EP1694621A1

EP1694621A1 - Method for producing tricyclodecandialdehyde

Info

Publication number: EP1694621A1
Application number: EP04803526A
Authority: EP
Inventors: Rainer Papp; Rocco Paciello; Christoph Benisch
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-12-09
Filing date: 2004-12-04
Publication date: 2006-08-30
Also published as: CN1890203A; US7321068B2; CN100400490C; WO2005058786A1; DE10357718A1; US20070100168A1

Abstract

The invention relates to a method for producing tricyclodecandialdehyde by hydroformulating dicyclopentadiene by means of a CO/H2-mixture in the presence of a non-ligand modified rhodium catalyst which can be dissolved in a homogenous manner in the hydroformulation medium at a high temperature and at high pressure. Hydroformulation is carried out at pressure of between 200 - 350 bar in at least two reaction zones. In a first reaction zone, the reaction temperature is adjusted from 80 to 120 DEG C and in a reaction zone, which follows on from the latter, the temperature is adjusted from 120 to 150 DEG C, with the proviso that the reaction temperature in the subsequent reaction area is at least 5 DEG C higher that in the previous reaction zone.

Description

Process for the preparation of tricyclodecane dialdehyde

description

The present invention relates to a process for the preparation of tricyclodecanedialdehyde by the hydroformylation of dicyclopentadiene using a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated temperature and under elevated pressure.

For the sake of simplicity, in connection with the description of the present invention, the term “tricyclodecanedialdehyde” is used for the mixture of dialdehydes with the tricyclo-Io [5.2.10 ² ' ⁶ ] decane carbon skeleton, the formula, obtainable by the hydroformylation of dicyclopentadiene

designated. Under the trivial name "dicyclopentadiene" used for the starting compound, the endo, exo mixture of tricyclo [5.2.10 ^{, 6} ] deca-3,8-diene of the formulas

endo exo

understood, which results from the spontaneous Diels-Aider reaction from two molecules of cyclopentadiene during its production, e.g. in cracking processes, according to reaction equation (1).

endo, exo mixture

This reaction is reversible, ie the dicyclopentadiene decomposes, for example when using higher temperatures, in a Retro-Diels-Alder reaction with the regression of the monomer cyclopentadiene. This Retro-Diels-Alder reaction already takes place under the conditions of the hydroformylation reaction, which is why - because of the comparatively high reaction temperatures required - the hydroformylation of dicyclopentadiene to tricyclodecane (“TCD”) - dialdehyde is expediently not otherwise the hydroformylation of customary cobalt catalysts is carried out (cf. Cornils et al; Chemiker-Zeitung 98, 70 (1974)).

Consequently, rhodium catalysts which are homogeneously soluble in the hydroformylation medium and are active because of their higher catalyst activity are also active at lower reaction temperatures than cobalt catalysts for the preparation of TCD-dialdehyde by way of the hydroformylation of dicyclopentadiene. But even at the lower temperatures of the rhodium-catalyzed hydroformylation compared to cobalt catalysis, the cleavage of the dicyclopentadiene into cyclopentadiene takes place - albeit at a slower rate. This is of considerable relevance for the economy of TCD dialdehyde production, since the cyclopentadiene forms hydroformylation-inactive complexes with the non-ligand-modified rhodium carbonyl catalyst that is usually used for TCD production, whereby it must be taken into account that the rhodium is usually used in hydroformylyl - Reaction reactions in amounts of less than 100 ppm by weight is present in the reaction medium. Apart from this, the formation of such rhodium-cyclopentadienyl complexes poses a risk of loss of the valuable precious metal rhodium.

Various measures have been proposed in the past to solve this problem, which can be subsumed under the following points a) to c):

a) use of the rhodium catalyst stabilizing ligands and increasing the hydroformylation activity,

b) increasing the concentration of non-ligand-modified rhodium catalyst in the hydroformylation medium in order to compensate for the inactivation of the rhodium catalyst by cyclopentadiene;

c) Lowering the hydroformylation temperature in order to reduce the rate of the Retro-Diels-Alder reaction to such an extent that the inactivation of the rhodium catalyst by cyclopentadiene released becomes largely negligible.

All of these measures have disadvantages which impair the economics of the processes based on them. To a): The hydroformylation of dicyclopentadiene with rhodium in the presence of excess triphenylphosphine (Pruett in Ann. NY Acad. Sci. 295, 239, 242 (1977)) and triphenylphosphite ligands (US Pat. No. 3,499,933; Pruett in Adv Organomet. Chem. 17, pp. 32-33, (1979)) leads to a yield of TCD-dialdehyde of 87% in two stages with a rhodium content of the reaction medium of 215 ppm by weight under mild conditions. As a result of the high boiling points of the TCD dialdehyde of 150 ° C at 5 mbar, corresponding to approx. 310 ° C at atmospheric pressure on the one hand, and the ligands triphenylphosphine - 377 ° C at atmospheric pressure - and triphenylphosphite - 360 ° C at atmospheric pressure - on the other hand, the distillative separation of the TCD-dialdehyde product from the ligand used in excess with respect to the rhodium is difficult and is associated with an uneconomically high energy consumption. In addition, the high thermal load leads to product losses because of the relatively long residence time of the TCD dialdehyde in the distillation apparatus - a separation of the dialdehyde from the ligand by flash evaporation is not possible due to the close boiling points.

Accordingly, in the preparation of bis (aminomethyl) tricyclicodecane (hereinafter referred to as “TCD diamine”), the rhodium catalyst modified with the triphenylphosphite ligand (rhodium concentration of the reaction mixture: approx. 223% by weight) is described in the preparation of bis (aminomethyl) -ppm) from the hydroformylation stage is not separated from the TCD dialdehyde, but instead the entire hydroformylation output after removal of the solvent toluene by distillation is used in the reductive amination to produce the TCD diamine on a Raney nickel catalyst Adsorption of the rhodium complex on the Raney nickel catalyst.

As a further alternative to separating the TCD dialdehyde from the ligand-containing hydroformylation mixture, various liquid-liquid extraction methods are proposed in WO 93/02024 and EP-A 1065 194, which, however, require a considerable amount of equipment on an industrial scale and thus the product expensive.

Regarding b): DE-A 1618 384 relates to a process for the preparation of TCD diols by the hydroformylation of dicyclopentadiene over rhodium-containing, non-ligand-modified catalysts and the subsequent hydrogenation of the TCD dialdehydes obtained, the product containing the TCD dialdehydes is hydrogenated from the hydroformylation stage without removing the rhodium-containing catalyst and without adding other hydrogenation catalysts by increasing the temperature to at least 200 ° C. with the synthesis gas. According to Example 1 of DE-A 1618 384, the hydroformylation of a 25% by weight % benzene solution of dicyclopentadiene at 130 ° C and a pressure of 200 at (corresponding to 196 bar) in the presence of about 160 ppm by weight (calculated as Rh) of the by reaction of dirhodium trioxide (Rh ₂ O ₃ ) with synthesis gas Rhodium catalyst performed. After the hydroformylation had ended, the temperature of the reaction mixture was raised to 240 ° C., the TCD dialdehyde then being hydrogenated to give the TCD diol, which was obtained in a yield of about 95%.

