DE102005029294A1 - New heterogeneous ruthenium catalyst comprising amorphous silicon dioxide, useful in the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group - Google Patents

Abstract

Heterogeneous ruthenium catalyst comprising an amorphous silicon dioxide as substrate (obtained by the impregnation of one or more carrier material with a ruthenium salt solution, followed by drying and reduction; and where the silicon dioxide carrier material exhibits a Brunauer-Emmett and Teller surface (BET surface, according to DIN 66131) of 250-400 m 2>/g, a pore volume (according to DIN 66134) of 0.7-1.1 ml/g and a pore diameter (according to DIN 66134) of 6-12 nm), is new. An independent claim is included for the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group comprising using heterogeneous ruthenium catalyst.

Description

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

The present invention relates to a ruthenium heterogeneous catalyst containing amorphous silica as a support material, prepared by one or more impregnation of the support material with a solution of a ruthenium salt, drying and reduction, and
a process for the catalytic hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group,
in particular a process for the preparation of a bis-glycidyl ether of the formula I.

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

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).

The two older ones Patent Applications PCT / EP / 04/014454 and PCT / EP / 04/014455 respectively from 18.12.04 (both BASF AG) concern specific Ru catalysts and their use in hydrogenation processes.

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 / ( l.h)), [product amount / (reactor volume · time)] (kg / (l _reactor · h)), based on the catalyst used, can be achieved in which the catalysts used without workup can be used repeatedly for hydrogenations and the used catalysts allow a stable continuous core hydrogenation. 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, gefunden.Accordingly, a ruthenium heterogeneous catalyst containing amorphous silica as a carrier material, prepared by one or more impregnation of the support material with a solution of a ruthenium salt, drying and reduction, which is characterized in that the silicon dioxide support material used is a BET surface area (according to DIN 66131 ) in the range of 250 to 400 m ² / g, a pore volume (according to DIN 66134) in the range 0.7 to 1.1 ml / g and a pore diameter (after 66134) in the range of 6 to 12 nm, and
a process for the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, in particular a process for the preparation of 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 one uses the above-mentioned ruthenium heterogeneous catalyst found.

An essential component of the catalysts according to the invention is the support material based on amorphous silicon dioxide. The term "amorphous" in this context means that the proportion of crystalline silicon dioxide phases makes up less than 10% by weight of the carrier material. However, the carrier materials used for the preparation of the catalysts may have superstructures, which are formed by regular arrangement of pores in the carrier material.
(See eg OW Flörke, "Silica" in Ullmann's Encyclopaedia of Industrial Chemistry 6th Edition on CD-ROM).

Suitable carrier materials are amorphous silicon dioxide types which consist of at least 90% by weight of silicon dioxide, wherein the remaining 10% by weight, preferably not more than 5% by weight, of the carrier material may also be another oxidic material , eg MgO, CaO, TiO ₂ , ZrO ₂ , Fe ₂ O ₃ and / or alkali metal oxide.

In a preferred embodiment of the invention, the support material is halogen-free, in particular chlorine-free, ie the content of halogen in the support material is less than 500 ppm by weight, for example 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 290 to 370 m ² / g, especially 300 to 360 m ² / g, especially 310 to 355 m ² / g (BET surface area to DIN 66131).

Suitable amorphous support materials based on silica are commercially available:
Siliperl AF 125 (Perlkat 97) from Engelhard is particularly preferred.

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.

Especially For the preparation of the catalyst, preference is given to the silicon dioxide carrier material in the form of spherical shaped bodies used.

The spherical shaped body preferably have a diameter in the range of 1 to 6 mm, especially 2 to 5.5 mm, in particular 3 to 5 mm.

