the application number EP 90403648.0 . EP-B-468 840 submitted on 04.07.91 to the European Patent Office with the application number EP 91401849.4 . US 5,283,360 and WO-A-98/28287 submitted on 22.12.97 to the European Patent Office with the application number PCT / EP97 / 07283 The catalysts described therein are incorporated in this application for the purposes of disclosure.

Especially Preferred catalysts are insoluble in the educt mixture and include silica, wherein titanium silicalite catalysts are particularly preferred.

Titanium silicalite catalysts are generally synthetic zeolites wherein the molar ratio of TiO ₂ to SiO ₂ in the zeolite is less than one. Preferably, the molar ratio of TiO ₂ to SiO ₂ according to the formula xTiO ₂ · (1-x) SiO ₂ , where x is in the range of 0.0001 to 0.04, more preferably in the range of 0.0055 to 0.036.

The Pore size of the titanium silicalite catalyst is preferably in the range of 1 to 50 nm, more preferably 5 to 30 nm.

These Catalysts can be particularly by condensation reaction of tetraalkyl orthosilicates and tetraalkyl orthotitanates.

According to the invention the reaction continuously in a reactor. The term "continuous" is known in the art. Under a continuous reaction are In particular, understand implementations in which a extended period of reactants added to a reactor and separating products from the reaction mixture taken from the reactor become.

The Implementation can be carried out at overpressure or underpressure. According to one particularly useful modification of the present Invention may be epoxidation at a pressure in the range of 200 to 2000 mbar, more preferably in the range of 500 to 1300 mbar be performed.

The reaction temperature depends in particular on the type of catalyst used. The higher the activity of the catalyst, the lower temperatures can be used in the reaction. For the economy of the process, in particular the selectivity of the reaction is essential. Surprising advantages can be achieved in particular at a reaction temperature which is in the range of 20 ° C to 60 ° C, more preferably in the range of 25 ° C to 35 ° C.

According to one particularly expedient embodiment of the present Process are at most 50 mol .-%, preferably at most 30 mol% and most preferably at most 10 mol% of the allyl (meth) acrylate fed into the reactor, without this being a limitation. These Indication does not refer to the turnover of the whole process, at the unreacted in preferred variants allyl (meth) acrylate returned and in further passes but to the proportions of allyl (meth) acrylate, after being fed to the reactor in the reacted reaction mixture are included.

Preferably, at most 60 mol%, preferably at most 40 mol% and very particularly preferably at most 30 mol% of the H ₂ O ₂ fed into the reactor are reacted. This information does not refer to the overall process, in which unreacted H ₂ O ₂ can be recycled in preferred variants and reacted in further runs, but on the proportions of H ₂ O ₂ , which after the feed into the reactor in the reaction mixture are included.

The previously shown sales values can be over regulate the residence time, in particular in the range of 1 minute to 180 minutes, more preferably in the range of 5 minutes to 60 minutes. Refer to the use of multiple reactors this information is based on the sum of the residence times in these reactors.

The previously explained parameters are preferably chosen that the selectivity of the reaction is at least 85%, especially preferably at least 90% and most preferably at least 94%.

The Implementation takes place in at least one reactor, the Art the reactor is not subject to any particular restriction. Thus, in particular isothermal or adiabatic reactors used to carry out the implementation, too in the form of loop reactors containing a return of material may be formed.

isotherm Reactors allow a very good control of the reaction temperature, However, they are relatively expensive to invest, operate and maintain connected.

Surprising Leave advantages in terms of cost-efficiency of the process in particular by the use of one or more adiabatic Achieve reactors. In adiabatic reactors, the reaction is common without heat exchange instead. Because the present reaction exothermic, but a very strong increase in temperature many times can lead to a lower selectivity, require the present reactors no complex isolation to prevent heat exchange. Accordingly In the context of the present invention, the term "adiabatic reactor" is used Reaction vessel understood that no active Cooling has to keep the reaction temperature within to keep the reaction volume constant. This reactor can have a have a particularly simple and therefore inexpensive construction.

A Improvement of the method, which is not readily predictable was and can be based on an increase in selectivity achieved, inter alia, by the use of an installation, having at least two adiabatic reactors, wherein the reaction mixture is cooled between the reactors. The number of adiabatic Reactors in this embodiment is preferably in the range of 2 to 8, more preferably 3 to 5.

by virtue of the lack of active cooling within the adiabatic Reactor generally takes the temperature of the reaction mixture within the reactor too. The dimensions of the adiabatic reactors are preferably chosen so that the temperature increase at most 20 ° C, more preferably at most 10 ° C. For example, the temperature the reaction mixture at the entrance to the reactor at most 45 ° C, preferably at most 35 ° C and completely more preferably at most 27 ° C. whereas the temperature of the reaction mixture as it exits the reactor preferably at most 55 ° C, more preferably at most 45 ° C and most preferably at most 31 ° C is.