A disadvantage of these processes is the high concentration of rhodium catalyst used for hydroformylation, which is used to compensate for the catalyst

Inactivation is required because of the cyclopentadiene formed under the hydroformylation conditions by the Retro-Diels-Alder reaction. In addition to the provision of large amounts of the expensive precious metal rhodium for carrying out the process on an industrial scale, which makes the process more expensive, there is a risk of considerable rhodium losses due to deposition on the reactor walls and in pipelines and apparatuses when using such large amounts of rhodium the process becomes uneconomical. The risk of rhodium loss is further increased in the subsequent stage of the hydrogenation of the TCD dialdehyde to the TCD diol by means of the same homogeneous rhodium catalyst, since at the hydrogenation temperature of

240 ° C decomposition of the catalytically active rhodium carbonyl compound already occurs. This is also illustrated by the fact that, according to DE-A 1618 384, the deposited rhodium is separated from the TCD diol by filtration after the hydrogenation.

As mentioned, the hydroformylation with non-ligand-modified rhodium harbors the risk that the thermoplastic rhodium catalyst (cf. US Pat. No. 4,400,547) will partially decompose to metallic rhodium as a result of the thermal stress during the distillative workup of the hydroformylation product deposits on the walls of the reactor and pipes.

The deposited rhodium metal cannot be returned to the hydroformylation reaction since it cannot be converted into the catalytically active rhodium compound under the hydroformylation conditions. This thermolability is particularly evident when, as is the case with working up by distillation, the non-ligand-modified one

Rhodium catalyst stabilizing high CO / H ₂ pressure prevailing under hydroformylation conditions must be lifted. However, decomposition of the non-ligand-modified rhodium catalyst takes place in a CO / H ₂ atmosphere at temperatures above 150 ° C. with the deposition of metallic rhodium on the reactor walls. A large number of processes have therefore been developed in order to stabilize the non-ligand-modified rhodium catalyst when working up the hydroformylation product. A An overview of such processes is given, for example, in WO 99/36382. Of course, the risk of rhodium loss increases, the more non-ligand-modified rhodium catalyst has to be used in the hydroformylation.

If, on the other hand, the rhodium concentration is reduced, as described in EP-B 348 832, the rate of hydroformylation drops and the hydroformylation product contains not only the TCD dialdehyde but also considerable amounts of tricyclodecane monoaldehyde (“TCD monoaldehyde”), the product of the Complete hydroformylation of dicylcopentadiene EP-B 348 832 relates to a process for the preparation of TCD diamine by the hydroformylation of dicyclopentadiene in the presence of non-ligand-modified rhodium carbonyl catalysts and subsequent reductive amination of the TCD dialdehyde obtained with hydrogen and ammonia in the presence of a hydrogenation catalyst - Tor, wherein the hydroformylation product - the TCD dialdehyde - is reductively aminated without removal of the rhodium catalyst. According to the example of EP-B 348 832, the hydroformylation of dicyclopentadiene in toluene solution at 135 ° C. and a pressure of 25 Mpa (corresponding 250 bar) in the presence of 50 ppm by weight Rhodium made, a product is obtained which contains TCD dialdehyde and TCD monoaldehyde in a ratio of about 4: 1.

As the inventors' own experiments have shown (see comparative examples), the rate of hydroformylation of dicyclopentadiene proceeds very slowly at a reaction temperature of 130 ° C. even at a reaction pressure of 600 bar if the rhodium concentration in the reaction mixture is reduced to 10 ppm by weight ,

A disadvantage of the stage of EP-B 348 832 following the hydroformylation, the reductive amination of the TCD dialdehyde over a heterogeneous hydrogenation catalyst, is the fact that the TCD dialdehyde is used without prior removal of the rhodium catalyst. The reason for this is stated in EP-B 348 832 that the distillative removal of the TCD dialdehyde from the hydroformylation discharge poses considerable difficulties which cannot be remedied even with the aid of gentle distillation processes, since the TCD dialdehyde is due to its high reactivity Formation of higher molecular condensation products tends. As a result, the rhodium catalyst is adsorbed on the heterogeneous hydrogenation catalyst used for the reductive amination - in the case of EP-B 348 832, a nickel catalyst - and can only be recovered by working up, ie destroying, the hydrogenation catalyst. In addition, the reaction temperature used for the reductive amination of 130 ° C. differs in the absence of the stabilizing carbon monoxide from the reactor walls considerable amounts of metallic rhodium.

Regarding c): Falbe et al. Described in Hydrogen-Chemie 48, 54 (1967) the hydroformylation of dicyclopentadiene to TCD-dialdehyde by means of a non-ligand-modified rhodium carbonyl catalyst which is reacted in situ in the reaction mixture by the action of synthesis gas on dirhodium trioxide ( Rh ₂ O ₃ ) is produced at a temperature of 115 ° C. In order to compensate for the slower reaction rate due to the lower reaction temperature, a high concentration of rhodium catalyst of about 160 ppm by weight, calculated as Rh, is set in the reaction mixture. When a 20% by weight solution of dicyclopentadiene in THF is hydroformylated, under these conditions and a pressure of 200 at (= 196 bar), only a moderate yield of 61% of TCD dialdehyde is achieved after a reaction time of five hours. As the inventors' own investigations showed, the hydroformylation of dicyclopentadiene to TCD-dialdehyde proceeds very slowly at a concentration of non-ligand-modified rhodium carbonyl catalyst in the reaction mixture of 10 ppm by weight at 110 ° C. and a pressure of 280 bar (see. Comparative example).

TCD dialdehyde serves as the starting material for the production of TCD diol or TCD diamine. TCD-diol is used as a diol component for the production of polyesters of unsaturated dicarboxylic acids, which are either used as such for glass fiber reinforced plastics or which are processed as styrene copolymers into solvent-free, fast-drying lacquers of particular hardness. Acrylic and methacrylic acid esters of TCD diol, which are available according to standard methods, serve as raw materials for adhesives. It also serves as a diol component in the production of polyglycidyl ethers and polyurethanes. TCD-diamine is used as a hardener for epoxy resins, for the production of polyamide resins and as a starting material for diisocyanates, which in turn are processed into polyurethanes. Further areas of application for TCD-diol and TCD-diamine are e.g. in Cornils et al, Chemiker-Zeitung 98, 70 (1974). The synthesis of TCD-dialdehyde is the key step in the production of the versatile TCD-diol and TCD-diamine products.

The present invention was therefore based on the object of finding an improved process for the preparation of TCD dialdehyde and, subsequently, TCD diol and TCD diamine, which does not have the disadvantages of the prior art. In particular, the process should enable TCD dialdehyde to be produced economically with a good space-time yield, without the risk of economically significant rhodium losses and without the need for economically disadvantageous ligand separations. and thus allow the inexpensive production of the secondary products TCD-diol or TCD-diamine.

Accordingly, a process for the preparation of tricyclodecanedialdehyde by the hydroformylation of dicyclopentadiene by means of a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated temperature and under increased pressure was found, which is characterized in that the Hydroformylation is carried out at a pressure of 200 to 350 bar in at least two reaction zones, a reaction temperature of 80 to 120 ° C. being set in a first reaction zone and a reaction temperature of 120 to 150 ° C. in a reaction zone following this reaction zone, with the proviso that that the reaction temperature in the subsequent reaction zone is at least 5 ° C. higher than in the preceding reaction zone.

According to the invention, the TCD dialdehyde of the formula II is prepared by the hydroformylation of dicyclopentadiene I using a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst in accordance with reaction equation (2),

the isolable intermediate tricyclodecene monoaldehyde being formed in the course of the reaction, which reacts further to give the TCD dialdehyde.