The Moldings, in particular the spherical moldings, advantageously have a (side) compressive strength of> 60 Newton (N), especially from> 70 N, further especially from> 80 N, further especially from> 100 N, for example in the range of 90 to 150 N.

to Determination of the (side) compressive strength has been made e.g. the catalyst tablet between two parallel plates on the shell side or e.g. the Catalyst ball between two parallel plates each with increasing Force loaded until break occurred. The force registered at the break is the (side) pressure resistance. The determination was made on one Testing device of the company Zwick, Ulm, with fixed turntable and free-moving, vertical Stamp, the molding pressed against the fixed rotary divider. The freely movable stamp was connected to a pressure cell to absorb the force. The Device was controlled by a computer which registered the readings and evaluated. From a well-mixed catalyst sample were 25 flawless (i.e., free of cracks and possibly without jagged edges) moldings taken from their (sides) determined compressive strength and then averaged.

Especially Preferably, the silica support material used for catalyst preparation has a Pore volume (according to DIN 66134) in the range 0.8 to 1.0 ml / g, e.g. 0.85 to 0.96 ml / g, on.

Farther has the silica support material used for catalyst preparation preferably has a pore diameter (according to 66134) in the range from 8 to 10 nm, e.g. in the range of 8.2 to 9.8 nm, especially in the range from 8.3 to 9.0 nm, up.

Preferably the content of ruthenium in the catalysts is in the range of From 0.5 to 4% by weight and in particular from 1 to 3% by weight, e.g. 1.5 to 2.5 wt .-%, each based on the weight of the silica support material and calculated as elemental ruthenium (for determination method see below).

Especially preferably contains the catalyst of the invention no Cu, Co, Zn, Rh, Pd, Os, Ir, Hg, Cd, Pb, Bi and / or Pt.

The preparation of the ruthenium catalysts according to the invention is preferably carried out by first treating the selected support material with a solution of a low molecular weight ruthenium compound, hereinafter referred to as (ruthenium) precursor, treated in such a way that the desired amount of ruthenium is absorbed by the support material. Preferred solvents here are glacial acetic acid, water or mixtures thereof. This step will also be referred to as potions. Subsequently, the thus treated support, preferably in compliance with the upper temperature limits specified below, dried. Optionally, the solid thus obtained is then re-mixed with the aqueous solution of Ruthenium precursors treated and dried again. This process is repeated until the amount of ruthenium compound absorbed by the carrier material corresponds to the desired ruthenium content in the catalyst.

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 RuCl _{3 are} preferably those ruthenium compounds, in particular ruthenium (III) - or ruthenium (IV) salts, 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 may 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 treating the catalyst with an oxygen-containing gas, for example air, but preferably with an inert gas mixture containing 1 to 10% by volume of oxygen , 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.

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.

In the catalyst shell, the Ru is in particular aggregated - agglomerated in front; in the catalyst core, the ruthenium concentration is lowest (At the core is the size of the ruthenium particles e.g. in the range of 1-2 nm).

In In a particularly preferred variant, the ruthenium is in the Shell and in the core fumed before.

The dispersity of the ruthenium in the catalyst is averaged preferably in the range from 30 to 60%, in particular in the range of 40 to 50%, (in each case measured by CO sorption according to DIN 66136-3, cf. below).

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), as far as nothing another is indicated.

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 may contain up to 10 wt .-% constitute 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.

Of the Ru catalyst according to the invention is particularly preferred after reduction by the following features characterized:

N ₂ sorption:

• BET (DIN 66131): in the range from 320 to 380 m ² / g, in particular 340 to 360 m ² / g, for example 344 to 357 m ² / g,
• Pore volume (DIN 66134): in the range of 0.8 to 0.9 ml / g, in particular 0.85 to 0.89 ml / g, e.g. 0.87 to 0.88 ml / g,
• Pore diameter (4V / A) (DIN 66134): 7.5 to 9 nm, in particular 7.8 to 8.7 nm, e.g. 8.0 to 8.5 nm.

Hg porosimetry (DIN 66133):

• Pore volume: in the range of 0.80 to 0.91 ml / g, in particular From 0.82 to 0.90 ml / g, e.g. 0.83 to 0.89 ml / g,
• Pore diameter (4V / A): 8 to 11 nm, especially 9 to 10.5 nm, e.g. 9.3 to 10.0 nm.

