DE102004055805A1 - Heterogeneous ruthenium catalyst on silica carrier, used in ring hydrogenation of carbocyclic compound, especially bisphenol A or F bisglycidyl ether, to corresponding cycloaliphatic compound, has alkaline earth metal ions on surface - Google Patents

Abstract

Heterogeneous ruthenium catalyst containing silica as carrier material contains alkaline earth metals ions on its surface.

Description

in der R CH₃ oder H bedeutet, durch Kernhydrierung des entsprechenden aromatischen Bisglycidylethers der Formel II

in Gegenwart eines Katalysators sowie mit diesem Verfahren herstellbare Bisglycidylethers der Formel I.The present invention relates to a ruthenium heterogeneous catalyst containing silica as a support material, a process for the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, in particular a process for the preparation of a bisglycidyl ether of the formula I.

in which R denotes CH ₃ or H, by nuclear hydrogenation of the corresponding aromatic bisglycidyl ether of the formula II

in the presence of a catalyst as well as bisglycidyl ethers of the formula I. which can be prepared by this process.

The Compound II with R = H is also bis [glycidyloxiphenyl] methane (molecular weight: 312 g / mol).

The compound II with R = CH ₃ is also called 2,2-bis [p-glycidyloxiphenyl] propane (molecular weight: 340 g / mol).

The Preparation of cycloaliphatic oxirane compounds I, the no have aromatic groups, is for the production of light and weatherproof Paint systems of particular interest. Basically, such compounds by hydrogenation of corresponding aromatic compounds II produced. The compounds I are therefore also termed "ring hydrogenated bisglycidyl ethers bisphenols A and F ".

The Compounds II have been used as components of paint systems for a long time (see J.W. Muskopf et al., "Epoxy Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).

Problematic is however the high reactivity the oxirane groups in the catalytic hydrogenation. Among those for hydrogenation of the aromatic nucleus usually required reaction conditions, these groups are often too Alcohol reduced. For this reason you have to hydrogenate the Connections II under possible perform mild conditions. Naturally, however, this requires a slowdown of the desired Aromatics.

US-A-3,336,241 (Shell Oil Comp.) Teaches the preparation of cycloaliphatic compounds with epoxy groups the hydrogenation of corresponding aromatic Epoxy compounds with rhodium and ruthenium catalysts. The activity of the catalysts decreases after hydrogenation so much that in a technical Process the catalyst to be changed after each hydrogenation got to. In addition, leaves the selectivity of there described catalysts to be desired.

DE-A-36 29 632 and DE-A-39 19 228 (both BASF AG) teach the selective hydrogenation of the aromatic moieties of bis [glycidyloxiphenyl] methane or of 2,2-bis [p-glycidyloxiphenyl] propane to ruthenium oxide hydrate. This improves the selectivity of the hydrogenation with respect to the aromatic groups to be hydrogenated. However, according to this teaching, it is advisable to regenerate the catalyst after each hydrogenation, wherein the separation of the catalyst from the reaction mixture is problematic proves.

EP-A-678 512 (BASF AG) teaches the selective hydrogenation of the aromatic moieties of aromatic compounds containing oxirane groups on ruthenium catalysts, preferably ruthenium oxide hydrate, in the presence of from 0.2 to 10% by weight Water, based on the reaction mixture. Due to the presence of water Although the separation of the catalyst from the reaction mixture relieved, the rest Disadvantages of these catalysts such as improved durability however, they will not be resolved.

EP-A-921 141 and EP-A1-1 270 633 (both Mitsubishi Chem. Corp.) the selective hydrogenation of double bonds in certain epoxy compounds in the presence of Rh and / or Ru catalysts with a specific surface or in the presence of catalysts containing metals of the platinum group.

JP-A-2002 226380 (Dainippon) discloses the nuclear hydrogenation of aromatic Epoxy compounds in the presence of supported Ru catalysts and a carboxylic acid ester as a solvent.

JP-A2-2001 261666 (Maruzen Petrochem.) Relates to a continuous process Nuclear hydrogenation of aromatic epoxide compounds in the presence of preferably on activated carbon or alumina supported Ru catalysts.

One Article by Y. Hara et al. in Chem. Lett. 2002, pages 1116ff the "Selective Hydrogenation of Aromatic Compounds Containing Epoxy Group over Rh / Graphite ".

Tetrahedron Lett. 36, 6, pages 885-88, describes stereoselective nuclear hydrogenation of substituted aromatics using colloidal Ru.

JP 10-204002 (Dainippon) relates to the use of specific, in particular Alkali-doped Ru catalysts in a kryrogenation process.

JP-A-2002 249488 (Mitsubishi) teaches hydrogenation processes in which a noble metal supported catalyst is used, the chlorine content is below 1500 ppm.

WO-A1-03 / 103 830 and WO-A1-04 / 009 526 (both Oxeno) relate to the hydrogenation of aromatic compounds, in particular the production of alicyclic polycarboxylic acids or their esters by nuclear hydrogenation of the corresponding aromatic polycarboxylic or their esters, and this suitable catalysts.

The Prior art processes have the disadvantage that the used Catalysts have low lifetimes and usually must be regenerated consuming after each hydrogenation. Also lets the activity the catalysts to be desired, so that under the for a selective hydrogenation required reaction conditions only low space-time yields, based on the catalyst used to be obtained. However, this is in view of the high cost for ruthenium and for that the catalyst economically unreasonable.

EP-A2-814 098 (BASF AG) relates inter alia. Process for the nuclear hydrogenation of organic Compounds in the presence of specific supported Ru catalysts.

WO-A2-02 / 100 538 (BASF AG) describes a process for the preparation of certain cycloaliphatic compounds containing side chains with epoxide groups have, by heterogeneous catalytic hydrogenation of a corresponding A compound containing at least one carbocyclic aromatic group and at least one side chain having at least one epoxide group has, on a ruthenium catalyst.

• i) ein oder mehrfaches Behandeln eines Trägermaterials auf Basis von amorphem Siliziumdioxid mit einer halogenfreien wässrigen Lösung einer niedermolekularen Rutheniumverbindung und anschließendes Trocknen des behandelten Trägermaterials bei einer Temperatur unterhalb 200°C,
• ii) Reduktion des in i) erhaltenen Feststoffs mit Wasserstoff bei einer Temperatur im Bereich von 100 bis 350°C,

wobei man und Schritt ii) unmittelbar im Anschluss an Schritt i) durchführt.The ruthenium catalyst is available through

• i) one or more treatment of an amorphous silica-based support material with a halogen-free aqueous solution of a low-molecular-weight ruthenium compound and subsequent drying of the treated support material at a temperature below 200 ° C.,
• ii) reduction of the solid obtained in i) with hydrogen at a temperature in the range of 100 to 350 ° C,

wherein one and step ii) immediately after step i) performs.

WO-A2-02 / 100538 teaches that the compounds used "both can be monomeric as well as oligomeric or polymeric compounds "(page 9 above).

WO-A2-02 / 100 538 teaches nothing the addition of alkaline earth metal ions.

It is an object of the present invention to provide an improved selective process for the hydrogenation of aromatic groups to the corresponding "core hydrogenated" groups, with high yields and space-time yields, [product amount / (catalyst volume · time)] (kg / ( I · h)), [product amount / (reactor volume · tent)] (kg / (I _reactor · h)), based on the catalyst used, and in which the catalysts used can be used repeatedly for hydrogenations without work-up. In particular, compared with the process of WO-A2-02 / 100 538, higher catalyst service lives should be achieved.

in der R CH₃ oder H bedeutet, durch Kernhydrierung des entsprechenden aromatischen Bisglycidylethers der Formel II

welches dadurch gekennzeichnet ist, dass man den o.g. Ruthenium-Heterogenkatalysator einsetzt, und Bisglycidylether der Formel I, herstellbar durch das o.g. Verfahren, gefunden.Accordingly, a ruthenium heterogeneous catalyst containing silica as a support material, which is characterized in that the catalyst ^surface contains alkaline earth metal ions (M ²⁺ ), has been a process for hydrogenating a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, in particular, a process for producing the bisglycidyl ethers of the formula I

in which R denotes CH ₃ or H, by nuclear hydrogenation of the corresponding aromatic bisglycidyl ether of the formula II

which is characterized in that the above-mentioned ruthenium heterogeneous catalyst is used, and bis-glycidyl ethers of the formula I, which can be prepared by the abovementioned process, are found.