The use of polymerization inhibitors during the reaction or purification of the unsaturated compounds is not necessary. Thus, in particular in the partial epoxidation of allyl (meth) acrylate can be dispensed with the use of polymerization inhibitors. In the purification, however, can be achieved by the use of polymerization inhibitors advantages in terms of plant life and yield. These compounds, such as hydroquinones, hydroquinone ethers, such as hydroquinone monomethyl ether or di-tert-butyl catechol, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, Me methylene blue or sterically hindered phenols are well known in the art. These compounds can be used singly or in the form of mixtures and are generally available commercially. For further details on the usual specialist literature, in particular on the Römpp-Lexikon Chemistry; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996) ; Reference "Antioxidants" and cited references cited here.

The inventive method can in substance, d. H. performed without using a solvent become. If desired, an inert solvent may also be used be used. According to a preferred embodiment of the method may in particular be a polar solvent can be used with which the starting materials can be mixed well. Preferably, the starting materials without miscibility are within the reaction temperature range miscible with the solvent. Particularly preferred solvents include especially methanol, ethanol and propanol.

One preferred mixture which can be introduced into the reactor, comprises from 10 to 50% by weight, particularly preferably from 20 to 40% by weight, of allyl (meth) acrylate, 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-% hydrogen peroxide, 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-% of water and 30 to 90 wt .-%, particularly preferably 50 to 70 wt .-% solvent.

The product mixture obtained after the reaction, which is taken from the reactor, can preferably be purified in a multi-stage process to separate off excess H ₂ O ₂ .

According to an expedient embodiment of the process, H ₂ O ₂ remaining in the product mixture can be removed from the mixture by distillation or by utilizing a miscibility gap, for example using a phase separator (separating vessel).

If, for example, a polar solvent such as methanol or ethanol has been used, in a first step, the solvent can be separated from the product mixture by distillation together with water (H ₂ O) contained, with part of the allyl (meth) acrylate together with the methanol can be distilled off from the mixture.

Preferably can dispense with a particularly fine separation in this step since allyl (meth) acrylate and the solvent in the reactor can be returned.

The Temperature of the sump in this first distillation is preferably less than 110 ° C, more preferably less than 100 ° C and most preferably less than 80 ° C. The pressure in the first distillation is preferably in the range of 0.2 to 2 bar absolute, more preferably in the range of 0.5 to 1.5 absolutely bar.

The Mixture comprising allyl (meth) acrylate and the solvent can be separated by a second distillation if the solvent For example, in a device for the production of hydrogen peroxide and allyl (meth) acrylate to be introduced into the reactor. The Temperature of the sump in this second distillation is preferred less than 120 ° C, more preferably less than 90 ° C. The pressure in the second distillation is preferably in the range from 0.1 to 1.5 bar absolute, more preferably in the range of 0.2 to 1 bar absolute.

By separating the solvent, it is preferable to leave a composition which may include a part of the allyl (meth) acrylate, glycidyl (meth) acrylate and unreacted hydrogen peroxide (H ₂ O ₂ ). Since the solubility of H ₂ O ₂ in allyl (meth) acrylate or glycidyl (meth) acrylate is limited, a portion of the hydrogen peroxide can first be separated in a phase separator. Furthermore, the glycidyl (meth) acrylate can be separated from remaining allyl (meth) acrylate and / or H ₂ O ₂ by further distillation.

The Temperature of the sump in this third distillation is preferred less than 140 ° C, more preferably less than 120 ° C and most preferably less than 110 ° C. The pressure in the third distillation is preferably in the range of 10 to 200 mbar absolute, more preferably in the range of 20 to 100 mbar absolute. In the glycidyl (meth) acrylate remaining hydrogen peroxide can first separated by a phase separator and then be returned to the reactor.

The glycidyl (meth) acrylate can be purified in a fine purification of by-products. For this purpose, first of all the hydrogen peroxide remaining in this mixture can be catalytically decomposed, as described, for example, in US Pat JP-A-09132571 is set forth.