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 in the range of 0 to <1000 ppm, e.g. 100 to <950 Ppm by weight, up.

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 = H a molecular weight in the range of 568 to 1338 g / mol, in particular 568 to 812 g / mol, and for R = CH _{3 has} a molecular weight in the range of 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 to 1 mol of starting material, use. In a continuous embodiment of the Hydrogenation is usually one the educt to be hydrogenated in an amount of 0.05 to 3 kg / (l (catalyst) · h), in particular 0.15 to 2 kg / (l (catalyst) · h), over the Catalyst lead.

Of course, the catalysts used in this process with decreasing activity after the for Noble metal catalysts such as ruthenium catalysts usual, be regenerated methods known in the art. Here are z. B. the treatment of the catalyst with oxygen as in the BE 882 279, the treatment with dilute, halogen-free mineral acids, such as in US-A-4,072,628 described or treatment with hydrogen peroxide, for. In Form of watery Solutions with a content of 0.1 to 35 wt .-%, or treatment with others oxidizing substances, preferably in the form of halogen-free solutions call. Usually one becomes the catalyst after the reactivation and before the renewed Use with a solvent, z. As water, rinse.

in der R CH₃ oder H bedeutet, gekennzeichnet, wobei der Hydrierungsgrad > 98%, ganz besonders > 98,5%, z.B. > 99,0%, 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 represents CH ₃ or H, wherein the degree of hydrogenation is> 98%, very particularly> 98.5%, for example> 99.0%, in particular> 99.5%, for example in the range of> 99.8 up 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, sind bevorzugt herstellbar durch das erfindungsgemäße Hydrierverfahren.Bisglycidyl ethers of the formula I.

in which R is CH ₃ or H, are preferably 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 51408-2 certain total chlorine content of ≤ 1000 Ppm by weight, in particular in the range of 0 to <1000 ppm by weight, e.g. In the range of 100 to <950 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 0.15 ppm by weight, e.g. in the range of 0 to 0.1 ppm by weight, on.

The Bisglycidyl ethers of the formula I preferably have a DIN EN ISO 6271-2 determined platinum cobalt color number (APHA color number) of less than 30, especially smaller than 25, e.g. in the range of 1 to 24, on.

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 230 g / equivalent, especially in the range of 180 to 225 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 900 mm ² / s, particularly less than 850 mm ² / s, for example in the range from 400 to 800 mm ² / s, in each case at 25 ° C., determined in accordance with DIN 51562 part 1 ,

The Bisglycidyl ethers of the 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 Range of 46-60% : 36-50% : 4-18%.

All The cis / cis: cis / trans: trans / trans isomer ratio is particularly preferred 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%, ganz besonders > 98,5%, z.B. > 99,0%, 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 denotes CH ₃ or H, the degree of hydrogenation being> 98%, very particularly> 98.5%, eg> 99.0%, in particular> 99.5%, eg in the range of> 99.8 up to 100%.

Preparation of a catalyst according to the invention

100 g Siliperl AF 125 (3-5 mm spheres, Engelhard, Lot 2960211: (sides) pressure resistance: 76 N (measurement method see above), BET: 353 m ² / g (according to DIN 66131), pore volume: 0.95 ml / g and average pore diameter: 8.6 nm (both according to DIN 66134)) with a water absorption of 9.7 ml / 10 g carrier were placed in a container / dish. 51.83 g of Ru acetate solution. (Umicore, w (Ru) = 4.34 lot No. 0255) was made up to 95 ml with demineralized water (= demineralized water). This impregnation solution was spread over the support and dried overnight at 120 ° C (oven, under air). The dried product was reduced for 2 h at 300 ° C under hydrogen (25 ° C-300 ° C in 90 min., With 60 l / h N ₂ then 50 l / h H ₂ - 10 l / h N ₂ ). Including it was cooled under nitrogen and passivated at room temperature (RT) (T <30 ° C) with dilute air (eg with 3 l / h of air - 50 l / h N ₂ ). The finished catalyst contained 2.0 wt% Ru.