One An essential component of the catalysts according to the invention is the support material based on amorphous silicon dioxide. The term "amorphous" is understood in In this context, that the proportion of crystalline silica phases less than 10% by weight of the carrier material accounts. The support materials used to prepare the catalysts can however superstructures have, by regular Arrangement of pores in the carrier material be formed.

The catalyst surface of the catalysts according to the invention contains alkaline earth metal ions (M ²⁺ ), ie M = Be, Mg, Ca, Sr and / or Ba, in particular Mg and / or Ca, very particularly Mg.

Suitable support materials are in principle amorphous silicon dioxide types which consist of at least 90% by weight of silicon dioxide, the remaining 10% by weight, preferably not more than 5% by weight, of the support material also being another oxidic material can, for example MgO, CaO, TiO ₂ , ZrO ₂ , Fe ₂ O ₃ and / or alkali metal oxide.

In a preferred embodiment The invention is the carrier material halogen-free, especially chlorine-free, d. H. the content of halogen in the carrier material is less than 500 ppm by weight, e.g. in the range of 0 to 400 ppm by weight.

Preference is given to support materials which have a specific surface area in the range from 30 to 700 m ² / g, preferably from 30 to 450 m ² / g (BET surface area to DIN 66131).

suitable amorphous carrier materials based on silica are familiar to the expert and commercial available See, for example, O.W. Flörke, "Silica" in Ullmann's Encyclopedia of Industrial Chemistry 6th Edition on CD-ROM). You can both natural Origin as well as artificial have been produced. Examples of suitable amorphous support materials based on silica are silica gels, diatomaceous earth, pyrogenic silicas and precipitated silicas. In a preferred embodiment According to the invention, the catalysts comprise silica gels as support materials on.

ever According to an embodiment of the invention, the carrier material may be different Have shape. Unless the process is a suspension process is configured, it is customary for the preparation of the catalysts of the invention the carrier material in the form of a finely divided powder. Preferably the powder particle sizes in the range of 1 to 200 μm in particular 1 to 100 μm on. When using the catalyst used in fixed catalyst beds usually moldings from the substrate, the e.g. are available by extrusion, extrusion or tableting and the e.g. the shape of spheres, tablets, cylinders, strands, rings or hollow cylinders, stars and the like may have. The dimensions this shaped body usually move in the range of 1 mm to 25 mm. Often become catalyst strands with strand diameters of 1.5 to 5 mm and strand lengths of 2 to 25 mm used.

Of the Content of ruthenium in the catalysts can be varied over a wide range become. It is preferably at least 0.1% by weight, preferably at least 0.2 wt .-% and often a value of 10 wt .-%, each based on the weight of the carrier material and calculated as elemental ruthenium, do not exceed. Preferably the content of ruthenium is in the range of 0.2 to 7 wt .-% and in particular in the range of 0.4 to 5% by weight, e.g. 1.5 to 2 wt .-%.

The content of alkaline earth metal ions (M ²⁺ ) in the catalyst surface is preferably 0.01 to 1% by weight, in particular 0.05 to 0.5% by weight, very particularly 0.1 to 0.25% by weight. -%, in each case based on the weight of the silica support material.

The Preparation of the ruthenium catalysts according to the invention is preferably carried out by first of all the carrier material with a solution of a low molecular weight ruthenium compound, hereinafter referred to as (ruthenium) precursor designated, treated in a way that the desired amount on ruthenium from the carrier material is recorded. Preferred solvents here are glacial acetic acid, water or mixtures thereof. This step is hereafter also called potions designated. Subsequently becomes the carrier thus treated, preferably in compliance with the upper temperature limits specified below, dried. Optionally, then the thus obtained solid again with the aqueous solution treated ruthenium precursor and dried again. This The process is repeated until the amount absorbed by the carrier material to ruthenium compound the desired Ruthenium content in the catalyst corresponds.

The Treat or soak of the carrier material can be done in different ways and is based in well-known Way after the shape of the substrate. For example, you can with the carrier material the precursor solution spray or rinse or the carrier material in the precursor solution suspend. For example, you can the carrier material in the aqueous solution of the ruthenium precursor and after a certain time from the aqueous supernatant Filter off. about the amount of liquid absorbed and the ruthenium concentration of the solution may then be the ruthenium content the catalyst can be controlled in a simple manner. The soaking of the support material For example, it can also be done by using the carrier a defined amount of the solution the ruthenium precursor treats the maximum amount of fluid corresponds to the carrier material can record. For this purpose, for example, the carrier material with the required amount of fluid spray. Suitable equipment for this are the ones for mixing liquids with solids usually used apparatus (see Vauck / Müller, basic operations chemical Process Engineering, 10th edition, German publishing house for primary industry, 1994, p. 405 ff.), For example tumble dryers, trough drums, Drum mixer, paddle mixer and the like. Monolithic carriers are commonly used with the watery Solutions of the Rinsed ruthenium precursors.

The solutions used for impregnating are preferably low in halogen, in particular low in chlorine, ie they contain no or less than 500 ppm by weight, in particular less than 100 ppm by weight of halogen, for example 0 to <80 ppm by weight of halogen, based on the total weight the solution. As Rutheniumprekursoren therefore, in addition to RuCl ₃ preferably those ruthenium compounds are used which contain no chemically bound halogen and which are sufficiently soluble in the solvent. These include, for example, ruthenium (III) nitrosyl nitrate (Ru (NO) (NO ₃ ) ₃ ), ruthenium (III) acetate and the alkali metal ruthenates (IV) such as sodium and potassium ruthenate (IV).

All particularly preferred Ru precursor is Ru (III) acetate. This Ru connection is usually dissolved in acetic acid or Glacial acetic acid, but it can also be used as a solid. Of the catalyst according to the invention can be made without using water.

Many ruthenium precursors are offered commercially as a solution, but the same solids can be used as well. These precursors can be dissolved or diluted either with the same component as the solvent offered, such as nitric acid, acetic acid, hydrochloric acid, or preferably with water. It is also possible to use mixtures of water or solvent with up to 50% by volume of one or more organic solvents which are miscible with water or solvents, for example mixtures with C ₁ -C ₄ -alkanols, such as methanol, ethanol, n-propanol or isopropanol become. All mixtures should be chosen so that there is a solution or phase. The concentration of the ruthenium precursor in the solutions naturally depends on the amount of ruthenium precursor to be applied and the absorption capacity of the carrier material for the solution, and is preferably in the range from 0.1 to 20% by weight.

The Drying can be done according to the usual Method of drying solids in compliance with the below Upper temperature limits occur. Compliance with the upper limit of Drying temperatures is for the quality, i.e. the activity of the catalyst important. A crossing The drying temperatures listed below lead to a significant loss in activity. A calcining of the vehicle at higher temperatures, e.g. above 300 ° C or even 400 ° C, as proposed in the prior art is not only superfluous, but also adversely affects the activity of the catalyst. to Achieving adequate drying rates is the Drying is preferred at elevated temperatures Temperature, preferably at ≤ 180 ° C, especially at ≤ 160 ° C, and at at least 40 ° C, in particular at least 70 ° C, especially at least 100 ° C, especially at least 140 ° C.

The Drying of the solid impregnated with the ruthenium precursor is usually carried out under normal pressure while promoting The drying can also be applied a reduced pressure. Frequently becomes one for promotion drying a gas stream over or through the material to be dried, e.g. Air or nitrogen.

The Drying time hangs by nature of that desired Degree of drying and drying temperature and is preferred in the range of 1 h to 30 h, preferably in the range of 2 to 10 H.

Preferably you lead the drying of the treated carrier material so far that the content of water or of volatile solvent components before the subsequent Reduction of less than 5% by weight, in particular not more than 2% by weight, based on the total weight of the solid. The specified Parts by weight are based on the weight loss of the Solid, determined at a temperature of 160 ° C, a Pressure of 1 bar and a duration of 10 min. In this way can the activity the invention used Catalysts are further increased.

Preferably the drying is carried out while moving the treated with the precursor solution Solid, for example, by drying the solid in one Rotary kiln or a rotary kiln. In this way, the activity the catalysts of the invention be further increased.

The transfer of the after drying obtained solid in its catalytically active Form takes place by reducing the solid in the above Temperatures in a conventional manner.