The hydroformylation process according to the invention is carried out with the aid of “non-ligand-modified” rhodium catalysts. The term “non-ligand-modified” rhodium catalysts is used in this application for rhodium hydroformylation catalysts which, in contrast to conventional rhodium hydroformylation catalysts, are among the Hydroformylation conditions are not modified with phosphorus-containing ligands such as phosphine or phosphite. In this sense, carbonyl or hydrido ligands are not understood as ligands. It is assumed in the specialist literature (see Falbe, Ed .: New Syntheses with Carbon Monoxide, Springer, Berlin 1980, pp. 38ff) that the rhodium compound HRh (CO) modifies the catalytically active rhodium species in the hydroformylation with non-ligand-modified Rhodium catalysts are, although this has not been clearly proven due to the many chemicals that run side by side in the hydroformylation reactor. This assumption is only used here for the sake of simplicity. The non-ligand-modified rhodium catalysts are formed under the conditions of the hydroformylation reaction from rhodium compounds, for example rhodium salting, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) acetate, rhodium (2-ethylhexanoate), rhodium (III) acetylacetonate, rhodium (III) suIfate or rhodium (III) ammonium chloride, from rhodium chalcogenides, such as rhodium (III) oxide or rhodium (III) sulfide, from salts of rhodium oxygen acids, for example the rhodates, from rhodium carbonyl compounds, such as rhodium dicarbonyl acetylacetonate, cycloocadadiene-rhodium acetate or chloride in the presence of CO / H ₂ - Mixtures commonly referred to as synthesis gas.

The process according to the invention for the preparation of TCD dialdehyde can be carried out in two or more, for example in three or four, reaction zones which differ with regard to the reaction temperature used, the hydroformylation of dicyclopentadiene at a temperature of generally 80 to in a first reaction zone 120 ° C, preferably at 105 to 115 ° C and the hydroformylation temperature of the discharge from the first reaction zone upon entry into the reaction zone following this first reaction zone to a temperature of generally above 120 ° C to 150 ° C, preferably from 130 to 140 ° C is increased. The reaction zones are generally operated at a CO / H ₂ pressure of 200 to 350 bar, advantageously from 250 to 300 bar. The process according to the invention is preferably carried out in two reaction zones.

A reaction zone in the sense of the present invention can comprise one or more reactors connected in series if these are operated within the specified temperature range for the reaction zone in question. For example, the first reaction zone can consist of a single hydroformylation reactor which is operated, for example, at a temperature of 90, 100 or 110 ° C., or it can consist of several, for example two or three, reactors connected in series in which the hydroformylation is carried out within of the specified temperature range is operated for the first reaction zone, these two or three reactors arranged in series at the same temperature or at different temperatures within the temperature range specified for the first reaction zone, for example at 90 ° C. in the first reactor, 100 ° C. in the second and 110 ° C in the third reactor in the series. It follows from this that a reaction zone can also comprise a plurality of reactors connected in series and / or in parallel which meet the criterion according to the invention for an individual reaction zone, namely working within the temperature range specified for the reaction zone in question. Conversely, a single hydroformylation reactor can be segmented into a plurality of reaction compartments by suitable internals, the reaction temperature in the individual reaction compartments in each case being set such that one or more of these reaction compartments form the first reaction zone and one of the subsequent reaction compartments of the Reactor form the subsequent reaction zone. The above explanations for carrying out the process according to the invention in the first reaction zone apply analogously for carrying out the process according to the invention in the subsequent reaction zone, that is to say in the temperature range from above 120 ° C. to 150 ° C.

In principle, all types of reactors suitable for hydroformylation reactions can be used as reactors in the process according to the invention, for example stirred reactors, bubble column reactors such as those e.g. in US-A 4778 929, circulation reactors as e.g. EP-A 1 114 017 relates to tubular reactors, the individual reactors of a number of different mixture characteristics being able to be used, e.g. described in EP-A 423769, furthermore compartmentalized reactors can be used, such as those e.g. The subject of EP-A 1 231 198 or of US-A 5 728 893 are.

If a reaction zone comprises several reactors, the same or different reactor types can be used in this reaction zone, and the same or different reactor types can also be used from reaction zone to reaction zone. Preferably the same types of reactors are used in the individual reaction zones, e.g. Gas circulation reactors or stirred tanks.

Characteristic of the hydroformylation process according to the invention is therefore the implementation of the hydroformylation in several, preferably two, reaction zones graded with respect to the reaction temperature used, the first reaction zone generally in the temperature range from 80 to 120 ° C. and the subsequent reaction zone generally in the temperature range from more than 120 ° C to 150 ° C is operated. The above explanations regarding the technical implementation of the individual reaction zones by means of one or more reactors and reactor types thus merely represent possible configurations of the process according to the invention, but are not critical to its success. Thus, with regard to the investment costs, it can be advantageous to use only one reactor per reaction zone when implementing the process according to the invention; on the other hand, depending on the reactors that may already be available at the respective location of such a plant, it may prove to be more advantageous to use one to operate the configurations mentioned above, depending on the planned plant capacity and available reactor capacity.

In general, the hydroformylation output from the first reaction zone is passed into the subsequent reaction zone without further working up.

In general, a pressure of 200 to 350 bar, preferably of 250 to 300 bar, is used in the hydroformylation process according to the invention in the two reaction zones. It is possible to use a lower or higher pressure. The pressure is usually generated by pressing the CO / H ₂ mixture required for the hydroformylation into the reactors. In the hydroformylation process according to the invention, CO / H ₂ mixtures with CO / H ₂ molar ratios of from 1:10 to 10: 1, preferably from 1: 2 to 2: 1, can be used. A synthesis gas with a CO / H ₂ molar ratio, as is produced in industrial synthesis gas plants, is particularly preferably used. The CO / H ₂ molar ratio of such synthesis gas is generally in the range from 39:61 to 41:59 CO / H ₂ .

The hydroformylation process according to the invention can be carried out in the presence or absence of solvents. Although there are in principle no restrictions with regard to the solvents usually used in hydroformylation processes when a solvent is used in the process according to the invention, those solvents are preferably used in the process according to the invention which can be easily removed by distillation from the relatively high-boiling TCD dialdehyde or whose removal is not necessary , The latter type of solvent includes TCD dialdehyde itself as well as TCD diol. Other suitable conventional solvents are aromatics, such as benzene, toluene and xylene or their mixtures, hydrocarbons or mixtures of hydrocarbons, esters of aliphatic carboxylic acids, such as ethyl acetate, ethers, such as tert-butyl methyl ether, tert-butyl ethyl ether and tetrahydrofuran, and also alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol and ketones, such as acetone or methyl ethyl ketone. So-called “ionic liquids” can also advantageously be used as solvents. These are liquid salts, for example N, N'-dialkylimidazolium salts, such as the N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts, such as the tetra-n -butylammonium salts, N-alkylpyridinium salts, such as the n-butylpyridinium salts, tetraalkylphosphonium salts, such as the tris-hexyl (tetradecyl) phosphonium salts, where the counterion in each case, for example, the tetrafluoroborate, the acetate, the tetrachloroaluminate or the hexasodium, the tos These ionic liquids can be separated from the hydroformylation mixture by phase separation.

The rhodium concentration to be used is not critical for the process according to the invention, i.e. In principle, it is possible to work with high and low rhodium concentrations without this having a negative effect on the hydroformylation result. The rhodium concentration in the liquid reaction mixture of the hydroformylation process in the process according to the invention is advantageously set to 2 to 20 ppm by weight, particularly preferably to 4 to 10 ppm by weight, in each case calculated as Rh. Of course, higher rhodium concentrations can also be used.