The carrier can be soaked by a known method; the drying can be carried out both moving and non-moving: preferably, a gentle movement should take place or be moved at the beginning and dried statically at the end, so that the ruthenium layer is not rubbed off. The reduction can be performed moving or unmoved. The passivation can be carried out according to the method known to the skilled person. ruthenium content: 2.0 wt .-% (others based on the above provision herge Catalysts contained in the range of 1.6 to 2.5% by weight Ru) Method description: 0.03 to 0.05 grams of the sample is in a Alsint crucible with 5 g of sodium peroxide mixed and egg on heating plate slowly heated. Subsequently, the substance Melting agent mixture initially over an open flame ge Melted and then over a fan flame to the Red hot heated. The digestion is finished as soon as a clear Melt is reached. The cooled melt cake is dissolved in 80 ml of water, the Solution heated to boiling (destruction of H ₂ O ₂ ) and then ßend - after cooling - mixed with 50 ml of hydrochloric acid. It is then made up to a volume of 250 ml with water. Measurement: This sample solution is measured by ICP-MS on isotope Ru 99. Ru dispersity: 45% (after CO sorption, assumed stoichiometry factor: 1; Sample Preparation: Reduction of the sample for 30 min. At 200 ° C with hydrogen and then with helium for 30 min 200 ° C rinsed - Measurement of the metal surface with pulses of the gas to be adsorbed in the inert gas stream (CO) to seed Chemisorption at 35 ° C. Saturation is reached until no CO is adsorbed more, ie, the areas of 3 to 4 on each other following peaks (detector signal) are constant and the peak similar to an unadsorbed pulse. Pulse volume is 1% exactly determined, pressure and temperature of the gas must ü be checked). (Method: DIN 66136-3).

Hydrogenation Example 1

When Reactor served with 75 ml of the o.g. Catalyst (31 g, 2.0% by weight) Ru on Siliperl AF 125 3-5 mm) filled, heated double-jacket reaction tube made of stainless steel (length 0.8 m; Diameter 12 mm), with a feed pump for dosing the feed solution, a separator for the separation of gas and liquid phase with stand attitude, Exhaust control and sampling was equipped. The plant was in flooded mode (i.e., in the flow direction from below to above) without liquid circulation operated. The temperature was at the beginning (entrance) and at the end (Exit) of the catalyst bed measured with a thermocouple (see table below).

In the hydrogenation, a 40 wt .-% solution of distilled oligomer poor bisphenol A bisglycidyl ether (2,2-di- [p-glycidoxiphenyl] propane, Epilox A 17-01 Fa. Leuna resins, batches 16/03 and 06/04: EEW = 172 g / eq.) in stabilizer-free THF containing 4.5% by weight of water. The hydrogenation was run at a catalyst loading of 0.15 kg _{starting material} / L _catalyst · h, a temperature of about 44-50 ° C (see the table below) and a hydrogen pressure of 250 bar and a hydrogen feed of 15 Nl / h. The reactor was operated in flooded mode.

The conversions, selectivities and ruthenium concentrations in the reactor discharge (after removal of the solvent) can be seen in the following table. The information on the feed amount supplied refers to the 40% solution of the oligomer-poor bisphenol A bisglycidyl ether.

Of the Catalyst showed over constant activity and selectivity throughout the experimental period.

Hydrogenation Example 2

In the experimental setup described in hydrogenation example 1, the partially reacted reaction effluent (reaction effluent was partially collected) from hydrogenation example 1 was subjected to posthydrogenation on the same catalyst in order to achieve the desired degree of conversion. The residual aromatic content of the partially hydrogenated product used was 10.1% according to H-NMR, corresponding to a conversion of 89.9%. The epoxy equivalent value was 195 g / equivalent. The hydrogenation was carried out at a temperature of about 44-50 ° C (see following table), a hydrogen pressure of 250 bar and a hydrogen feed of 15 Nl / h (Nl = standard liters = volume converted to normal conditions). The reactor was operated in flooded mode.

