WO2003014074A1 - Production de peroxydes de l'ethylbenzene et leur utilisation - Google Patents

Production de peroxydes de l'ethylbenzene et leur utilisation Download PDF

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Publication number
WO2003014074A1
WO2003014074A1 PCT/EP2002/007868 EP0207868W WO03014074A1 WO 2003014074 A1 WO2003014074 A1 WO 2003014074A1 EP 0207868 W EP0207868 W EP 0207868W WO 03014074 A1 WO03014074 A1 WO 03014074A1
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WIPO (PCT)
Prior art keywords
ethylbenzene
mol
radical
reaction
catalyst
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PCT/EP2002/007868
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German (de)
English (en)
Inventor
Adolf KÜHNLE
Carsten Jost
Roger Arthur Sheldon
Sandrine M. M. Chatel
Isabelle W. C. E. Arends
Original Assignee
Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Creavis Gesellschaft Für Technologie Und Innovation Mbh filed Critical Creavis Gesellschaft Für Technologie Und Innovation Mbh
Publication of WO2003014074A1 publication Critical patent/WO2003014074A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • C07C409/08—Compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds

Definitions

  • the invention relates to a process for the preparation of peroxides of ethylbenzene and their use for the oxidation of olefins, in particular for the epoxidation of propene.
  • Epoxidized propene or propylene oxide is very important in the chemical industry. Among other things, it serves as a basic raw material for the production of propylene glycols, glycol ethers, glycerin, isopropanolamines and for various propoxylation products for polyurethanes.
  • propylene oxide is in contrast to e.g. B. ethylene oxide and butylene oxide difficult to manufacture.
  • the hydrogen of the allyl-containing methyl group is preferably subject to oxidation, so that predominantly acrolein is formed.
  • NHPI N-hydroxyphthalimide
  • a further development of the system is the use of co-catalysts.
  • Metal compounds, in particular heavy metal salts, enzymes or strong Bronsted acids can be used as co-catalysts.
  • Ishii et al. Showed that NHPI in combination with redox metal salts as cocatalyst can have advantages over oxidation with NHPI without cocatalyst (e.g. EP 0878234, EP 0864555, EP 0878458, EP 0858835, JP 11180913, J Mol. Catalysis A. 1997, 117, 123-137).
  • the disadvantage of this system is the high amount of NHPI used. To ensure a satisfactory reaction rate, at least 10 mol% of catalyst must be used.
  • Another disadvantage is that the redox metals used partially catalyze further reactions of the products and thus reduce the selectivity of the reaction.
  • EP 0 927 717 generally describes a process for the preparation of hydroperoxides from hydrocarbons.
  • the focus of this invention is on the isopropyl derivatives of benzene, that is - on account of the tertiary carbon atom - on easily oxidizable substrates and on sterically hindered piperidine derivatives (so-called TEMPO products) as catalysts.
  • TEMPO products sterically hindered piperidine derivatives
  • examples of the use of NHPI are also given, the examples showing that this catalyst is present in very small amounts (approx. 0.1 mol%) and a relatively high content of radical initiator (approx. 20 mol%) is used becomes.
  • the person skilled in the art can at best conclude from the examples and comparative examples that NHPI has no effect.
  • the reaction is also started with a very large excess of radical initiator (200 times the amount of catalyst).
  • the present invention therefore relates to a process according to claim 1 for the preparation of hydroperoxides of ethylbenzene by catalytic oxidation in the side chain to the corresponding hydroperoxide, which is characterized in that Ethylbenzene with a compound of formula I.
  • R 1 , R 2 H, aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each with 1 to 20 carbon atoms, SO 3 H, NH 2 , OH, F, Cl, Br, I and / or NO 2 , where R 1 and R 2 are identical or denote different radicals or R 1 and R 2 can be linked to one another via a covalent bond, with
  • X, Z C, S or CH 2
  • the present invention also relates to the use of a hydroperoxide prepared according to claims 1 to 9 for the oxidation of linear and cyclic olefins, for the epoxidation of linear and cyclic olefins or for the epoxidation of propene.
  • the process according to the invention has the advantage that hydroperoxides of hydrocarbons, in particular ethylbenzene, can be obtained with significantly higher selectivity than according to processes according to the prior art.
  • hydroperoxides of hydrocarbons in particular ethylbenzene
  • considerably fewer radical starters are required.