Surprisingly, the procedure according to the invention enables staggered temperature control in two or more reaction zones despite being very low Rhodium concentrations in the hydroformylation reaction mixture very good space-time yields in the production of TCD dialdehyde from dicyclopentadiene. This minimizes the risk of economically disadvantageous rhodium losses due to the decomposition of the uncomplexed rhodium catalyst. Without wishing to be bound in any form by the following theory, it is assumed that at the low reaction temperature used in the first reaction zone the strained double bond of the cyclopentadienyl ring of the dicyclopentadiene is hydroformylated, as a result of which the ring system is not a retro-Diels-Alder - Reaction can enter more, which is why the rate of hydroformylation of the relatively less reactive second double bond can then be accelerated in the second reaction zone without the risk of the formation of hydroformylation-inactive cyclopentadienyl complexes of rhodium.

Since the starting material dicyclopentadiene is present as a mixture of endo- and exo-isomers, the attack of the rhodium catalyst can take place at geometrically different positions of the two double bonds and also with respect to the plane of the ring system, stereochemically different from above or below, is used as the hydroformylation product Obtain a mixture of regio- and stereoisomeric dialdehydes which, as mentioned at the beginning, is referred to as TCD dialdehyde in the context of this application. This mixture can either be traded as such or subsequent implementations, e.g. the hydrogenation to TCD diol or the reductive amination to TCD diamine.

The process according to the invention can be carried out either batchwise or continuously, the continuous mode of operation being preferred.

The process according to the invention is generally carried out using the liquid discharge process. The liquid hydroformylation mixture is drawn off from the first reaction zone and passed in liquid form into the subsequent reaction zone. The hydroformylation output from the first reaction zone can be worked up before it is introduced into the subsequent reaction zone, but in general the hydroformylation output from the first reaction zone is fed to the second reaction zone without working up. The second reaction zone is operated at the selected reaction temperature which differs from that of the first reaction zone. For the reaction in the second reaction zone, the same or a lower or higher pressure than in the first reaction zone can be used - in general, the second reaction zone is operated under the same or approximately the same pressure as in the first reaction zone.

If desired, the liquid reaction discharge from the second reaction zone can be fed to one or more further reaction zones, but it is preferably worked up. For working up, the discharge from the second reaction zone is ne continuously removed from the hydroformylation reactor and for the separation of gases dissolved therein, such as unreacted CO / H ₂ mixture, CO ₂ and nitrogen, to a pressure which is generally 1 to 35 bar, preferably 3 to 10 bar, lower as that prevailing in the hydroformylation reactor, is released into an expansion vessel. If desired, the gases released in the expansion vessel can be recycled back into one or both of the preceding reaction zones, it being expedient to feed this gaseous recycle stream to a wash or an intermediate condensation in a heat exchanger to remove entrained TCD aldehydes and / or dicyclopentadiene and / or tricyclodecane undergo or discharge a partial stream of this recycle stream to avoid the accumulation of inert gases in the reaction system. The liquid product mixture obtained in the expansion vessel can then, if necessary after prior removal of the rhodium catalyst, for example by methods as described in WO 99/36382, via one or more expansion stages, the number of expansion stages generally being geared to the apparatus conditions of the plant in question, to atmospheric pressure or if the TCD dialdehyde is then to be further processed to TCD diol or TCD diamine, to the pressure to be used for the subsequent reaction. If isolation of the TCD dialdehyde is desired, the solvent optionally added to the reaction mixture is expediently removed in a conventional manner, for example by distillation or by phase separation if an ionic liquid is used.

In a preferred embodiment of the process according to the invention, the working up of the liquid hydroformylation discharge from the second reaction zone is carried out in such a way that, as described above, it is first placed in an expansion vessel to a pressure which is 5 to 30 bar abs., Preferably 5 to 10 bar abs., lower than that prevailing in the second reaction zone, relaxed, the resulting product liquid, which is still at a high CO / H ₂ level, is passed over an ion exchanger to remove the rhodium catalyst and the demetallized product mixture is then either in one or more relaxation stages to atmospheric pressure or to the pressure required for any subsequent reaction, for example hydrogenation to TCD diol or reductive amination to TCD diamine. The removal of the rhodium catalyst is advantageously carried out as described in DE-A 1954 315 or WO 02/20451, on a primary, secondary, tertiary or quaternary amine group in base form containing ion exchange resin based on styrene-divinylbenzene copolymers, for example Amberlite® IR45 or Dowex ® 4. Macroreticular ion exchanger types such as Amberlyst® A21, Lewatit® MP62, Lewatit® MP64, Imac® A20, Zerolit® G, Amberlite® IRA93, Amberlyst® A26 or Amberlyst® A27 are particularly suitable. Macroporous, macroreticular sulfonic acid group-containing ion exchange resins are also suitable for removing the rhodium from the hydroformylation discharge Basis of styrene-divinylbenzene copolymers, such as the ion exchanger Amberlyst® 15, which is mentioned for this purpose in US Pat. No. 5,208,194. The removal of the rhodium catalyst from the hydroformylation product at a still relatively high pressure has the advantage that the rhodium catalyst can be replaced by the CO / H ₂ mixture dissolved in the product mixture is sufficiently stabilized so that there is no decomposition of the rhodium carbonyl compound with the deposition of elemental rhodium on the walls of the apparatus and associated rhodium losses. The rhodium can be recovered virtually quantitatively from the ion exchange resins loaded with it in a simple manner, for example by ashing them as described in US Pat. Nos. 5208,194 and WO 02/20451.

In another preferred embodiment of the process according to the invention, the liquid hydroformylation output from the second reaction zone can be let down to about 1 to 10 bar, preferably to atmospheric pressure. The temperature of the liquid hydroformylation discharge can be reduced to generally 40 to 100 ° C., preferably to 60 to 90 ° C., by additional cooling, as a result of which the temperature-sensitive rhodium catalyst is also stabilized. The relaxation can be done in one step or in several steps. The relaxed and cooled liquid hydroformylation discharge can then be treated with a suitable ion exchanger in order to separate off the rhodium catalyst in the manner described above.

The process according to the invention for the production of TCD dialdehyde by the hydroformylation of dicyclopentadiene can also be used in a smoothly analogous manner for the hydroformylation of the tricyclopentadiene isomers purple and IIIb to the corresponding pentacyclopentadecane dialdehydes IVa and IVb.

purple IVa (3)

lllb IVb

The pentacyclopentadecane dialdehydes obtainable in an analogous manner by hydrogenation or reductive amination from the pentacyclopentadecane dialdehydes or dimethylols or di- aminomethyl derivatives are used in applications similar to TCD diol or TCD diamine.

As already mentioned, the preparation of the TCD dialdehyde is the key step for the economical production of the secondary products 3 (4), 8 (9) -dimethyloϊtricyclo-

[5.2.10 ^2.6 ] decane (TCD-diol) and 3 (4), 8 (9)) - diaminomethyltricyclo [5.2.10 ^2ι6 ] decane (TCD-diamine), which in a conventional manner by hydrogenation or reductive amination of the TCD dialdehyde can be obtained. Consequently, the economy of the process for the production of TCD dialdehyde has a decisive influence on the economy of the processes for the production of TCD diol and TCD diamine.