A preferred plant for carrying out the process according to the present invention comprises at least one apparatus for producing H ₂ O ₂ and at least one reactor, which is connected via a line to a first distillation column, wherein the column head via a line with a second distillation column in Compound, and the bottom of the first distillation column via a line with a third Destil lationskolonne is in communication, wherein the head of the second distillation column is connected via a line with the device for producing H ₂ O ₂ . Such a system is also an object of the present invention.

A convenient plant for the preparation of glycidyl (meth) acrylate comprises at least one device for the production of H ₂ O ₂ . Such units are known per se, with preferred methods and systems, in particular in EP-B 0 274 830 . EP-A 0 366 419 . EP-A 0 579 109 . DE-A 41 27 918 . EP-B 0 504 741 . EP-B 0 492 064 . EP-B 0 498 166 . EP-A-0 787 681 . EP-A-0 978 316 . EP-A-1 127 839 . WO 02/092501 are set out.

This H ₂ O ₂ is preferably a so-called direct synthesis, is reacted in the H ₂ directly with O ₂ to H ₂ O _2, in the presence of an alcohol such as, inter alia, in EP-A-0 787 681 or EP-A-0 978 316 is set forth.

The Plant for carrying out the inventive Method may include one or more reactors, wherein in this Reference is made to the above explanations becomes. Particularly preferred are one or more adiabatic reactors used, preferably plants with 2 to 8, particularly preferably 3 up to 5 reactors can be used. In this embodiment For example, the product mixture can be cooled between the reactors become.

Preferably For example, the reactor may essentially be in relation to the earth's surface be aligned vertically, d. H. the angle of inclination is about 90 °, with smaller deviations, for example from less than 10 °, preferably less than 5 °, many times can be tolerated. According to one particularly expedient embodiment of the invention The method becomes the substantially vertically oriented reactor flows down the top, so that the flow direction has a directional component perpendicular to the earth's surface is aligned.

The Plant may comprise one, two or more phase separators, in particular for the separation of water or hydrogen peroxide from the respective Serve mixtures.

The Components of the plant that come into contact with hydrogen peroxide come, especially the reactor, the pumps and the phase separator are preferably made of an oxidation-stable metal, for example Zirconium, tantalum, titanium or stainless steel or a coated one Metal, for example, an enamel layer or a zirconium layer has built up. Furthermore, plastics, for example PTFE coated components, graphitized components or workpieces made of graphite, especially in pumps.

The The foregoing will now be based on a non-limiting drawing exemplified.

1 schematically represents a preferred system for carrying out the method according to the invention. Via one or more lines 1a and 1b are the compounds required for the production of hydrogen peroxide, in particular a gas mixture comprising hydrogen and oxygen and optionally a solvent, for. As methanol in the apparatus for the production of hydrogen peroxide 2 initiated. The resulting product mixture, which may in particular comprise hydrogen peroxide and optionally a solvent, is then passed via line 3 , in the over line 4 Allyl (meth) acrylate can be introduced into the reactor 5a . 5b . 5c and 5d transferred, which in this case consists of several partial reactors 5a . 5b . 5c and 5d is constructed, wherein between or after the partial reactors 5a . 5b . 5c and 5d each cooling of the reaction mixture is carried out, for example, by heat exchangers 6a . 6b . 6c and 6d can be achieved.

The in the reactor 5a . 5b . 5c and 5d obtained product mixture is first in accordance with the present embodiment of the system in a gas separator 7 transferred, with gaseous by-products via line 8th can be derived from the plant. The liquid reaction mixture can then be passed via line 9 in a first distillery 10 be initiated, the compounds obtained via the head via line 11 in a second distillery 12 be transferred.

The second distillery 12 In particular, the mixture introduced may comprise allyl (meth) acrylate, water and solvents, for example methanol. The second distillery 12 separated solvent is passed overhead over line 13 in the apparatus for the production of hydrogen peroxide 2 transferred. The second distillery 12 The mixture discharged from the bottom generally comprises allyl (meth) acrylate and water, this mixture being passed via line 14 into a first phase separator 15 is initiated and separated.

The recovered allyl (meth) acrylate is passed over line 16 , which in this case with management 3 connected to the reactor 5a . 5b . 5c and 5d transferred. Separated water can via line 17 be taken from the plant.

The from the first still 10 Mixture separated via the bottom may in particular comprise allyl (meth) acrylate, hydrogen peroxide and glycidyl (meth) acrylate. The over the swamp separate mixture can be via line 18 in a third distillery 19 be introduced and separated, wherein the overhead composition, which may comprise in particular allyl (meth) acrylate and hydrogen peroxide, via line 20 in the reactor 5a . 5b . 5c and 5d is initiated. This can be done in particular by that line 20 with lead 3 connected is.