  • the reaction can even be started without the addition of a radical starter. This is then either formed beforehand as an intermediate or is still present in traces from previous reactions. Since the product obtained as hydroperoxide is usually reused as a radical initiator, the overall yield of the process according to the invention is significantly higher than in the processes according to the prior art due to the smaller amount of radical initiator required to start the reaction.
  • the larger amount of catalyst to be used, however, is irrelevant, since the catalyst is not consumed, but can be separated from the reaction mixture and reused.
  • the process according to the invention also manages without heavy metals or strong acids as co-catalysts for the oxidation of ethylbenzene and its derivatives to the corresponding hydroperoxides and is therefore more environmentally friendly and more economical than corresponding processes in which these co-catalysts are used.
  • the process according to the invention is characterized in that for the preparation of hydroperoxides of ethylbenzene by catalytic oxidation in the side chain to the corresponding hydroperoxide, the ethylbenzene with a compound of the formula I
  • R 1 , R 2 H, aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each with 1 to 20 carbon atoms, SO 3 H, NH 2 , OH, F, Cl, Br, I and / or NO 2 , where R 1 and R 2 are identical or different
  • the molar ratio of the catalyst to ethylbenzene is preferably from 0.3 mol% to 5 mol% or from 5 mol% to 10 mol%, in particular from 0.5 mol% to 2.5 mol%, from 2.5 to 5 mol -%, from 5 to 7.5 mol% or from 7.5 to 10 mol% and very particularly preferably from 0.5 to 2.0 mol%.
  • Examples of compounds of formula I are e.g. B. N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxyhetimide, N-hydroxyhimimide, N-hydroxytrimellitimide, N-hydroxy- benzene-l, 2,4-tricarboximide, N, N'-dihydroxy-pyromellitic acid diimide, N, N'-dihydroxy-benzophenone-3,3 ', 4,4'-tetracarboxylic acid diimide, N-hydroxymaleimide, N-hydroxy-pyridine-2 , 3-dicarboximide, N-hydroxysuccinimide, N-hydroxy tartarimide, N-hydroxy-5-norbonen-2,3-dicarboximide, exo-N-hydroxy-7-oxabicyclo [2.2.
  • the process is preferably carried out in organic solvents in the absence of strong acids, and the use of an aqueous solution, the pH of which can range from weakly acidic to basic, is also possible.
  • the reaction is particularly preferably carried out in a solvent system which has at least 50% by weight, preferably 95% by weight and very particularly preferably at least 99.9% by weight of ethylbenzene. Carrying out in pure ethylbenzene is very particularly preferred Solvent, which means that the reaction is carried out in bulk.
  • the ethylbenzene is oxidized to the hydroperoxide in the liquid phase at a temperature of 0 to 300 ° C., preferably at a temperature of 20 to 200 ° C., in particular at a temperature of 40 to 150 ° C.
  • a solvent or solvent mixture and the ethylbenzene itself can be used as the solvent.
  • the process according to the invention is advantageous with ethylbenzene as the substrate to be oxidized.
  • the selectivity in the oxidation of ethylbenzene without a catalyst suffers in particular from the fact that it takes place on a secondary carbon atom.
  • it is much easier to oxidize cumene, in practice even often without a catalyst since a tertiary carbon atom capable of forming stable radicals is oxidized here.
  • two neighboring methyl groups stabilize the radical.
  • a radical initiator is added to the reaction mixture, which is either itself a radical or disintegrates to form radicals, such as.
  • examples of such compounds are cumene hydroperoxide, cyclohexylbenzene hydroperoxide, cyclododecylbenzene hydroperoxide, 1,4-di (2-neodecanoyl-peroxyisopropyl) benzene, acetylcyclohexanesulfonylperoxide, cumylperoxyneodecanoate, di-cyclohexylperyl (4-cyclohexyl) (4-cyclohexyl) (4) hexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate,
  • a radical initiator which is an azo compound or contains an oxygen atom bonded to a carbon atom is preferably used.
  • a radical initiator which contains an oxygen atom bonded to a secondary or tertiary carbon atom is particularly preferably used.
  • the radical initiator is derived from the end product.
  • the radical initiator is usually added separately, but it can also be generated as an intermediate prior to the actual reaction (e.g. from the solvent) or can still be present from previous reactions.
  • the radical initiator is present in a molar ratio of less than 12 mol%, preferably less than 10 mol%, particularly preferably less than 1 mol% and very particularly preferably less than 0.5 mol%.
  • the molar content of the radical initiator at the beginning of the reaction is preferably from 0.2 mol% to 10 mol%, particularly preferably from 0.5 mol% to 5 mol% or from 5 mol% % to 10 mol% and very particularly preferably from 0.2 to 0.7 mol% or from 0.7 mol% to 2.5 mol%.