To For this purpose you bring the carrier material at the temperatures given above with hydrogen or a Mixture of hydrogen and an inert gas in contact. The hydrogen absolute pressure is for the result of the reduction of minor importance and will e.g. be varied in the range of 0.2 bar to 1.5 bar. Often done the hydrogenation of the catalyst material at normal hydrogen pressure in the hydrogen stream. Preferably, the reduction is done by moving of the solid, for example by reducing the solid in a rotary kiln or a rotary kiln. This way you can the activity the catalysts of the invention be further increased.

The Reduction can also be achieved by means of organic reduction reagents such as Hydrazine, formaldehyde, formates or acetates done.

Following the reduction, the catalyst can be passivated in a known manner to improve the handling, for example by briefly mixing the catalyst with an oxygen-containing gas, For example, air, but preferably with a 1 to 10 vol .-% oxygen-containing inert gas mixture treated. CO ₂ or CO ₂ / O ₂ mixtures can also be used here.

Of the active catalyst can also be added under an inert organic solvent, e.g. Ethylene glycol, be kept.

to Preparation of the catalyst according to the invention can in a preferred embodiment of the Ruthenium catalyst precursor, e.g. as prepared above or as in WO-A2-02 / 100538 (BASF AG) prepared with a solution of one or more alkaline earth metal (II) salts waterproof become.

preferred Alkaline earth metal (II) salts are corresponding nitrates, in particular Magnesium nitrate and calcium nitrate.

preferred solvent for the Alkaline earth metal (II) salts in this impregnation step is water. The Concentration of the alkaline earth metal (II) salt in the solvent is e.g. 0.01 to 1 mol / liter.

For example, the Ru / SiO ₂ catalyst incorporated in a pipe is contacted with a stream of an aqueous solution of the alkaline earth metal salt. The catalyst to be impregnated may also be treated with a supernatant solution of the alkaline earth metal salt.

Such saturation of the Ru / SiO ₂ catalyst, in particular its surface, preferably takes place with the alkaline earth metal ion (s).

Excess alkaline earth metal salt and non-immobilized alkaline earth metal ions are / are flushed by the catalyst (N ₂ O purging, catalyst washing).

For simplified Handling, e.g. Installation in a reactor tube, the catalyst of the invention can after impregnation be dried. The drying can be done e.g. in an oven at <200 ° C, e.g. at 50 to 190 ° C, particularly preferably at <140 ° C, z. B. at 60 to 130 ° C, carried out become.

This impregnation process can be carried out ex situ or in situ: ex situ means before installation of the catalyst in the reactor, in situ means in the reactor (according to the catalyst installation).

In a process variant, the impregnation of the catalyst surface with Alkaline earth metal ions also take place in situ by dissolving the solution of to be hydrogenated aromatic substrate (educts) alkaline earth metal ions, e.g. in the form of solved Alkaline earth metal salts. For this purpose, e.g. the corresponding Amount of salt first dissolved in water and then the substrate dissolved in an organic solvent added.

Of the Content of the solution of the aromatic substrate to be hydrogenated to alkaline earth metal ions is in Generally 1 to 100 ppm by weight, in particular 2 to 10 ppm by weight.

According to one Variant, it proves to be particularly advantageous when in the hydrogenation process according to the invention the catalyst of the invention in combination with an alkaline earth metal ion-containing solution of is used to be hydrogenated aromatic substrate.

the preparation, the ruthenium is in the catalysts of the invention as metallic ruthenium in front. Electron microscopic studies (SEM or TEM) have further shown that a shell catalyst is present: the ruthenium concentration within a catalyst grain decreases from outside to inside, wherein on the grain surface a ruthenium layer is located. In preferred cases, in the shell by means of SAD (Selected Area Diffraction) and XRD (X-Ray Diffraction) Crystalline Ruthenium be detected.

By the use of halogen-free, in particular chlorine-free, ruthenium precursors and solvents in the preparation of the halide content, in particular chloride content, the catalysts of the invention moreover, below 0.05% by weight (0 to <500 ppm by weight, for example in the range of 0 - 400 Ppm by weight), based on the total weight of the catalyst.

Of the Chloride content is e.g. by the method described below ion chromatographic certainly.

In This document is to be understood as ppm by weight (Ppm by weight), unless stated otherwise.

In a selected variant, it is preferred that the percentage ratio of the Q ₂ and Q ₃ structures Q ₂ / Q ₃ determined by means of ²⁹ Si solid-state NMR is less than 25, preferably less than 20, particularly preferably less than 15, eg is in the range of 0 to 14 or 0.1 to 13. This also means that the degree of condensation of the silica in the carrier used is particularly high.

The identification of the structures Q _n (n = 2, 3, 4) and the determination of the percentage ratio is effected by means ²⁹ Si solid state NMR. Q _n = Si (OSi) _n (OH) _4-n with n = 1, 2, 3 or 4.

One finds Q _n for n = 4 at -110.8 ppm, n = 3 at -100.5 ppm and n = 2 at -90.7 ppm (standard: tetramethylsilane) (Q ₀ and Q ₁ were not identified). The analysis is performed under the conditions of "magic angle spinning" at room temperature (20 ° C) (MAS 5500 Hz) with circular polarization (CP 5 ms) and using dipolar decoupling of the ¹ H. Because of the partial superimposition of the signals, the The line shape analysis was performed with a standard software package from Galactic Industries, whereby a least square fit was calculated iteratively.

The support material preferably contains not more than 1% by weight and in particular not more than 0.5% by weight and in particular <500 ppm by weight of aluminum oxide, calculated as Al ₂ O ₃ .

There the condensation of the silica is also influenced by aluminum and iron can be, the concentration of Al (III) and Fe (II and / or III) in total preferably less than 300 ppm, more preferably less 200 ppm, and is e.g. in the range of 0 to 180 ppm.

The proportion of alkali metal oxide preferably results from the preparation of the support material and can be up to 2 wt .-%. Often it is less than 1 wt .-%. Also suitable are alkali metal oxide-free carrier (0 to <0.1 wt .-%). The proportion of MgO, CaO, TiO ₂ or ZrO ₂ can be up to 10 wt .-% of the support material and is preferably not more than 5 wt .-%. Also suitable are support materials which contain no detectable amounts of these metal oxides (0 to <0.1 wt .-%).

Because Al (III) and Fe (II and / or III) can form incorporated acid sites in silica, it is preferred that charge compensation with alkaline earth metal cations (M ²⁺ , M = Be, Mg, Ca, Sr, Ba) in the Carrier is present. This means that the weight ratio of M (II) to (Al (III) + Fe (II and / or III)) is greater than 0.5, preferably> 1, particularly preferably greater than 3.

The Roman Numbers in parentheses after the element symbol indicate the oxidation state of the element.

at the carbocyclic aromatic group in the organic to be hydrogenated Compound is in particular a benzene ring, the Can carry substituents.

Examples of compounds having a benzene ring which can be hydrogenated by the process according to the invention to give the corresponding compound having a saturated carbocyclic 6-membered ring are listed in the following table:

• – Reaktionsprodukte aus Bisphenol A bzw. Bisphenol F oder vergleichbaren Alkylen- oder Cycloalkylen-verbrückten Bisphenol-Verbindungen mit Epichlorhydrin. Bisphenol A bzw. Bisphenol F oder vergleichbare Verbindungen können mit Epichlorhydrin und Basen in bekannter Weise (z.B. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, VCH (1987), Vol. A9, S. 547) zu Glycidylethern der allgemeinen Formel IIa umgesetzt werden,
  
  R² für Wasserstoff oder eine C₁-C₄-Alkylgruppe, z.B. Methyl, steht oder zwei an ein Kohlenstoffatom gebundene Reste R² eine C₃-C₅-Alkylengruppe bilden und m für Null bis 40 steht.
• – Phenol- und Kresolepoxynovolake IIb Novolake der allgemeinen Formel IIb sind durch säurekatalysierte Reaktion von Phenol bzw. Kresol und Umsetzung der Reaktionsprodukte zu den entsprechenden Glycidylethern erhältlich (s. z.B. Bis[4-(2,3-epoxypropoxy)phenyl]methan):
  
  wobei R² für Wasserstoff oder eine Methylgruppe und n für 0 bis 40 steht (siehe J.W. Muskopf et al. "Epoxy Resins 2.2.2" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).
• – Glycidylether von Reaktionsprodukten aus Phenol und einem Aldehyd: Durch säurekatalysierte Umsetzung von Phenol und Aldehyden und anschließende Umsetzung mit Epichlorhydrin sind Glycidylether zugänglich, z.B. ist 1,1,2,2-Tetrakis-[4-(2,3-epoxypropoxy)phenyl]ethan aus Phenol und Glyoxal zugänglich (siehe J.W. Muskopf et al. "Epoxy Resins 2.2.3" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).
• – Glycidylether von Phenol-Kohlenwasserstoffnovolacken, z.B. 2,5-Bis[(glycidyloxy)phenyl]octahydro-4,7-methano-5H-inden und dessen Oligomere.
• – Aromatische Glycidylamine: Beispielhaft sind die Triglycidylverbindung von p-Aminophenol, 1-(Glycidyloxy)-4-[N,N-bis(glycidyl)amino]benzol, und die Tetraglycidylverbindung von Methylendiamin Bis{4-[N,N-bis(2,3-epoxypropyl)amino]phenyl}methan zu nennen.