The achieved sales, selectivities and ruthenium concentrations in the reactor effluent (after removal of the solvent) can taken from the following table.

The conversion was determined by means of ¹ H-NMR (decrease of the signals of the aromatic protons vs. increase of the signals of the aliphatic protons). The conversion indicated in the examples relates to the hydrogenation of the aromatic groups.

The reaction product generated in hydrogenation example 2 was partially collected, combined and analyzed:
Conversion = 98.6% (H-NMR), epoxy equivalent = 204 g / equivalent, selectivity = 87%

The previously combined reaction product from hydrogenation Example 2 was in a thin-film evaporator with double jacket of glass (area = 0.1 m ² , circumference = 0.25 m) under reduced pressure (800 mbar), a temperature of 140 ° C (oil-temperature double jacket ) and freed at a feed rate of 2500 g / h of the solution from the solvent mixture. The transition temperature was 85 ° C. The distillate was condensed in a glass condenser operated with cooling medium at 15 ° C. The dosage was controlled by a balance with a dosing pump. In total, 13.32 kg of reaction product from hydrogenation example 2 were freed from the solvent. The resulting bottoms discharge was with a metering pump via a second thin-film evaporator with double jacket made of glass (area = 0.046 m ² , circumference = 0.11 m) under reduced pressure (5-10 mbar), a temperature of 140 ° C (oil-temperature double jacket ), to residual amounts of solvents and by-products of hydrogenation such. As epoxypropanol, 1,2- and 1,3-propanediol to remove isopopylcyclohexane.

This gave 5.30 kg of a hydrogenated bisphenol A bisglycidyl ether, which had the following properties: Residual aromatic content ( ¹ H-NMR): 98.6% Epoxyid equivalent value (determination based on ASTM D1652-88): 204 g / equivalent Selectivity: 87% Platinum-cobalt color number (determination based on DIN EN ISO 6271-2) 5 Kinematic viscosity at 25 ° C (determined according to DIN 51562 part 1): 595 mm ² · s ^-1 Density at 25 ° C (determined according to DIN 53217 part 5): 1.05 g / ml Ruthenium content (according to ICP-MS, see below): 0.1 ppm (ICP-MS) Content of volatile compounds (based on DIN 16945 4.8) <2.5% by weight Total chlorine content (determination according to DIN 51408-2) <1000 mg / kg

Hydrogenation Example 3

When Reactor was used with 90 ml of the o.g. Catalyst (31 g, 2.0% Ru on Siliperl 3-5 mm) filled, heated Double-jacket reaction tube made of stainless steel (length 1.4 m, diameter 12 mm), with a feed pump for dosing the feed solution, a Separator for separation of gas and liquid phase with stance, Exhaust control, fluid feedback (pitch circle) and sampling was. The plant was operated in a sprung mode (i.e., in the flow direction from top to bottom) without liquid circulation operated. The temperature was at the beginning (entrance) and at the end (Exit) of the catalyst bed measured with a thermocouple (see table below).

In the hydrogenation, a 40% strength by weight solution of distilled oligomer-poor bisphenol A bisglycidyl ether (2,2-di- [p-glycidoxyphenyl] -propane, Epilox A 17-01 from the company Leuna-Harze, batch: 08 / 04, EEW = 172 g / eq.) In stabilizer-free THF containing 4.5% by weight of water. The hydrogenation was carried out at a catalyst loading of 0.12 kg _{starting material} / L _catalyst · h, a temperature of about 43-45 ° C, a hydrogen pressure of 250 bar, a hydrogen feed of 25 Nl / h and a circulation rate of 3.1 kg / h operated over a period of 161 h. A sample after 161 hours of operation was freed from the solvent on a rotary evaporator at 110 ° C. under reduced pressure (10 mbar) and analyzed.

Of the Conversion was 90% (H-NMR), the epoxide equivalent value was 209 g / equivalent, according to a selectivity of 85%. The ruthenium content in the solvent-free discharge was 0.1 ppm.