  • the molar ratio of oxidation catalyst to radical initiator at the beginning of the reaction can be decisive for the speed and selectivity of the reaction. This is therefore preferably at least 1: 1, based on mol%. This means that the oxidation catalyst should be in excess at the start of the reaction and should not be less than the amount of radical initiator at the start of the reaction.
  • the oxidation product formed can be isolated as such, but the direct further conversion of this compound into the desired epoxidized product is also possible.
  • Existing plants are expediently used for the production of propylene oxide and only the oxidation to ethylbenzene hydroperoxide is modified according to the invention. According to the invention, the process can be carried out either batchwise or continuously.
  • the process according to the invention can be carried out using an oxygen-containing gas as the oxidizing agent.
  • the proportion of oxygen in the gas can be between 5 to 100% by volume.
  • Atmospheric oxygen or pure oxygen is preferably used as the oxidizing agent. It is important to ensure that the liquid and gaseous phases are thoroughly mixed. This can e.g. B. in stirred tanks by a corresponding stirring speed or by internals and in tubular reactors with packing elements and with bubble acids.
  • the process according to the invention can be carried out at a temperature of 0 to 300 ° C., preferably at a temperature of 20 to 200 ° C., in particular at a temperature of 40 to 150 ° C.
  • the pressure can be both at atmospheric pressure (1 bar) and at increased pressure up to 100 bar.
  • a pressure of 1 bar to 50 bar is preferred, a pressure of 1 bar to 20 bar is particularly preferred.
  • the ethylbenzene hydroperoxide produced can be used for the oxidation of linear and cyclic olefins, for the epoxidation of linear and cyclic olefins or for the epoxidation of propene.
  • Example 1 (according to the invention):
  • Example 4 (not according to the invention, with cobalt catalyst): 30 mmol of ethylbenzene are in a round-bottomed flask with a reflux condenser at a temperature of 56 ° C. with 0.6 mmol of N-hydroxyphthalimide and 0.6 mmol of Co (II) acetate in 100 ml of acetone are added. The reaction mixture is stirred for 8 hours at the temperature mentioned while passing air at 5 l / h. It is not the target product but acetophenone with a selectivity of approx. 22%, benzaldehyde approx. 9%, as well as a lot of different products (approx. 64%) and oligomers (rest) with an ethylbenzene conversion of 12.3%.
  • Example 5 (not according to the invention, analogous to EP 0 927 717 (1997), temperature 56 ° C.) 30 mmol of ethylbenzene are in a round-bottomed flask with a reflux condenser at a temperature of 56 ° C. with 0.03 mmol of N-hydroxyphthalimide and 6 mmol of 1- Cumene hydroperoxide in 100 ml acetone. The reaction mixture is 8 hours at mentioned temperature stirred while passing air of 5 1 / h. There is obtained ethylbenzene hydroperoxide with a selectivity of 12.3% with an ethylbenzene conversion of 0.3%.
  • Example 6 (not according to the invention, analogous to EP 0927717 (1997), temperature 105 ° C.)
  • the conversion of the oxidation reaction was determined on the one hand by titration of the peroxide with iodine and on the other hand by GC analysis with an internal standard (naphthalene).
  • the selectivity of the oxidation reaction was also determined by GC analysis with an internal standard (also naphthalene).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour la production d'hydroperoxydes de l'éthylbenzène par oxydation catalytique et leur utilisation pour l'oxydation d'oléfines. Selon l'invention, on utilise comme catalyseur d'oxydation un composé de formule (I) en présence d'un initiateur radicalaire. Dans la formule (I), R1 et R2 représentent H, un reste alcoxy, carboxyle, alcoxycarbonyle ou hydrocarbure aliphatique ou aromatique, comprenant respectivement 1 à 20 atomes de carbone, SO¿3?H, NH2, OH, F, Cl, Br, I ou NO2, R?1 et R2¿ étant identiques ou représentant des restes différents ou R1 et R2 pouvant être liés l'un à l'autre par une liaison covalente ; X et Z représentent C, S ou CH¿2? ; Y représente O ou OH ; k vaut 0, 1 ou 2 ; l vaut 0, 1 ou 2 et m vaut 1 à 3. Selon l'invention, le rapport molaire du catalyseur à l'éthylbenzène est compris entre 0,15 mole % et 10 mole %.
PCT/EP2002/007868 2001-08-09 2002-07-16 Production de peroxydes de l'ethylbenzene et leur utilisation WO2003014074A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10139212.5 2001-08-09
DE2001139212 DE10139212A1 (de) 2001-08-09 2001-08-09 Herstellung von Peroxiden des Ethylbenzols und deren Verwendung