Accordingly, the present invention further relates to a process for the preparation of tricyclodecanedimethylol by the hydroformylation of dicyclopentadiene by means of a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated temperature and under elevated pressure to give tricyclodecanedialdehyde Separation of the rhodium catalyst from the tricyclodecanedialdehyde and hydrogenation of the tricyclodecanedialdehyde by means of a gas containing molecular hydrogen over a heterogeneous catalyst at elevated temperature and at elevated pressure, which is characterized in that the hydroformylation is carried out at a pressure of 200 to 350 bar in at least two reaction zones, wherein in a first reaction zone a reaction temperature of 80 to 120 ° C and in a reaction zone following this reaction zone a reaction temperature of 120 to 150 ° C is set, mi t the proviso that the reaction temperature in the subsequent reaction zone is at least 5 ° C higher than in the preceding reaction zone.

According to the invention, the key step for the economical production of TCD diol, namely the synthesis of TCD dialdehyde, is carried out as in the process according to the invention for the production of TCD dialdehyde.

As already mentioned in the description of the hydroformylation process according to the invention, the discharge of the hydroformylation process, which essentially contains the TCD dialdehyde, the rhodium catalyst and optionally the solvent added, after the rhodium catalyst has been separated off, can be used directly in the hydrogenation to give the TCD diol become. Any solvent contained in the hydroformylation discharge can be separated from the hydrogenation before it is fed into the hydrogenation — in particular when using ionic liquids as a solvent, preferably — especially when using conventional solvents — the hydroformylation discharge is passed into the hydrogenation reactor without prior removal of the solvent. Molecular hydrogen-containing gases which can be used in the process according to the invention are both hydrogen and gas mixtures of hydrogen and a gas which is inert under the hydrogenation conditions, such as nitrogen, carbon dioxide, argon and / or methane. Preferably only hydrogen is used.

The hydrogenation catalyst to be used for the hydrogenation of TCD dialdehyde to TCD diol is not the subject of the present invention. Consequently, the following list of suitable hydrogenation catalysts is only for the purpose of illustration and is only exemplary, but not restrictive.

Practically all heterogeneous catalysts suitable for the hydrogenation of carbonyl groups can be used as hydrogenation catalysts for the hydrogenation of the TCD dialdehyde to TCD diol, for example those as described in Houben-Weyl, Methods of Organic Chemistry, Volume IV, 1 c, pp. 16-26 , Thieme-Verlag, Stuttgart, 1980. The hydrogenation catalysts can be in the process according to the invention in a fixed bed or mobile, e.g. be arranged in a fluidized bed in the reactor.

Those heterogeneous hydrogenation catalysts which contain one or more elements from groups Ib, Vlb, Vllb and Vlllb of the Periodic Table of the Elements are preferably used. To promote their catalytic activity and selectivity, these catalysts can furthermore contain one or more elements from groups la, lla, lila, IVa and Va of the periodic table of the elements. Preferred catalysts are in particular those which are used as catalytically active components e.g. Copper, chromium, rhenium, cobalt, nickel, rhodium, ruthenium, iridium, palladium, iron or platinum or mixtures of several of these elements and, if appropriate, as further components which influence their catalytic activity and selectivity, e.g. Contain indium, tin or antimony. Hydrogenation catalysts which contain cobalt, nickel and / or copper are particularly preferably used for the hydrogenation of the TCD dialdehyde.

Both heterogeneous catalysts and so-called precipitation catalysts, which have been produced by applying the catalytically active component to a support material, can be used as heterogeneous catalysts.

The precipitation catalysts can be prepared by removing their catalytically active components from their salt solutions, in particular from the solutions of their nitrates and / or acetates, by adding solutions of alkali metal and / or alkaline earth metal hydroxide and / or carbonate solutions, for example as poorly soluble hydroxides, oxide hydrates , basic salts or carbonates precipitates, then dries the precipitate obtained and then converts it to the corresponding oxides, mixed oxides and / or mixed-valent oxides by caicination at generally 300 to 700 ° C, in particular 400 to 600 ° C, which by a treatment are reduced with hydrogen or hydrogen-containing gases at generally 50 to 700 ° C., in particular at 100 to 400 ° C., to the metals and / or oxidic compounds of low oxidation level in question and converted into their actual, catalytically active form. Instead of hydrogen, other suitable reducing agents, for example hydrazine, can also be used for this purpose, but the use of hydrogen is preferred. As a rule, the process is reduced until practically no more hydrogen is consumed. In the production of precipitation catalysts which contain a support material, the catalytically active components can be precipitated in the presence of the support material in question. The catalytically active components can, however, advantageously also be precipitated from the relevant salt solutions at the same time as the support material. Suitable carrier materials are, for example, the oxides of aluminum, titanium, zinc oxide, zirconium dioxide, silicon dioxide, clays, for example montmorriilonite, silicates such as magnesium or aluminum silicates, diatomaceous earth or zeolites such as ZSM-5 or ZSM-10 zeolites. Mixtures of such carrier materials can also be used. If desired, the dried precipitate from the precipitation before the caicination can be admixed with shaping aids such as graphite, talc or stearin and / or with pore formers such as cellulose, methyl cellulose, starch, wax, paraffin and / or a polyalkylene glycol, and to give shaped catalyst bodies such as tablets, spheres , Rings or strands are pressed or extruded.

Hydrogenation catalysts are preferably used which contain the metals or metal compounds which catalyze the hydrogenation deposited on a support material. In addition to the above-mentioned precipitation catalysts, which, in addition to the catalytically active components, also contain a support material, generally suitable support catalysts for the preparation of the TCD diol are those in which the catalytically active components e.g. have been applied to a carrier material by impregnation.

The manner in which the catalytically active metals are applied to the support is generally not critical and can be accomplished in a variety of ways. The catalytically active metals can be on these support materials, for example by impregnation with solutions or suspensions of the salts or oxides of the elements in question, drying and subsequent reduction of the metal compounds to the metals in question or compounds with a low oxidation state using a reducing agent, for example with hydrogen, hydrogen-containing gases or hydrazine , preferably with gases containing hydrogen. The reduction of the metal compounds deposited on the support material can be carried out under the same conditions as previously described for the precipitation catalysts. Another possibility for applying the catalytically active metals to these supports is to provide the supports with solutions of salts which are easily decomposable thermally, for example with nitrates or complex compounds which are readily decomposable thermally, for example To impregnate carbonyl or hydrido complexes of the catalytically active metals and to heat the support soaked in order to thermally decompose the adsorbed metal compounds to temperatures of 300 to 600 ° C. This thermal decomposition is preferably carried out under a protective gas atmosphere. Suitable protective gases are, for example, nitrogen, carbon dioxide, hydrogen or the noble gases. Furthermore, the catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying. In this case, metal wire nets or metal foils can also serve as carrier materials.

The content of the supported catalysts in the catalytically active metals is in principle not critical for the success of the hydrogenation. It goes without saying for the person skilled in the art that higher levels of these supported catalysts in catalytically active metals can lead to higher space-time conversions than lower levels. In general, supported catalysts are used whose content of catalytically active metals is 0.1 to 90% by weight, preferably 0.5 to 40% by weight, based on the total catalyst. Since this content information relates to the entire catalyst including the support material, but the different support materials have very different specific weights and specific surfaces, this information can also be exceeded or fallen short of, without this having an adverse effect on the result of the process according to the invention. Of course, several of the catalytically active metals can also be applied to the respective carrier material. Furthermore, the catalytically active metals can be applied to the support, for example by the processes of DE-A 25 19 817, EP-A 147219 and EP-A 285420. In the catalysts according to the above-mentioned documents, the catalytically active metals are present as alloys, which can be obtained by thermal treatment and / or reduction of e.g. by impregnation on a support deposited salts or complexes of the aforementioned metals.