Examples of starting compounds for the hydrogenation process according to the invention include the following substance classes and substances:

• - Reaction products of bisphenol A or bisphenol F or comparable alkylene- or cycloalkylene-bridged bisphenol compounds with epichlorohydrin. Bisphenol A or bisphenol F or comparable compounds can be reacted with epichlorohydrin and bases in a known manner (for example Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, VCH (1987), Vol. A9, p. 547) to give glycidyl ethers of the general formula IIa,
  
  R ^{2 is} hydrogen or a C ₁ -C ₄ -alkyl group, for example methyl, or two R ² radicals bonded to a carbon atom form a C ₃ -C ₅ -alkylene group and m is 0 to 40.
• Phenol and cresol epoxy novolacs IIb Novolaks of the general formula IIb are obtainable by acid-catalyzed reaction of phenol or cresol and reaction of the reaction products to the corresponding glycidyl ethers (see, for example, bis [4- (2,3-epoxypropoxy) phenyl] methane):
  
  wherein R ^{2 is} hydrogen or a methyl group and n is 0 to 40 (see JW Muskopf et al., "Epoxy Resins 2.2.2" in Ullmann's Encyclopaedia of Industrial Chemistry, 5th Edition on CD-ROM).
• Glycidyl ethers of reaction products of phenol and an aldehyde: Glycidyl ethers are accessible by acid-catalyzed reaction of phenol and aldehydes and subsequent reaction with epichlorohydrin, eg 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane from phenol and glyoxal (see JW Muskopf et al., "Epoxy Resins 2.2.3" in Ullmann's Encyclopaedia of Industrial Chemistry, 5th Edition on CD-ROM).
• Glycidyl ethers of phenolic hydrocarbon novolacs, eg 2,5-bis [(glycidyloxy) phenyl] octahydro-4,7-methano-5H-indene and its oligomers.
• Exemplary are the triglycidyl compound of p-aminophenol, 1- (glycidyloxy) -4- [N, N-bis (glycidyl) amino] benzene, and the tetraglycidyl compound of methylenediamine Bis {4- [N, N-bis ( 2,3-epoxypropyl) amino] phenyl} methane.

in the individual are also to be mentioned: tris [4- (glycidyloxy) phenyl] methane isomers and glycidyl esters of aromatic mono-, di- and tricarboxylic acids, e.g. phthalic and isophthalic acid diglycidyl ester.

in der R CH₃ oder H bedeutet, kernhydriert.In a particular embodiment of the process according to the invention, aromatic bisglycidyl ethers of the formula II

in which R is CH ₃ or H, ring hydrogenated.

Prefers used aromatic bisglycidyl ethers of the formula II have a Content of chloride and / or organically bound chlorine of ≤ 1000 ppm by weight, especially <950 Ppm by weight, in particular in the range of 0 to <800 ppm by weight, e.g. 600 to 1000 ppm by weight, on.

Of the Content of chloride and / or organically bound chlorine is e.g. with the methods described below ion chromatographic or determined coulometrically.

According to one particular embodiment this variant of the method according to the invention it was recognized that it was surprisingly additionally proves advantageous if the used aromatic bisglycidyl ether of the formula II a content of corresponding oligomeric bisglycidyl ethers of less than 10% by weight, especially less than 5% by weight, especially less than 1.5% by weight, especially less than 0.5% by weight, e.g. in the range of 0 to <0.4 % By weight.

It was according to this particular embodiment found this variant of the process according to the invention, that the oligomer content in the feed has a decisive influence on the life of the catalyst, i. the turnover stays on longer high level. When using a e.g. distilled and thus oligomer poor Bisglycidyl ether II is compared to a corresponding commercial Standard product (for example: ARALDIT GY 240 BD of the company Vantico) a slowed down Catalyst deactivation observed.

The oligomer content of the aromatic bisglycidyl ethers of the formula II used is preferred detected by GPC (gel permeation chromatography) or by determining the evaporation residue.

Of the evaporation residue is obtained by heating the aromatic bisglycidyl ether for 2 h 200 ° C and for further 2 hours at 300 ° C each determined at 3 mbar.

To the other respective conditions for the determination of the oligomer content see below.

R = CH₃ oder H. n = 1, 2, 3 oder 4.The corresponding oligomeric bisglycidyl ethers generally have a molecular weight determined by GPC measurement in the range from 380 to 1500 g / mol and have, for example, the following structures (cf., for example, Journal of Chromatography 238 (1982), pages 385-398, page 387):

R = CH ₃ or H. n = 1, 2, 3 or 4.

The corresponding oligomeric bisglycidyl ethers have, for R = N, a molecular weight in the range from 568 to 1338 g / mol, in particular 568 to 812 g / mol, and for R = CH ₃ a molecular weight in the range from 624 to 1478 g / mol, in particular 624 to 908 g / mol, on.

The Separation of the oligomers succeeds, e.g. by chromatography or on a larger scale preferably distillatively, e.g. in the laboratory scale in a batch distillation or on an industrial scale in a thin film evaporator, preferably in a short path distillation, each under vacuum.

at a batch distillation for oligomer separation is e.g. at a pressure of 2 mbar, the bath temperature at about 260 ° C and the transition temperature at the head at about 229 ° C.

The oligomer separation can also be carried out under milder conditions, for example under reduced pressures in the range of 1 to 10 ^-3 mbar. At a working pressure of 0.1 mbar, the boiling point of the oligomer-containing starting material is lowered by 20-30 ° C depending on the starting material and thus also the thermal product load. To minimize the thermal load, the distillation is preferably carried out in a continuous procedure in a thin-film evaporation or particularly preferably in a short-path evaporation.

in the inventive method the hydrogenation of the starting materials, e.g. the compounds II, preferred in liquid Phase. The hydrogenation can be solvent-free or in an organic solvent respectively. Due to the z.T. high viscosity of the compounds II this is preferably as a solution or mixture in an organic solvent.

When organic solvents come in principle those which contain the educt, e.g. the compound II, if possible Completely to solve capital or with this completely and are inert under the hydrogenation conditions, i. Not be hydrogenated.

Examples for suitable solvent are cyclic and acyclic ethers, e.g. Tetrahydrofuran, dioxane, Methyl tert-butyl ether, dimethoxyethane, dimethoxypropane, dimethyl diethylene glycol, aliphatic alcohols such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert-butanol, carboxylic esters such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, and aliphatic ether alcohols such as methoxypropanol.

The Concentration of starting material, e.g. at compound II, in the to be hydrogenated liquid Phase can basically freely selected are and often are in the range of 20 to 95 wt .-%, based on the total weight of Solution / mixture. Under reacting sufficiently flowable educts can be the Perform hydrogenation even in the absence of a solvent.

In addition to carrying out the reaction (hydrogenation) under anhydrous conditions, it has been found in proven in a number of cases to carry out the reaction (hydrogenation) in the presence of water. The proportion of water, based on the mixture to be hydrogenated, up to 10 wt .-%, for example 0.1 to 10 wt .-%, preferably 0.2 to 7 wt .-% and in particular 0.5 to 5 wt .-%, amount.