There in the third distillery 19 obtained bottom product may comprise larger amounts of hydrogen peroxide, this bottoms product is present via line 21 into a second phase separator 22 initiated, in which glycidyl (meth) acrylate is separated from hydrogen peroxide. To improve the separation performance, the second phase separator 22 Water are supplied, in which case from the first phase separator 15 obtained water can be used.

The glycidyl (meth) acrylate obtained in the second phase separator can be introduced via line 23 be taken from the plant. Furthermore, the obtained glycidyl (meth) acrylate can be subjected to a fine cleaning, which is not shown in the present figure.

The recovered from the third phase separator hydrogen peroxide can via line 24 in the illustrated embodiment in line 3 flows into the reactor 5a . 5b . 5c and 5d be transferred.

Next the previously explicitly illustrated components can be an inventive Plant further components, in particular pumps, sump evaporator etc., which in the figure for the sake of better Comprehensibility are not shown.

example

The performance of a shown in 1 Preferred embodiment of the plant for the production of glycidyl methacrylate was investigated.

The educts H ₂ O ₂ in methanol, fed via line 3 , and allyl methacrylate (AMA), fed via line 4 , together with the returned streams ( 16 ) 20 ) and ( 24 ) are fed sequentially arranged adiabatic fixed bed reactors ( 5a d). Between the reactors, the product is cooled by means of cooling water ( 6a d). Apart from the first reactor, which is operated at a lower temperature, an adiabatic temperature increase from 27 ° C to 31 ° C is achieved with the same distribution of the conversion to 4 reactors.

The product is after passing through a separating container 7 a distillery or column 10 fed in the top product is separated 99% MeOH; High boilers, the product GMA and H ₂ O ₂ are completely over the sump or pipe 18 discharged. A simultaneous, complete separation of AMA is not achieved in the present embodiment.

The over line 11 discharged overhead product is in another distillery 12 separated to a MeOH-free bottoms phase via line 14 is discharged, consisting of water and AMA and a MeOH-rich head phase, via pipe 13 is discharged to produce. AMA and water can be passed through a phase separator or separation vessel 15 into a sewage stream (line 17 ) and a recycled AMA stream (line 16 ).

The bottoms product, discharged via line 18 , the first distillery or column 10 contains the product GMA together with high-boiling, unreacted H ₂ O ₂ and AMA. The further separation of the high-boiling product GMA from AMA and H ₂ O ₂ takes place in a further distillation column 19 instead of.

The product GMA, discharged via wire 23 , comprises high boilers or traces of AMA, so that a further separation column for product fine cleaning can be used, which in 1 not shown. A stream of about 147 kg / h AMA and about 45.6 kg / h H ₂ O ₂ gave, with a hydrogen peroxide conversion of about 26% within the reactor, a flow of about 144.0 kg / h glycidyl methacrylate.

Example 2

Example 1 was essentially repeated except that the hydrogen peroxide conversion was changed from about 26% to 49.4%. A flow of about 148 kg / h AMA and about 43.4 kg / h H ₂ O ₂ gave a flow of about 106.1 kg / h glycidyl methacrylate.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 2525026 A [0003]
• - EP 190609 A [0004, 0005, 0005, 0020]
• - EP 638362 A [0004, 0020]
• - JP 09059269A [0004, 0020]
• - JP 10158198A [0004, 0020]
• - JP 08188575 A [0004, 0006, 0020]
• - JP 09132571 A [0004, 0007, 0020, 0048]
• - JP 10168072A [0004, 0020]
• - JP 11165074A [0004, 0020]
• - JP 09235439A [0004, 0020]
• - JP 09301966 A [0004, 0020]
• - CA 2033047A [0004, 0020]
• - EP 434546 B [0004, 0020]
• - EP 468840 B [0004, 0020]
• - DE 69125540 [0004]
• - US 5283360 [0004, 0020]
• WO 98/28287 A [0004, 0020]
• - EP 86100825 [0020]
• - EP 94112508 [0020]
• - EP 90403648 [0020]
• - EP 91401849 [0020]
• EP 97/07283 [0020]
• EP 0 274 830 B [0050]
• EP 0366419 A [0050]
• - EP 0579109 A [0050]
• - DE 4127918 A [0050]
• EP 0504741 B [0050]
• EP 0492064 B [0050]
• EP 0498166 B [0050]
• EP 0787681 A [0050, 0051]
• - EP 0978316 A [0050, 0051]
• - EP 1127839A [0050]
• WO 02/092501 [0050]