Generally the oxides of aluminum, titanium, zinc oxide, zirconium dioxide, silicon dioxide, clays, e.g. Montmorillonites, silicates such as magnesium or aluminum silicates, zeolites such as ZSM-5 or ZSM-10 zeolites, and activated carbon can be used. Preferred carrier materials are aluminum oxides, titanium dioxide, silicon dioxide, zirconium dioxide, kieselguhr or activated carbon. Mixtures of different support materials can of course also serve as supports for hydrogenation catalysts.

Examples of hydrogenation catalysts which can be used for the hydrogenation of TCD-dialdehyde to TCD-diol are as follows: cobalt on activated carbon, cobalt, cobalt on silicon dioxide, cobalt on aluminum oxide, iron on activated carbon, manganese on activated carbon, nickel, nickel on silicon dioxide, nickel Diatomaceous earth, copper on activated carbon, copper on silicon dioxide, copper on aluminum oxide, Copper chromite, copper / nickel precipitation catalysts, and the catalysts according to DE-A 3932 332, WO 01/87809, EP-A 44444, EP-A 224 872, DE-A 39 04083, DE-A 23 21 101, EP-A 415202, DE-A 23 66 264, DE-A 2628 987, EP-A 394 842 and EP-A 100 406.

The hydrogenation conditions, ie pressure and temperature, are not subject to any particular requirements with regard to the starting material TCD dialdehyde and the hydrogenation product TCD diol. In view of the variety of different suitable hydrogenation catalysts, some of which are commercially available, some of which can be produced according to the published state of the art, hydrogenation conditions are generally selected first that correspond to the optimal working conditions of the hydrogenation catalyst used in each case and how they are available in the case of commercially available catalysts relevant operating instructions or in the case of catalysts known from the prior art, are disclosed in the relevant documents. The hydrogenation conditions set in this way can then be further optimized in routine tests.

The hydrogenation of the TCD dialdehyde can be carried out in stirred tanks using a suspension of fine hydrogenation catalyst particles, e.g. Raney nickel or Raney cobalt, are carried out, the hydrogenation catalyst is preferably arranged in a fixed bed in the hydrogenation reactor, via which the reaction mixture can be passed in a bottoms or downflow mode. Suitable reactors for this are e.g. Tube reactors or loop reactors through which the reaction mixture is pumped in a circle over the fixed catalyst bed. A cooling device e.g. in the reactor loop can advantageously be attached in the form of a heat exchanger for removing the heat of hydrogenation. With regard to the high amount of heat released during the hydrogenation, it can also be advantageous to carry out the hydrogenation stepwise in two or more hydrogenation reactors connected in series, if necessary with intermediate cooling of the reaction mixture before it enters the second reactor and only up to one in the first reactor To hydrogenate partial conversion of the TCD dialdehyde.

To suppress side reactions, such as acetal formation or aldol condensation, water can be added to the TCD dialdehyde in an amount of up to 0% by weight before it is introduced into the hydrogenation reactor.

After releasing the hydrogenation effluent and separating off any solvents and water contained therein by distillation, the TCD diol can be purified by distillation, preferably under reduced pressure. According to a preferred embodiment of the process, the TCD diol can be separated from low-boiling impurities by means of steam distillation, if desired at reduced pressure. With this cleaning method, the low boilers are stripped from the raw TCD diol product using steam. Since the starting material is TCD dialdehyde in Is used in the form of an isomer mixture in the hydrogenation, the TCD diol is also obtained as a mixture of isomers.

The present invention further relates to a process for the preparation of diamino-methyl-tricyclodecane by the hydroformylation of dicyclopentadiene using a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated pressure and at elevated temperature, followed by separation of the Rhodium catalyst of tricyclodecanedialdehyde and reductive amination of tricyclodecanedialdehyde over a heterogeneous catalyst in the presence of a molecular hydrogen-containing gas and ammonia at elevated temperature and pressure, which is characterized in that the hydroformylation is carried out at a pressure of 200 to 350 bar in at least two reaction zones is carried out, a reaction temperature of 80 to 120 ° C. in a first reaction zone and a reaction temperature of 120 to 150 ° C. in a reaction zone following this reaction zone, with which Ma ß addition that the reaction temperature in the subsequent reaction zone is at least 5 ° C higher than in the previous reaction zone.

According to the invention, the final step for the economical production of TCD diamine, namely the hydroformylation of dicyclopentadiene to TCD dialdehyde, is carried out as in the hydroformylation process according to the invention.

As already mentioned in the description of the hydroformylation process according to the invention, the discharge of the hydroformylation process, which essentially contains the TCD dialdehyde, the rhodium catalyst and optionally the solvent added, after the rhodium catalyst has been separated off, can be used directly in the reductive amination to give the TCD diamine , Any solvent contained in the hydroformylation discharge can be separated from it before it is fed into the amination, in particular when ionic liquids are used as the solvent, preferably - especially when using conventional solvents - the hydroformylation discharge is passed into the amination reactor without prior removal of the solvent ,

If TCD-diol was used as the solvent in the hydroformylation, this is also converted to TCD-diamine on the amination catalyst. This is due to the fact that the nature of the amination catalysts are hydrogenation catalysts which, as such, also effect the dehydrogenation of alcohols to aldehydes as an equilibrium reaction. The TCD diol which may be present in the TCD dialdehyde is consequently first dehydrated on the amination catalyst to give the TCD dialdehyde which, together with the ammonia fed to the amination reactor, forms an imine which is then hydrogenated on the amination catalyst to give the amine. Accordingly, in the reductive amination of TCD dialdehyde, hydrogen in a stoichiometric amount is used as a re- reduction of the imine is consumed, whereas in the amination of the TCD diol hydrogen is first released by dehydrogenation, which is then used in the subsequent reaction to hydrogenate the imine to the amine. Both reactions run side by side on the amination catalyst. Even if no hydrogen is formally consumed in the amination of the TCD diol, the presence of molecular hydrogen is mandatory when the TCD diol is aminated to activate the amination catalyst. It follows from the above that instead of TCD dialdehyde, if desired, its mixtures with TCD diol can also be used in the amination.

The reductive amination of the TCD dialdehyde to the TCD diamine by means of molecular hydrogen-containing gases and ammonia can be carried out in a conventional manner at a pressure of generally 1 to 400 bar, preferably 10 to 250 bar and particularly preferably 30 to 200 bar and at a reaction temperature of generally 50 to 250 ° C, preferably from 80 to 200 ° C and particularly preferably from 100 to 200 ° C. The molecular hydrogen-containing gases used in the process according to the invention are both pure hydrogen and gas mixtures of hydrogen and a gas which is inert under the hydrogenation conditions, such as nitrogen, carbon dioxide, argon and / or methane.

The ammonia can be used in a stoichiometric amount with respect to the two carbonyl groups present in the TCD dialdehyde, in general the ammonia is used in a 5 to 250 times, preferably in a 10 to 100 times to reduce the formation of secondary or tertiary amines particularly preferably fed in a 25 to 80-fold molar excess per mole of carbonyl group to be aminated. The molecular hydrogen is generally added in an amount of from 0.5 to 40, preferably from 2 to 30 and particularly preferably from 4 to 30, mol / mol of carbonyl group to be aminated. Even if TCD diol is contained in the starting material, a hydrogen excess of 0.5 to 40, preferably 2 to 30, in particular 4 to 30 mol / mol of methylol group to be aminated is generally used.