The actual hydrogenation usually takes place in analogy to the known hydrogenation process, as described in the beginning mentioned prior art described. This is the Starting material, e.g. the compound II, preferably as a liquid phase, contacted with the catalyst in the presence of hydrogen. Of the Catalyst can be suspended both in the liquid phase (Suspension procedure) or you introduce the liquid phase over Fluidized catalyst bed (Fluidized bed mode of operation) or a fixed catalyst bed (fixed bed mode). The hydrogenation can be configured both continuously and discontinuously become. Preferably leads the process according to the invention in trickle reactors according to the fixed bed procedure by. The hydrogen can both in cocurrent with the solution of the starting material to be hydrogenated as well as in countercurrent over be passed the catalyst.

suitable Apparatus for carrying out a hydrogenation by the suspension procedure as well as the hydrogenation at the catalyst fluid bed and on the fixed catalyst bed are known in the art, e.g. from Ullmann's Encyclopaedia of Technical Chemistry, 4th Edition, Volume 13, p. 135 ff., as well as from P. N. Rylander, "Hydrogenation and dehydrogenation "in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. on CD-ROM.

The hydrogenation according to the invention can be used both at normal hydrogen pressure and at elevated hydrogen pressure, e.g. at a hydrogen absolute pressure of at least 1.1 bar, preferably at least 10 bar performed become. In general, the hydrogen absolute pressure becomes a value of 325 bar and preferably 300 bar. Especially preferred the hydrogen absolute pressure is in the range from 20 to 300 bar, e.g. in the range of 50 to 280 bar.

The Reaction temperatures are in the process of the invention in general at least 30 ° C and become common a value of 200 ° C do not exceed. In particular, leads the hydrogenation process at temperatures in the range of 40 to 150 ° C, e.g. 40 to 100 ° C, and more preferably in the range of 45 to 80 ° C by.

When Reaction gases come next to hydrogen and hydrogen-containing gases which are not catalyst poisons such as carbon monoxide or sulfurous Contain gases, e.g. Mixtures of hydrogen with inert gases such as Nitrogen or reformer exhaust gases, the usual still volatile Contain hydrocarbons. Preference is given to pure hydrogen (Purity ≥ 99.9 Vol .-%, especially ≥ 99.95 Vol .-%, in particular ≥ 99.99 Vol .-%).

by virtue of the high catalyst activity needed Comparatively small amounts of catalyst based on the used educt. This is how the discontinuous suspension method is used preferably less than 5 mol%, e.g. 0.2 mol% to 2 mol% ruthenium, based on 1 mol of starting material, use. With continuous design the hydrogenation process is usually the educt to be hydrogenated in an amount of 0.05 to 3 kg / (I (catalyst) · h), in particular 0.15 to 2 kg / (I (catalyst) · h), over the Catalyst lead.

Of course, the catalysts used in this process can be regenerated with decreasing activity according to the usual for noble metal catalysts such as ruthenium catalysts, known in the art methods. Here are, for example, the treatment of the catalyst with oxygen as in the BE 882 279 described treatment with dilute, halogen-free mineral acids, as described in US-A 4,072,628, or the treatment with hydrogen peroxide, for. B. in the form of aqueous solutions containing from 0.1 to 35 wt .-%, or treatment with other oxidizing substances, preferably in the form of halogen-free solutions. Usually, the catalyst after reactivation and before re-use with a solvent, for. As water, rinse.

in der R CH₃ oder H bedeutet, gekennzeichnet, wobei der Hydrierungsgrad > 98 %, besonders > 98,5 %, ganz besonders > 99 %, z.B. > 99,3 %, insbesondere > 99,5 %, beträgt, z.B. im Bereich von > 99,8 bis 100 % liegt.The hydrogenation process according to the invention is preferably characterized by the complete hydrogenation of the aromatic nuclei of the bisglycidyl ether of the formula II used

in which R denotes CH ₃ or H, wherein the degree of hydrogenation is> 98%, particularly> 98.5%, very particularly> 99%, for example> 99.3%, in particular> 99.5%, eg in the range from> 99.8 to 100%.

The degree of hydrogenation (Q) is defined after
Q (%) = ([number of cycloaliphatic C6 rings in the product] / [number of aromatic C6 rings in the starting material]) × 100

The ratio, eg molar ratio, of the cycloaliphatic and aromatic C6 rings can preferably be determined by means of ¹ H-NMR spectroscopy (integration of the aromatic and corresponding cycloaliphatic ¹ H signals).

in der R CH₃ oder H bedeutet, herstellbar durch das erfindungsgemäße Hydrierverfahren.The invention likewise relates to bisglycidyl ethers of the formula I.

in which R is CH ₃ or H, preparable by the hydrogenation process according to the invention.

(in der R CH₃ oder H bedeutet) mit n = 1, 2, 3 oder 4, von weniger als 10 Gew.-%, besonders weniger als 5 Gew.-%, insbesondere weniger als 1,5 Gew.-%, ganz besonders weniger als 0,5 Gew.-%, z.B. im Bereich von 0 bis < 0,4 Gew.-%, auf.The bisglycidyl ethers of the formula I preferably have a content of corresponding oligomeric ring-hydrogenated bisglycidyl ethers of the formula

(in which R denotes CH ₃ or H) with n = 1, 2, 3 or 4, of less than 10% by weight, especially less than 5% by weight, in particular less than 1.5% by weight, especially less than 0.5% by weight, for example in the range from 0 to <0.4% by weight.

Of the Content of oligomeric ring hydrogenated bisglycidyl ethers is preferred by heating the aromatic bisglycidyl ether for 2 h 200 ° C and for further 2 hours at 300 ° C at 3 mbar or by GPC measurement (gel permeation chromatography) certainly.

To the other respective conditions for the determination of the oligomer content see below.

The Bisglycidyl ethers of the formula I preferably have one according to DIN 51408 certain total chlorine content of less than 1000 ppm by weight, in particular less than 800 ppm by weight, especially less than 600 ppm by weight, e.g. in the range of 0 to 400 ppm by weight, on.

The Bisglycidyl ethers of the formula I preferably have one with mass spectrometry with inductively coupled plasma (ICP-MS) determined ruthenium content of less than 0.3 ppm by weight, in particular less than 0.2 ppm by weight, completely especially less than 0.1 ppm by weight, e.g. in the range of 0 to 0.09 ppm by weight, on.

The bis-glycidyl ethers of the formula I preferably have a platinum-cobalt color number (APHA color number) determined according to DIN ISO 6271 of less than 30, especially less than 25, very particularly less than 20, for example in Be rich from 0 to 18, up.

The Bisglycidyl ethers of the formula I preferably have the standard ASTM-D-1652-88 certain epoxy equivalents in the range of 170 to 240 g / equivalent, especially in the range of 175 to 225 g / equivalent, especially in the range of 180 to 220 g / equivalent, on.

The Bisglycidyl ethers of the formula I preferably have one according to DIN 53188 certain proportion of hydrolyzable chlorine of less than 500 ppm by weight, especially less than 400 ppm by weight, especially less than 350 ppm by weight, e.g. in the range of 0 to 300 ppm by weight, on.

The bisglycidyl ethers of the formula I preferably have a kinematic viscosity of less than 800 mm ² / s, particularly less than 700 mm ² / s, very particularly less than 650 mm ² / s, for example in the range from 400 to 630 mm ² / s, determined in accordance with DIN 51562 , each at 25 ° C on.

The Bisglycidylether of formula I preferably have a cis / cis: cis / trans: trans / trans isomer ratio in Range of 44-63 %: 34-53 %: 3-22 % on.

Especially the cis / cis: cis / trans: trans / trans isomer ratio is preferably in the Range of 46-60%: 36-50%: 4-18%.

All Particularly preferred is the cis / cis: cis / trans: trans / trans isomer ratio in Range of 48-57 %: 38-47 %: 5-14 %.

Especially is the cis / cis: cis / trans: trans / trans isomer ratio in Range of 51-56 %: 39-44%: 5-10%.

in der R CH₃ oder H bedeutet, erhalten, wobei der Hydrierungsgrad > 98 %, besonders > 98,5 %, ganz besonders > 99 %, z.B. > 99,3 %, insbesondere > 99,5 %, beträgt, z.B. im Bereich von > 99,8 bis 100 % liegt.The bisglycidyl ethers of the formula I are particularly preferably obtained by complete hydrogenation of the aromatic nuclei of a bisglycidyl ether of the formula II

in which R is CH ₃ or H, the degree of hydrogenation being> 98%, especially> 98.5%, very particularly> 99%, eg> 99.3%, in particular> 99.5%, eg in the range from> 99.8 to 100%.