Determination of volatile Connections (extract from DIN 16945 4.8)

Approximately 5 g hydrogenated bisphenol A bisglycidyl ether (mass weight: mE) are placed in a sheet metal lid with a flat bottom (75 ± 5 mm Diameter, with about 12 mm edge height) weighed to 1 mg and Unless otherwise specified, 3 h in a warming cabinet stored at 140 ± 2 ° C. After cooling to room temperature is weighed back (Mass weight: mA).

The mass loss (= percentage of volatile compounds) in% is calculated as follows:

The conversion and the degree of hydrogenation were determined by means of ¹ H-NMR: amount of sample: 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).

Of the in the examples indicated conversion is based on the hydrogenation of the aromatic Groups related.

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).

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

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 determined by GPC measurement in area% (area%) 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 from 180 to <380 g / mol:> 98.5 fl.%,
in the range 380 - <520 g / mol: <1.3% by volume,
in the range of 520 - <860 g / mol: <0.80 Fl.% and
in the range of 860-1500 g / mol: <0.15% by fl.

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).

Determination of, 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.

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). Measurement conditions: Device: ICP-MS spectrometer, eg Agilent 7500s 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.

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 aqueous 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 module 753 50 mmol H ₂ SO ₄ ; ultrapure water (Flow about 0.4 ml / min) Calibration: 0.01 mg / L to 0.1 mg / L

coulometric Determination of organically bound chlorine (total chlorine), according to DIN 51408, Part 2, "Determination the chlorine content "

• Literatur: F. Ehrenberger, „Quantitative organische Elementaranalyse", ISBN 3-527-28056-1.

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 (27)

Heterogeneous ruthenium catalyst comprising amorphous silica as the support material, obtainable by single or multiple impregnation of the support material with a solution of a ruthenium salt, drying and reduction, characterized in that the used silica support material has a BET surface area (DIN 66131) in the range of 250 to 400 m ² / g, a pore volume (according to DIN 66134) in the range 0.7 to 1.1 ml / g and a pore diameter (according to DIN 66134) in the range of 6 to 12 nm. Ruthenium catalyst according to claim 1, characterized in that the silicon dioxide support material used has a BET surface area in the range of 290 to 370 m ² / g. Ruthenium catalyst according to claims 1 or 2, characterized, the used silica support material has a pore volume in the range 0.8 to 1.0 ml / g. Ruthenium catalyst according to one of the preceding Claims, characterized in that the silicon dioxide support material used has a pore diameter in the range of 8 to 10 nm. Ruthenium catalyst according to one of the preceding Claims, characterized in that the catalyst is in the range of 0.5 up to 4% by weight of ruthenium, based on the weight of the silica support material, contains. Ruthenium catalyst according to one of claims 1 to 4, characterized in that the catalyst in the range of 1 to 3 wt .-% ruthenium, based on the weight of the silica support material contains. Ruthenium catalyst according to one of the preceding Claims, producible by single or multiple impregnation of the silica support material with an aqueous solution of ruthenium (III) acetate. Ruthenium catalyst according to one of the preceding claims, characterized in that the Catalyst preparation, the silica support material is used in the form of spherical moldings. Ruthenium catalyst according to the preceding claim, characterized in that the spherical shaped body has a diameter in the range from 3 to 5 mm. Ruthenium catalyst according to one of the two preceding Claims, characterized in that the shaped body a (sides) pressure resistance of> 60N. 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 predominantly as a shell on the catalyst surface is concentrated. 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 ruthenium is highly dispersed. Ruthenium catalyst according to the preceding claim, characterized in that the Ru dispersity is in the range of 30 to 60% (measured by CO sorption according to DIN 66136-3). 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 16 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 19, characterized 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 19, characterized 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 17 to 22, 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 17 to 23, characterized that the hydrogenation at a hydrogen absolute pressure in the range from 10 to 325 bar. Method according to one of Claims 17 to 24, characterized that the hydrogenation is carried out on a fixed catalyst bed. Method according to one of Claims 17 to 24, 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 19 to 26, 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 in the range from 0.1 to 10% by weight, based on the solvent, Contains water.