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WO2003014074A1 true WO2003014074A1 (fr) 2003-02-20

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459810A (en) * 1965-12-30 1969-08-05 Halcon International Inc Process for the preparation of ethylbenzene hydroperoxide
US4299991A (en) * 1979-12-28 1981-11-10 The Standard Oil Company Formation of hydroperoxides
US5030739A (en) * 1985-04-17 1991-07-09 Hoffman-La Roche Inc. Process for the catalytic oxidation of isoprenoids having allylic groups
EP0927717A1 (fr) * 1997-07-09 1999-07-07 Mitsui Chemicals, Inc. Procede servant a preparer des hydroperoxydes
EP0990631A1 (fr) * 1998-03-27 2000-04-05 Daicel Chemical Industries, Ltd. Procede permettant de co-oxyder des composes organiques, procede permettant de produire des composes epoxy et procede permettant de produire des esters ou des lactones

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459810A (en) * 1965-12-30 1969-08-05 Halcon International Inc Process for the preparation of ethylbenzene hydroperoxide
US4299991A (en) * 1979-12-28 1981-11-10 The Standard Oil Company Formation of hydroperoxides
US5030739A (en) * 1985-04-17 1991-07-09 Hoffman-La Roche Inc. Process for the catalytic oxidation of isoprenoids having allylic groups
EP0927717A1 (fr) * 1997-07-09 1999-07-07 Mitsui Chemicals, Inc. Procede servant a preparer des hydroperoxydes
EP0990631A1 (fr) * 1998-03-27 2000-04-05 Daicel Chemical Industries, Ltd. Procede permettant de co-oxyder des composes organiques, procede permettant de produire des composes epoxy et procede permettant de produire des esters ou des lactones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ISHII Y ET AL: "ALKANE OXIDATION WITH MOLECULAR OXYGEN USING A NEW EFFICIENT CATALYTIC SYSTEM: N-HYDROXYPHTHALIMIDE (NHPI) COMBINED WITH CO(ACAC)N (N = 2 OR 3)", JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 61, no. 14, 12 July 1996 (1996-07-12), pages 4520 - 4526, XP000591064, ISSN: 0022-3263 *

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