1. Preparation of catalysts according to the invention 1 to 3

A defined amount of the carrier material was placed in a dish and impregnated with 90-95% of the amount of a solution of Ru (III) acetate (about 5% Ru in 100% acetic acid) in water, which can be absorbed by the carrier material maximum. The following carriers were selected:
Silica gel strands (diameter (d) = 1.5-4 mm, length (I) = 1 to 10 mm) with an SiO ₂ content> 99.5 wt .-% (0.3 wt .-% Na ₂ O), a specific BET surface area of 100-200 m ² / g, a water absorption (WA) of 0.85-1.0 g / g and a pore volume of 0.5-0.9 ml / g (DIN 66131 ), such as

• ** Data from Hg sorption according to DIN 66134

C15 from Grace (BET surface area 181 m ² / g, pore volume of 1.1 ml / g, Q ₂ / Q ₃ = 13%, M (II) :( Al (III) + Fe (II and / or III)) = 7.0), (M (II) = Ca (II) + Mg (II)), and
Davicat ^® S557 (Grade 57) meters from the Fa. Grace-Davison (BET surface area 340 ² / g, pore volume of 1.1 ml / g, Q ₂ / Q ₃ = 8.8%, M (II) :( Al (III) + Fe (II and / or III)) = 4.6), (M (II) = Ca (II) + Mg (II)).

The substance thus contained was dried at 120 ° C overnight. The dried material was reduced for 2 h at 300 ° C in a stream of hydrogen at atmospheric pressure in a rotary ball furnace. After cooling and inerting (N ₂ ), the catalyst was passivated at room temperature with dilute air. The reduced and passivated catalyst contained about 1.6-2 wt .-% Ru, based on the total mass of the resulting catalyst.

TEM analysis:

The Ruthenium concentration within a catalyst grain of the catalyst absorbs from outside inside out, with up to about 200 nm thick at the grain surface Ru layer is located. Inside the catalyst grain, the Ru particles are up to about 2 nm in size. Below the ruthenium shell are aggregated in places and / or agglomerated Ru particles observed. In this area, the size of the Ru individual particles is up to approx. 4 nm. In the shell, SAD forms crystalline ruthenium demonstrated.

XRD Analysis gives a ruthenium crystallite size of about 8 nm.

The Pore volume was determined by nitrogen sorption according to DIN 66131.

The identification of the Q _n structures (n = 2, 3, 4) and the determination of the percentage ratio were carried out by means of ²⁹ Si solid-state NMR.
Q _n = Si (OSi) _n (OH) _4-n where n = 1, 2, 3 or 4.

One finds Q _n for n = 4 at -110.8 ppm, n = 3 at -100.5 ppm and n = 2 at -90.7 ppm (standard: tetramethylsilane) (Q ₀ and Q ₁ were not identified). The analysis was carried out under the conditions of "magic angle spinning" at room temperature (20 ° C.) (MAS 5500 Hz) with circular polarization (CP 5 ms) and using dipolar decoupling of ¹ H. Because of the partial superimposition of the signals, the The line shape analysis was performed with a standard software package from Galactic Industries, whereby a least square fit was calculated iteratively.

Table overview:

• *) Oxidation states: Fe (II and / or III), Al (III), Ca (II), Mg (II).

The support of catalyst A from WO 02/100 538 corresponds to the support of catalyst B from WO 02/100 538 (same chemical composition), with the difference that the BET surface area is 68 m ² / g and the pore volume is 0.8 ml / g.

For the preparation of catalysts according to the invention, the catalysts 1 to 3 are each impregnated with a Mg ²⁺ salt solution, for example with an 80 mM (millimolar) aqueous Mg (NO ₃ ) ₂ solution at room temperature, for example 15 min. The impregnated catalyst is rinsed with water and dried at 80 ° C.

2. Preparation of the catalysts A and B

Catalyst A (without Mg impregnation, not according to the invention)

Of the Catalyst was prepared on the basis of WO-A2-02 / 100 538.

Silica strands (diameter d = 3 mm) with an SiO ₂ content> 99.5% by weight (0.3% by weight Na ₂ O), a pore volume of 0.7 ml / g (DIN 66131), with a BET surface area of about 118 m ² / g and a water absorption of 0.87 g / g carrier. The carrier was placed in a dish and soaked with a Ru-acetate solution at 95% water absorption. The soaked product was dried at 120 ° C overnight. The reduction proceeded for 2 h at 300 ° C in a hydrogen stream at atmospheric pressure in a rotary ball furnace. After cooling and inerting (N ₂ ), the catalyst was passivated at room temperature with dilute air. The catalyst thus obtained was used in this way (= catalyst A) or converted into the catalyst B (see below).

Catalyst B (with Mg impregnation, Inventive)

Catalyst A (20 wt .-%) was Mg solution (Mg (NO _{3) 2} · 6H ₂ O) was impregnated with 80 wt .-% of a 82.5 mM for 15 min. At room temperature. The impregnated catalyst was rinsed with water and dried at 80 ° C.

 3. hydrogenation examples

The conversion and the degree of hydrogenation were determined by means of ¹ H-NMR:
Sample volume: 20-40 mg, solvent: CDCl ₃ , 700 μL with TMS as reference signal, sample tube: 5 mm diameter, 400 or 500 MHz, 20 ° C; Decrease of the signals of the aromatic protons vs. Increase in the signals of the aliphatic protons). The conversion indicated in the examples relates to the hydrogenation of the aromatic groups.

The Determination of the decrease of the epoxide groups was carried out by comparison Epoxy equivalent (EEW) before and after the hydrogenation, each determined according to the standard ASTM-D-1652-88.

The Determination of ruthenium in the effluent freed from THF and water was done with inductively coupled plasma mass spectrometry (ICP-MS, see below).

example 1

In In a 300 ml autoclave, 150 g of a 30% by weight solution of 2,2-di- [p-glycidoxyphenyl] -propane (Oligomer-containing standard product, ARALDIT GY 240 BD from Vantico, EEW = 182) in THF with 3 wt .-% water at 250 bar and 50 ° C for 10 h. In each case 0.5 mol% (mol% Ru based on 2,2-di- [p-glycidoxiphenyl] propane) the catalysts A and B used. (Batch procedure). After completion of the Reaction became after distillative separation of THF and water Turnover, selectivity and Ru content determined.

• 1. Der Ru-Katalysator A ist ein leistungsfähiger Hydrierkontakt für aromatische Bisglycidylether.
• 2. Die Imprägnierung des Katalysators mit einem Magnesiumsalz (Kontakt B) verändert weder Aktivität noch Selektivität, erhöht jedoch die Stabilität erheblich.

The example shows:

• 1. The Ru catalyst A is a powerful hydrogenation contact for aromatic bisglycidyl ethers.
• 2. The impregnation of the catalyst with a magnesium salt (contact B) does not alter activity or selectivity, but does increase the stability considerably.

Example 2 (comparison)

When Reactor served with a 75 ml of catalyst A filled, heated reaction tube made of stainless steel (length 0.8 m; Diameter 12 mm) with an inlet pump for the educt and a separator with stand attitude for sampling and emission control equipped was.

In the hydrogenation initially a 30 wt .-% solution of 2,2-di- [p-glycidoxiphenyl] propane (distilled goods, EEW = 171) in THF was used, which contained 3 wt .-% water. The hydrogenation was carried out at a catalyst loading of 0.15 kg / l _cat. · H, an inlet / circulation ratio of 8, a temperature of 50 ° C and a hydrogen pressure of 250 bar. The reactor was operated in a sump.

To operating hours of 46 hours, sales of 95.4% were added a selectivity of 69.3% (EEW = 255). The test drive was due intensive Ru-leaching (Ru content in the discharge, without THF and water:> 4 ppm) stopped. (Ru-Leaching = detachment of the precious metal from the carrier).

The example shows:
When using a supported Ru contact such as catalyst A in a continuous driving the contact shows leaching and is thus in need of improvement in terms of an economic technical process.

Example 3

When Reactor was a filled with 75 ml of catalyst B, heated reaction tube made of stainless steel (length 0.8 m; Diameter 12 mm) with an inlet pump for the educt and a separator with stand attitude for sampling and emission control equipped was.

In the hydrogenation initially a 30 wt .-% solution of 2,2-di- [p-glycidoxiphenyl] propane (distilled goods, EEW = 172) in THF was used, which contained 3 wt .-% water. The hydrogenation was run at a Kat.-load of 0.15 kg / l _cat. · H, an inlet / circulation ratio of 8, a temperature of 50 ° C and a hydrogen pressure of 250 bar. The reactor was operated in a sump.