The heterogeneous catalyst used for the reductive amination is not the subject of the present invention. All heterogeneous catalysts usually used for the reductive aminations can also be used for the reductive amination of the TCD dialdehyde. Since the heterogeneous catalysts for reductive amination are hydrogenation catalysts, practically the same catalysts as those mentioned for the hydrogenation of TCD dialdehyde to TCD diol can also be used for the reductive amination of TCD dialdehyde or TCD Diol to TCD diamine can be used. Such catalysts are preferably used which contain up to 100% by weight of at least one element or at least one compound of an element from group VIII of the Periodic Table of the Elements in the active catalyst mass, ie from the group consisting of Fe, Ru, Os, Co , Rh, Ir, Ni, Pd and Pt. In a preferred embodiment, the active catalyst composition can furthermore contain up to 50% by weight of at least one element or at least one compound of an element from group IB of the periodic table of the elements, that is to say from the group consisting of Cu, Ag and Au , preferably Cu. In a further preferred embodiment, the amount of metal or compound of a metal from group IB is 1 to 30% by weight, in particular 10 to 25% by weight, based on the total amount of the active catalyst composition.

The catalysts can be used as precipitation catalysts or in supported form. When using supported catalysts, the proportion of the support in the total mass of the catalyst (active composition plus support) is generally 10 to 90% by weight.

All known suitable supports can be used as supports, for example activated carbon, silicon carbide or metal oxides. The use of metal oxides is preferred. Of the metal oxides, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide or mixtures thereof, which are optionally doped with alkali and / or alkaline earth metal oxides, are preferably used. Γ-aluminum oxide, silicon dioxide, zirconium dioxide or titanium dioxide or mixtures thereof, in particular Al ₂ O ₃ , are particularly preferred. The carriers can be used in any form, for example as extrudates (in the form of strands), pellets, tablets, monoliths, woven fabrics, knitted fabrics or in powder form. The supported catalysts can be produced by generally known processes.

The reductive amination of the TCD dialdehyde can be carried out on conventional reactors which are conventionally used for reductive amination reactions. For example, the TCD-diamine can be prepared in stirred tanks with finely divided catalysts, such as Raney nickel or Raney cobalt, suspended in the reaction mixture. The amination catalyst is preferably arranged in one or more fixed beds which can be installed in conventional tubular or loop reactors and through which the liquid reaction mixture can be passed in a bottom or trickle mode. To remove the heat of reaction generated in the reductive amination, the reactors are advantageously equipped with cooling devices, for example heat exchangers. In view of the heat of reaction which arises in the case of reductive amination, it can also be advantageous to carry out the reductive amination stepwise in two or more reactors connected in series or on a plurality of fixed beds, if desired with intermediate cooling of the reaction mixture before it enters the subsequent reactor or the subsequent one Make fixed catalyst bed and carry out the reaction in the preceding reactor or on the previous fixed bed only up to a partial conversion of the TCD dialdehyde.

After relaxation of the reaction discharge from the amination reactor and, if desired, recycling of unreacted hydrogen and ammonia into the reductive amination and, if appropriate, removal of the solvent contained in the reaction mixture by distillation and water formed by the reductive amination, the TCD diamine can, if desired, be purified, preferably under reduced pressure become. Since the starting material TCD-dialdehyde and optionally TCD-diol is used in the form of an isomer mixture in the reductive amination, the TCD-diamine is also obtained as a mixture of isomers.

Instead of ammonia, primary and secondary amines, for example C to C ₁₀ monoalkylamines, N, N-Cr to C ₁₀ dialkylamines or arylamines, preferably d to C monoalkylamines or N, NC to C ₄ dialkylamines, can also be used as starting material the reductive amination are used, in which case the corresponding substituted TCD diamines are formed on the nitrogen atom.

The invention is illustrated by the following examples and comparative examples.

analytics:

All product mixtures were analyzed by gas chromatography and the proportions of the individual components were given in% by area. Differences in the sensitivity of the detection of the individual components by the GC detector were not corrected by calibration.

Comparative Example 1

Hydroformylation of dicyclopentadiene at 130 ° C and 600bar

5 mg Rh (CO) ₂ (acac) = 47 ppm by weight were dissolved in 100 g dicyclopentadiene, which

Batch filled in an autoclave and pressed 200 bar CO / H ₂ (1: 1). The mixture was then heated to 130 ° C. and, after the temperature had been reached, the pressure was adjusted to 600 bar using CO / H ₂ (1: 1). The temperature and pressure were held for ten hours. After cooling, a sample was examined by gas chromatography: dicyclopentadiene 0.3 FI .-%

TCD monoaldehyde 65.2 FI .-%

TCD dialdehyde 5.9 FI .-%

Sum of high boilers 27.2 FI .-%

FI .-%: area percent = area of individual peaks in the gas chromatogram based on the total area of all peaks x 100 acac = acetylacetonate

Comparative example 1 shows that even with a rhodium concentration of 47 ppm by weight at a relatively high hydroformylation temperature of 130 ° C. and even under a very high CO / H ₂ pressure of 600 bar, even after a reaction time of 10 hours in the hydroformylation of dicyclopentadiene little TCD dialdehyde is formed and the hydroformylation reaction stops at the TCD monoaldehyde level.

Comparative Example 2

Hydroformylation of dicyclopentadiene at 110 ° C and 280 bar

500 g of dicyclopentadiene and 400 g of toluene were introduced into an autoclave and 20 bar CO / H ₂ (1: 1) were injected. The autoclave was then heated to 110 ° C. and the pressure was adjusted to 220 bar with CO / H ₂ (1: 1). The catalyst solution consisting of

25.8 mg Rh (CO) ₂ (acac) (= 12 ppm by weight Rh based on the entire reaction mixture) in 100 g toluene was added via a lock and the pressure was adjusted to 280 bar. A temperature of 110 ° C and a pressure of 280 bar were maintained for ten hours.

Samples were taken from the autoclave and examined by means of gas chromatography (data in area%, toluene removed):

Compound after 1 h after 2 h dicyclopentadiene 1, 7 0.3 TCD monoaldehyde 91, 5 71, 5 TCD dialdehyde 3.9 22.8 Sum of high boilers 1, 3 1, 6

Comparative example 2 proves that the hydroformylation of dicyclopentadiene at a relatively low reaction temperature of 110 ° C. at a CO / H ₂ pressure of 280 bar and a Rh concentration of 12 ppm by weight is very slow and only with a very small space. Time yield runs. After a reaction time of two hours, the TCD-dialdehyde / TCD-monoaldehyde ratio is only 1: 3.

Example 3

Hydroformylation of dicyclopentadiene at 110/130 ° C and 280 bar

500 g of dicyclopentadiene and 400 g of toluene were introduced into an autoclave and 20 bar CO / H ₂ (1: 1) were injected. The autoclave was then heated to 110 ° C. and the pressure was adjusted to 220 bar with CO / H ₂ (1: 1). The catalyst solution consisting of 25.8 mg Rh (CO) ₂ (acac) (= 12 ppm by weight based on the total reaction mixture) in 100 g toluene was added via a lock and the pressure was adjusted to 280 bar; this pressure was maintained over the entire reaction time. The temperature was kept at 110 ° C. for the first hour, then the temperature was raised to 130 ° C. and the reaction was continued for a further three hours.