Cited non-patent literature

• - Römpp Lexicon Chemistry; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10 th edition (1996) [0037]

Claims (28)

A continuous process for the preparation of glycidyl (meth) acrylate comprising reacting allyl (meth) acrylate with H ₂ O ₂ in at least one reactor in the presence of a catalyst, wherein unreacted allyl (meth) acrylate is separated from the product mixture and into at least one reactor is recycled, characterized in that unreacted H ₂ O _{2 is separated} from the product mixture and recycled to at least one reactor. Process according to claim 1, characterized characterized in that the reaction is at a temperature in the range from 20 ° C to 60 ° C is performed. Process according to claim 2, characterized characterized in that the reaction is at a temperature in the range from 25 ° C to 35 ° C is performed. Method according to at least one of the preceding claims, characterized in that the reaction was carried out in an adiabatic reactor becomes. A method according to claim 4, characterized characterized in that the adiabatic reactor is substantially vertical is aligned and the reaction mixture from the bottom of the reactor flows through the top. A method according to claim 4 or 5, characterized in that the reaction is carried out in a plant which has at least two adiabatic reactors, wherein the reaction mixture is cooled between the reactors. Method according to at least one of claims 4 to 6, characterized in that the temperature the reaction mixture at the entrance to the reactor at most 35 ° C. Method according to at least one of claims 4 to 7, characterized in that the temperature the reaction mixture at the exit from the reactor at most 45 ° C is. Method according to at least one of the preceding claims, characterized in that the reaction is carried out with a catalyst, which is insoluble in the reaction mixture. A method according to claim 9, characterized characterized in that the reaction using a titanium silicalite catalyst is carried out. Process according to at least one of the preceding claims, characterized in that the molar ratio of the reaction mixture used of allyl (meth) acrylate to H ₂ O _{2 is} greater than 1. Process according to at least one of the preceding claims, characterized in that the molar ratio of allyl (meth) acrylate to H ₂ O _{2 is} in the range from 10: 1 to 1: 1. Method according to at least one of the preceding claims, characterized in that at most 50 mol .-% of the fed into the reactor Allyl (meth) acrylates are reacted. Process according to at least one of the preceding claims, characterized in that at most 60 mol% of the H ₂ O ₂ fed into the reactor are reacted. Method according to at least one of the preceding claims, characterized in that the reactant mixture introduced into the reactor is a solvent includes. A method according to claim 15, characterized characterized in that the solvent is methanol, ethanol or propanol. Method according to at least one of the preceding claims, characterized in that the reacted reaction mixture worked up by a method which comprises at least two distillations. Process according to Claim 17, characterized in that, in a first distillation, the solvent, H ₂ O obtained and a part of the allyl (meth) acrylate used are separated overhead from H ₂ O _{2 used} and glycidyl (meth) acrylate obtained. A method according to claim 18, characterized characterized in that the first distillation at a sump temperature less than 110 ° C is performed. A method according to any one of claims 17 to 19, characterized in that in a second distillation, the solvent is separated overhead from the allyl (meth) acrylate used, wherein obtained H ₂ O via the bottom with the allyl (meth) acrylate from the still is removed. A method according to claim 20, characterized in that the H ₂ O is separated from the allyl (meth) acrylate by a phase separator. Process according to at least one of Claims 17 to 21, characterized in that H ₂ O ₂ used in a third distillation and a Part of the allyl (meth) acrylate used is separated overhead from the resulting glycidyl (meth) acrylate. A method according to claim 22, characterized characterized in that the third distillation at a bottom temperature less than 120 ° C is performed. A method according to any one of claims 17 to 23, characterized in that a part of the H ₂ O _{2 is} separated from the glycidyl (meth) acrylate by a phase separator. Plant for carrying out a process according to at least one of claims 1 to 24, characterized in that the plant comprises at least one apparatus for producing H ₂ O ₂ and at least one reactor which is connected via a line to a first distillation column, wherein the column head is connected via a line to a second distillation column, and the bottom of the first distillation column is connected via a line with a third distillation column, wherein the head of the second distillation column is connected via a line to the device for producing H ₂ O ₂ . Plant according to claim 25, characterized characterized in that the plant has at least two adiabatic reactors having. Plant according to claim 25 or 26, characterized in that the head of the third distillation column via a conduit communicates with the reactor. Plant according to at least one of claims 25 to 27, characterized in that the system at least two phase separator having.