After an operating time of 256 hours, 5 ppm by weight of Mg (based on bisglycidyl ether used (= BGE), calculated 100%) in the form of Mg (NO ₃ ) ₂ .H ₂ O were added to the feed.

To an operating time of 346 h was the BGE concentration in the feed increased to 40, however, maintain the Mg concentration. The feed / circulation ratio was 11th

The achieved sales, selectivities and Ru concentrations in the reactor effluent (without solvent) may be as follows Table be taken.

• 1. Die Mg-Imprägnierung führt dazu, dass der geträgerte Ru-Kontakt, wie im Batchversuch gezeigt, auch in kontinuierlicher Betriebsweise erheblich an Stabilität gewinnt (Bilanz 1–7).
• 2. Nach einiger Zeit (~ 208 Stunden) ist ein leichtes Ru-Leaching zu beobachten (Bilanz 8–9). Ursache ist vermutlich das Herauswaschen des Magnesiums.
• 3. Dem kann entgegengewirkt werden, indem man dem Feed eine kleine Menge Mg-Salz beifügt (10–14). Der Ru-Gehalt im Austrag kann so < 0,1 ppm gehalten werden.
• 4. Unter diesen Bedingungen kann auch eine 40 Gew.-%ige BGE-Lösung problemlos hydriert werden (Bilanz 15–20).
• 5. Reduziert man die beigefügte Mg-Menge allerdings deutlich unter 5 ppm (2,5 bzw. 1,25 ppm) so ist wieder leichtes (0,9 ppm) bzw. starkes (1,4 ppm) Leaching zu beobachten (Bilanz 21–28).

The example shows:

• 1. The Mg impregnation leads to the fact that the supported Ru contact, as shown in the batch experiment, also gains considerable stability in continuous operation (balance sheet 1-7).
• 2. After some time (~ 208 hours) a slight Ru-leaching is observed (balance 8-9). The cause is probably the washing out of the magnesium.
• 3. This can be counteracted by adding a small amount of Mg salt to the feed (10-14). The Ru content in the discharge can be kept <0.1 ppm.
• 4. Under these conditions, a 40 wt .-% BGE solution can be easily hydrogenated (balance 15-20).
• 5. However, if the amount of Mg added is significantly below 5 ppm (2.5 or 1.25 ppm), light (0.9 ppm) or strong (1.4 ppm) leaching can again be observed (balance 21 -28).

4. Oligomer content:

Molmasse von 2,2-Di-[p-glycidoxiphenyl]-propan: 340 g/mol According to the invention, it was also recognized that the oligomer content in the feed has an influence on the service life of the catalyst: When using a distilled feed ("oligomer-poor" feed), a slower catalyst deactivation is observed in comparison to a commercially available standard product ("oligomer-rich" feed). The oligomer content can be determined, for example, by means of GPC measurement (gel permeation chromatography):

Molecular weight of 2,2-di- [p-glycidoxyphenyl] -propane: 340 g / mol

5. Description the GPC measurement conditions

• Stationary Phase: 5 styrene-divinylbenzene gel columns "PSS SDV linear M" (each 300 × 8 mm) the company PSS GmbH (temperature: 35 ° C).
• Mobile phase: THF (flow: 1.2 ml / min).
• Calibration: MG 500-10 000 000 g / mol with PS calibration kit from Polymer Laboratories. In the oligomer range: Ethylbenzene / 1,3-diphenylbutane / 1,3,5-Triphenylhexan / 1,3,5,7-Tetraphenyloktan / 1,3,5,7,9-Pentaphenyldekan.
• Evaluation limit: 180 g / mol.
• Detection: RI (refractive index) Waters 410, UV (at 254 nm) Spectra Series UV 100.

The given molar masses because of different hydrodynamic Volumes of the individual polymer types in solution Relative values for polystyrene as a calibrant and therefore not absolute sizes.

Of the Oligomer content in area% (FL%) determined by GPC measurement can be converted to wt% by means of internal or external standard become.

The GPC analysis of an aromatic bisglycidyl ether of the formula II (R =CH ₃ ) used in the hydrogenation process according to the invention showed, for example, in addition to the monomer, the following content of corresponding oligomeric bisglycidyl ethers:
Molar masses in the range of 180- <380 g / mol:> 98.5 FL%,
in the range of 380- <520 g / mol: <1.3 FL%,
in the range of 520- <860 g / mol: <0.80 Fl.% and
in the range of 860-1500 g / mol: <0.15 FL%.

6. Description the method for determining the evaporation residue

From Each sample was weighed approx. 0.5 g into a weighing glass. The weighing glasses were subsequently at room temperature in a plate-heated vacuum oven put and the drying oven evacuated. At a pressure of 3 mbar, the temperature was 200 ° C elevated and the sample for Dried for 2 h. For for a further 2 h, the temperature was increased to 300 ° C, then in Desiccator cooled to room temperature and weighed.

Of the residue determined by this method (oligomer content) in standard product (ARALDIT GY 240 BD from Vantico) was 6.1 Wt .-%.

Of the residue determined by this method (oligomer content) in distilled standard product was 0 wt .-%. (Distillation conditions: 1 mbar, bath temperature 260 ° C and transition temperature at the head 229 ° C).

7. Determination of the, cis / cis-cis / trans-trans / trans isomer ratios

A product effluent of hydrogenated bisphenol A bisglycidyl ether (R = CH ₃ ) was analyzed by gas chromatography (GC and GC-MS). Three signals were identified as hydrogenated bisphenol A bisglycidyl ether.

By The hydrogenation of the bisphenol A unit of the bisglycidyl ether can be several Isomers are formed. Depending on the arrangement of the substituents on the cyclohexane rings a cis / cis, trans / trans or cis / trans isomerism may occur.

To identify the three isomers, the products of the respective peaks were preparatively collected by means of a columnar circuit. Subsequently, each fraction was characterized by NMR spectroscopy ( ¹ H, ¹³ C, TOCSY, HSQC).

For the preparative GC came a GC system with a column circuit for use. The sample was placed on a Sil-5 capillary (l = 15 m, ID = 0.53 mm, df = 3 μm) pre-separated. The signals were using a DEANS circuit cut on a 2nd GC column. This pillar served to review the Goodness of the preparative Section. Finally Each peak was collected using a fraction collector. It 28 injections of an approximately 10% by weight solution of the sample were prepared, which is about 10 μg Each component corresponds.

The Characterization of the isolated components was then by NMR spectroscopy.

For the determination the isomer ratios a hydrogenated bisphenol F bisglycidyl ether (R = H) the corresponding applies.

8. Determination of ruthenium in the ring-hydrogenated bisglycidyl ether of the formula I

The sample was diluted by a factor of 100 with a suitable organic solvent (eg NMP). In this solution, the ruthenium content was determined by inductively coupled plasma mass spectrometry (ICP-MS). Device: ICP-MS spectrometer, eg Agilent 7500s Measurement conditions: calibration: External calibration in organic matrix atomizer: Meinhardt Dimensions: Ru102

The Eichstraade was chosen that in the diluted measurement solution the necessary delivery value could be reliably determined.

 9. Determination of chloride and organically bound chlorine

The Determination of chloride was carried out by ion chromatography.

Sample preparation:

It About 1 g of the sample was dissolved in toluene and washed with 10 ml ultrapure water extracted. The watery Phase was measured by ion chromatography.

Measurement conditions:

Ion chromatography system: Metrohm Guard column: DIONEX AG 12 Column: DIONEX AS 12 eluent: (2.7 mmol Na ₂ CO ₃ + 0.28 mmol NaHCO ₃ ) / liter water Foot: 1 ml / min. detection: conductivity after chemical suppression suppressor: Metrohm Modul 753 50 mmol H ₂ SO ₄ ; Ultrapure water (flow approx. 0.4 ml / min.) Calibration: 0.01 mg / L to 0.1 mg / L

Coulometric determination of organically bound chlorine (total chlorine), in accordance with DIN 51408, Part 2, "Determination the chlorine content "

The sample was burned in an oxygen atmosphere at a temperature of about 1020 ° C. The bound chlorine in the sample is converted to hydrogen chloride. The nitrous gases, sulfur oxides and water produced during combustion are removed and the purified combustion gas is introduced into the coulometer cell. Here, the coulometric determination of the chloride formed according to Cl ^- + Ag ⁺ → AgCl. Einwaagebereich: 1 to 50 mg Limit of quantitation: about 1 mg / kg (substance dependent) Device: Fa. Euroglas (LHG), "ECS-1200"

• Literature: F. Ehrenberger, "quantitative organic elementary analysis", ISBN 3-527-28056-1.