Compound after 1 h after 2 h after 2.5 h dicyclopentadiene 0.3 0.1 0.1 TCD monoaldehyde 97.2 9.8 2.9 TCD dialdehyde 2.1 89.9 93.4 Sum of high boilers 9 , 6 2.3 0.2

Example 4

Continuous hydroformylation of dicyclopentadiene in a miniplant with subsequent hydrogenation of the TCD dialdehyde to the TCD diol.

The description of the construction and operation of the Miniplant refers to the schematic drawing attached to the application.

The dicyclopentadiene dissolved in pentanol (1) was pumped into the reactor 3. The synthesis gas (2; CO: H2 = 1: 1) is also metered into the olefin stream. The catalyst was already dissolved in the olefin as Rh (CO) ₂ (acac) (acac = acetylacetonate). The reaction mixture passed from the first reactor 3 into the second reactor 4 and from there into the separator 5. An off-gas stream was taken off at the top and the liquid phase in the sump was passed over the ion exchanger bed 7. After the ion exchanger bed 7, the reaction mixture passed into the low-pressure separator 8, where gas (9) and liquid phase (10) were again separated. The liquid phase 10 was conveyed into a hydrogenation reactor 13. Water (11) and hydrogen (12) were also metered into this reactor. The discharge of the hydrogenation reactor 13 was freed of the gas in a gas separator 14 and the raw alcohol 16 was removed.

The Miniplant was operated with the following parameters:

Olefin feed 1

400 g / h dicyclopentadiene pentanol = 50:50 w / w

10 ppm by weight of rhodium reactor 3

110 ° C, 280 bar Reactor 4 130 ° C, 280 bar flue gas 6 and 9 approx. 50 Nl / h The residence time in both reactors was approx. 3 hours, ion exchanger bed 7 80 ° C, 7 bar Amberlyst® A21 water metering 11 40 g / h

Hydrogenation reactor 13 170 to 180 ° C, 280 bar

In the hydrogenation reactor operated in giant mode, two hydrogenation catalysts were arranged in fixed beds. The first catalyst bed located at the inlet to the reactor consisted of 1 l of a cobalt precipitation catalyst of the following composition:

67% by weight cobalt, calculated as CoO 19% by weight copper, calculated as CuO

7% by weight of manganese, calculated as Mn ₃ O 4% by weight of molybdenum, calculated as MoO ₃ 3% by weight of phosphorus, calculated as H PO ₄ .

The second catalyst bed located towards the reactor outlet consisted of a nickel on silica-supported catalyst of the following composition:

8% by weight of nickel, calculated as Ni

13% by weight of molybdenum, calculated as MoO ₃ residue: SiO ₂ .

After the hydrogenation, the reaction mixture according to the gas chromatogram had the following composition in area%: pentanol 45% TCD mono alcohol 5% TCD diol 50%

940 g of this discharge were distilled in a laboratory apparatus and 460 g of TCD diol with an OH number of 550 mg KOH / g sample were obtained. The OH number, also called the hydroxyl number, is defined as the measure that indicates how many milligrams of potassium hydroxide are equivalent to the amount of acetic acid that is bound by 1 g of substance during the acetylation. The sample is used to determine the OH number with acetic acid. boiled reanhydride-pyridine and titrated the resulting acid with KOH solution

(DIN 53240 and DIN 16945). TCD-diol has a theoretical OH number of 572 mg

KOH / g sample. The TCD diol content in the sample is (550/572) x 100 «

96%.

Example 5

Reducing amination of TCD dialdehyde

TCD dialdehyde from the miniplant was reductively aminated on Raney-Ni in tetrahydrofuran. For this purpose, 20 g of TCD dialdehyde (with 90% purity) in 70 g of THF and 30 g of NH _{3 were} reacted with 5 g of Raney Ni over a period of 10 hours in an autoclave at 100 ° C./200 bar H ₂ .

After the end of the experiment, the catalyst was filtered off and the solvent was removed. The residue was examined by means of GC-MS coupling: the isomeric diamines were found, as well as unreacted dialdehyde. The amine number determined from the solvent-free discharge was 504 mg KOH / g (theory: 583 mg KOH / g). The amine number is the amount of potassium hydroxide in mg which is equivalent to the amine content of 1 g of substance. To determine it, the sample is titrated with hydrochloric acid in methanol and the hydrochloric acid consumption is converted into KOH equivalents in accordance with DIN 53176. TCD diamine has a theoretical amine number of 583 mg KOH / g sample. The TCD diamine content in the sample is (504/583) x 100 * 86%.

Claims

claims

1. A process for the preparation of tricyclodecanedialdehyde by the hydroformylation of dicyclopentadiene using a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated temperature and at elevated pressure, characterized in that the hydroformylation is carried out at one pressure from 200 to 350 bar in at least two reaction zones, a reaction temperature of 80 to 120 ° C. being set in a first reaction zone and a reaction temperature of 120 to 150 ° C. in a reaction zone following this reaction zone, with the proviso that the reaction temperature in the subsequent reaction zone is at least 5 ° C higher than in the previous reaction zone.

2. The method according to claim 1, characterized in that one carries out the hydroformylation at a concentration of the rhodium catalyst, calculated as Rh, of 2 to 20 ppm by weight in the hydroformylation medium.

3. Process according to claims 1 and 2, characterized in that one carries out the hydroformylation at a reaction temperature of 105 to 115 ° C in the first reaction zone and at a reaction temperature of 130 to 140 ° C in the subsequent reaction zone.

4. The method according to claims 1 to 3, characterized in that one carries out the hydroformylation in two reaction zones.

5. The method according to claims 1 to 4, characterized in that the reaction temperature in the subsequent reaction zone is at least 15 ° C higher than in the preceding reaction zone.

6. Process for the preparation of tricyclodecanedimethylol by the hydroformylation of dicyclopentadiene by means of a CO / H mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated temperature and under elevated pressure to form tricyclodecanedialdehyde, followed by separation of the rhodium clodecandialdehyde from the tricyclodecandialdehyde Hydrogenation of the tricyclodecanedialdehyde by means of a gas containing molecular hydrogen over a heterogeneous catalyst at elevated temperature and pressure, characterized in that the hydroformylation is carried out at a pressure of 200 to 350 bar in at least two reaction zones, a reaction temperature of in a first reaction zone 80 to 120 ° C and in a reaction zone following this reaction zone, a reaction temperature of 120 to 150 ° C is set, 1st draft. with the proviso that the reaction temperature in the subsequent reaction zone is at least 5 ° C. higher than in the preceding reaction zone.

Process for the preparation of diaminomethyl-tricyclodecane by the hydroformylation of dicyclopentadiene using a CO / H ₂ mixture in the presence of a non-ligand-modified rhodium catalyst homogeneously dissolved in the hydroformylation medium at elevated pressure and at elevated temperature, subsequent separation of the rhodium catalyst from the tricyclodecanedi- aldehyde Amination of the tricyclodecanedialdehyde over a heterogeneous catalyst in the presence of a molecular hydrogen-containing gas and ammonia at elevated temperature and pressure, characterized in that the hydroformylation is carried out at a pressure of 200 to 350 bar in at least two reaction zones, in a first reaction zone a reaction temperature of 80 to 120 ° C and in one of these

Reaction zone subsequent reaction zone a reaction temperature of 120 to 150 ° C is set, with the proviso that the reaction temperature in the subsequent reaction zone is at least 5 ° C higher than in the preceding reaction zone.