Claims (45)

Ruthenium heterogeneous catalyst containing silicon dioxide as support material, characterized in that the catalyst ^surface contains alkaline earth metal ions (M ²⁺ ). Ruthenium catalyst according to claim 1, characterized in that the catalyst ^surface contains magnesium ions (Mg ²⁺ ). Ruthenium catalyst according to Claims 1 or 2, characterized in that the catalyst contains 0.1 to 10% by weight of ruthenium and the catalyst surface contains 0.01 to 1% by weight of the alkaline earth metal ion (s) (M ²⁺ ), each based on the weight of the silica support material. Ruthenium catalyst according to Claims 1 or 2, characterized in that the catalyst contains 0.2 to 5% by weight of ruthenium and the catalyst surface contains 0.05 to 0.5% by weight of the alkaline earth metal ion (s) (M ^{2 +} ), in each case based on the weight of the silica support material. Ruthenium catalyst according to one of the preceding Claims, wherein the catalyst by single or multiple impregnation of the support material with a solution a ruthenium (III) salt, drying and reduction produces. Ruthenium catalyst according to one of the preceding claims, characterized in that the alkaline earth metal ions (M ²⁺ ) are introduced by impregnation of a preliminary ruthenium heterogeneous catalyst with a solution of an alkaline earth metal (II) salt in the catalyst surface. Ruthenium catalyst according to the preceding claim, characterized in that it is in the solution of an alkaline earth metal (II) salt around a watery solution of magnesium nitrate and / or calcium nitrate. Ruthenium catalyst according to one of the preceding claims, characterized in that the support material based on amorphous silicon dioxide has a BET surface area (according to DIN 66131) in the range from 30 to 700 m ² / g. Ruthenium catalyst according to one of the preceding Claims, characterized in that the catalyst is less than 0.05% by weight Halide (determined by ion chromatography), based on the total weight of the catalyst. Ruthenium catalyst according to one of the preceding Claims, characterized in that the ruthenium concentrates as a shell on the catalyst surface is. Ruthenium catalyst according to the preceding claim, characterized in that the ruthenium in the shell partially or completely present in crystalline form. Ruthenium catalyst according to one of the preceding Claims, characterized in that the or the Erdalkalimetallion / s highly dispersed in the catalyst surface is present / present. Ruthenium heterogeneous catalyst according to one of the preceding claims, characterized in that in the silicon dioxide carrier material, the percentage ratio of the signal intensities of the Q ₂ and Q ₃ structures Q ₂ / Q ₃ determined by means of ²⁹ Si solid-state NMR is less than 25. Ruthenium catalyst according to one of the preceding Claims, characterized in that in the silica support material the concentration of Al (III) and Fe (II and / or III) in total smaller 300 ppm by weight. Process for the hydrogenation of a carbocyclic aromatic Group to the corresponding carbocyclic aliphatic group, characterized in that one comprises a ruthenium heterogeneous catalyst according to one the claims 1 to 14 starts. Process according to the preceding claim for hydrogenation a benzene ring to the corresponding carbocyclic 6-ring. Method according to one of the two preceding claims for the preparation of a bis-glycidyl ether of the formula I.

in which R denotes CH ₃ or H, by nuclear hydrogenation of the corresponding aromatic bisglycidyl ether of the formula II

Method according to claim 17, characterized in that in that the aromatic bisglycidyl ether of the formula II used a content of corresponding oligomeric bisglycidyl ethers of less than 10 wt .-% has. Method according to claim 17, characterized in that in that the aromatic bisglycidyl ether of the formula II used a content of corresponding oligomeric bisglycidyl ethers of less than 5 wt .-% has. Method according to one of the two preceding claims, characterized in that the oligomeric bis-glycidyl ethers for R = H have a molecular weight in the range of 568 to 1338 g / mol and for R = CH _{3 have} a molecular weight in the range of 624 to 1478 g / mol. Method according to one of claims 15 to 20, characterized that the hydrogenation is carried out at a temperature in the range of 30 to 200 ° C carried out. Method according to one of claims 15 to 21, characterized that the hydrogenation at a hydrogen absolute pressure in the range from 10 to 325 bar. Method according to one of claims 15 to 22, characterized that the hydrogenation is carried out on a fixed catalyst bed. Method according to one of claims 15 to 22, characterized that the hydrogenation in liquid Phase containing the catalyst in the form of a suspension is carried out. Method according to one of Claims 17 to 24, characterized that the aromatic bisglycidyl ether of the formula II as a solution in one opposite the hydrogenation of inert organic solvent, wherein the solution 0.1 to 10 wt .-%, based on the solvent, water. Method according to one of claims 15 to 25, characterized in that a solution of the substrate to be hydrogenated is used which contains alkaline earth metal ions (M ²⁺ ). Method according to one of claims 15 to 25, characterized in that a solution of the substrate to be hydrogenated is used, which contains magnesium ions (Mg ²⁺ ). Method according to one of the two preceding claims, characterized characterized in that the content of the solution of alkaline earth metal ions 1 to 100 ppm by weight is. Method according to claim 26 or 27, characterized that the content of the solution of alkaline earth metal ions is 2 to 10 ppm by weight. Bisglycidyl ethers of the formula I.

in which R denotes CH ₃ or H, preparable by a process according to one of Claims 15 to 29. Bisglycidyl ethers according to the preceding claim, characterized in that they contain a content of corresponding oligomeric ring-hydrogenated bis-glycidyl ethers of the formula

with n = 1, 2, 3 or 4, of less than 10 wt .-% have. Bisglycidyl ethers according to the preceding claim, characterized in that it has a content of corresponding oligomeric ring-hydrogenated bis-glycidyl ethers of less than 5% by weight exhibit. Bisglycidyl ether according to claim 31, characterized in that that they have a content of corresponding oligomeric ring hydrogenated Bisglycidyl ethers of less than 1.5 wt .-% have. Bisglycidyl ether according to claim 31, characterized in that that they have a content of corresponding oligomeric ring hydrogenated Bisglycidyl ethers of less than 0.5 wt .-% have. Bisglycidyl ether according to claims 31 to 34, characterized that the content of oligomeric ring hydrogenated Bisglycidylethern means Heating the aromatic bisglycidyl ether for 2 h at 200 ° C and for more 2 hours at 300 ° C is determined at 3 mbar each. Bisglycidyl ether according to claims 31 to 34, characterized that the content of oligomeric ring hydrogenated Bisglycidylethern means GPC measurement (gel permeation chromatography) is determined. Bisglycidyl ethers according to the preceding claim, wherein the by GPC measurement certain content of oligomeric bisglycidyl ethers in area% one Content in wt .-% equals. Bisglycidyl ethers according to any one of claims 30 to 37, characterized in that they are intended according to DIN 51408 Have total chlorine content of less than 1000 ppm by weight. Bisglycidyl ethers according to any one of claims 30 to 38, characterized in that they have one with mass spectrometry with inductively coupled plasma (ICP-MS) determined ruthenium content of less than 0.3 Ppm by weight. Bisglycidyl ethers according to any one of claims 30 to 39, characterized in that it is determined according to DIN ISO 6271 Platinum Cobalt Color Number (APHA Color Number) of less than 30 have. Bisglycidyl ethers according to any one of claims 30 to 40, characterized in that it according to the standard ASTM-D-1652-88 certain epoxy equivalents in the range of 170 to 240 g / equivalent exhibit. Bisglycidyl ethers according to any one of claims 30 to 41, characterized in that they are intended according to DIN 53188 Share of hydrolyzable chlorine of less than 500 ppm by weight. Bisglycidylether according to one of claims 30 to 42, characterized in that they have a DIN 51562 certain kinematic viscosity of less than 800 mm ² / s at 25 ° C. Bisglycidyl ethers according to any one of claims 30 to 43, characterized in that it has a cis / cis: cis / trans: trans / trans isomer ratio in Range of 44-63 %: 34-53 %: 3-22 % exhibit. Bisglycidyl ether according to one of claims 30 to 44, characterized in that the bisglycidyl ether by complete hydrogenation of the aromatic nuclei of a bisglycidyl ether of formula II

in which R denotes CH ₃ or H, the degree of hydrogenation being> 98.