DE2653850A1 - TRANSITION METAL SUPPORT CATALYST, PROCESS FOR ITS MANUFACTURING AND USING IT - Google Patents

Description

There is an improved method of making an immobilized Transition metal catalyst described which contains about 60 percent by weight bound transition metal. the This catalyst is prepared by adding a hydroxylic support with an excess of a transition metal alkoxide heated in an inert hydrocarbon and in the presence of water.

The above immobilized supported transition metal catalyst is used to make esters. According to this, either by direct esterification or by ester interchange Produce esters and polyesters with particularly favorable characteristics that have virtually no residual metal catalyst contain more.

Numerous heavy metals, especially transition metals, have already been on the surface of various carrier materials by converting a metal compound with the on the Hydroxyl groups located on the carrier surface. on

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• V

In this way, supported catalysts for the most varied Produce applications, such as for polymerizations, esterifications, hydrogenations, oxidations or Hydroformylations.

Probably the most common method of binding a metal to a support is to implement the an Support surface located hydroxyl groups with a metal halide compound. From US Pat. No. 3,166,543, for example, the conversion of carbon black, for example sewer black, goes on the surface of which are hydroxyl groups, with a transition metal halide such as titanium tetrachloride, followed by Heating with a silane compound results in a suitable for the polymerization of olefins Catalyst results. Similarly, US Pat. No. 3,166,542 describes polymerization catalysts which can be produced in practically the same way, in which the carrier material, however, is a finely divided inorganic Solid is such as aluminum oxide, titanium dioxide, zirconium dioxide, thorium oxide, magnesium oxide, silicates or aluminates.

Other methods of bonding metals to supports are also known. Hydroformylation catalysts, the units the formula

Z-O-Si-Q

J
where Z is the support and Q is a phosphorus-containing group bonded to a transition metal, are described, for example, in US Pat. No. 3,832,404. These catalysts are prepared by (i) a transition metal compound. with a compound containing silicon and phosphorus, for example a compound of the formula (CH ^ O) ₃ Si (CH-) ₂ PR_, to form a compound containing a transition metal bonded to phosphorus, and this compound then with an inorganic solid containing hydroxyl groups Reaction brings about, or by

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• he ·

(ii) the inorganic solid with the silicon and phosphorus Reacts containing compound and then the product obtained with the transition metal compound for reaction brings. From US-PS 3,392,160 it is also apparent that transition metal amine compounds, such as Tetrakis diethylaminotitan, Tetrakisdxmethylaminozircon or dichlorodibutylaminotitan, with hydroxyl-containing finely divided lumpy carriers react, the resulting materials then being activated by reaction with an organometallic compound. In US Pat. No. 3,816,340, olefin disproportionation catalysts are described which, by reacting a practically inert Matrix with a hydroxylic surface with a transition metal complex such as tetrakis (TT ^ allyl) tungsten or Tetrakis (// - allyl) molybdenum.

It is also already known to combine various metal compounds which contain one or more alkoxy groups with hydroxy groups Implement carrier materials. For example, US Pat. No. 3,326,877 describes polymerization catalysts which by reacting a finely divided inorganic support with compounds of the formula T (Q), wherein T is a metal stands in groups IVa, Va or VIa of the Periodic Table of the Elements and Q is an alkoxy or aryloxy radical and the compounds obtained thereby are then further reacted with an organometallic compound. at In this process, the carrier and any diluent or carrier gases must be virtually anhydrous when using the transition metal ester matches with the wearer. The presence of water affects the desired chemical reaction, which results in an unsatisfactory catalyst component, or this also causes the subsequent reaction adversely affected with the organometallic compound. There is no more per hydroxyl group on the surface transition metal is present as an atom, and only very small amounts of transition metal are bound to the support. In Similarly, US Pat. No. 3,817,931 describes catalysts using which polyesters can be formed.

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~ * ~ 2353850

• 3.

These catalysts are produced by reacting a hydroxyl-containing carrier with metal compounds including of germanium, titanium, zirconium and hafnium alkoxides in addition to metal halides and the organometallic compound. Each metal atom is attached to the carrier by 1 to n-1 (where η corresponds to the valence of the metal) oxygen bridges (-O-) bound, the concentration of bound metal being very low.

Finally, US Pat. No. 3,622,522 discloses olefin polymerization catalysts described containing up to 15 weight percent gallium and / or tin together with up to 50 percent by weight of chromium. The manufacture of these catalysts is carried out by Deposition of a chromium compound, such as chromium trioxide, and at least a compound from the group of the gallium or tin alkoxides or aryl oxides on a carrier and then Heating this material to a temperature of at least 927 C. The deposition of the metal compounds on the support is preferably carried out from a non-aqueous solvent or diluent and the subsequent heating is carried out on best in a practically anhydrous (less than 0.1 percent by weight water) air stream or one containing oxygen Electricity carried out.

There are also a number of processes for the production of simple or polymeric esters. This includes a direct Synthesis by reacting an organic alcohol with an organic carboxylic acid or exchange reactions which an acyl radical present on an ester

(R-C-)

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or alkoxy radical (-OR) against another acyl radical or alkoxy rest is replaced (see Kirk-Othmer "Encyclopedia of Chemical Technology" Volume 8, pages 356 to 365, John Wiley & Sons, New York, 1965). Examples of such reactions are the acidolysis (reaction of the ester with a carboxylic acid under Exchange of acyl residues) and the alcoholysis (reaction of the ester with an alcohol with exchange of alkoxy residues).

For the corresponding transesterification, two ester products are heated, which leads to an exchange of the acyl groups and the alkoxy groups:

ο ο ο ο

R ^ COR "+ R * -C0R **> R-i-COR ** '+

These ester exchange reactions are particularly suitable if one of the products obtained is relatively low boils and can be removed by distillation, since this shifts the equilibrium and the reaction can drain completely. In the production of polyesters, for example Form high molecular weight polymers. Triglycerides can also be obtained by appropriately redistributing the acyl radicals or modify similar compounds containing a number of ester groups, thereby making a number more useful Products.

In the above procedures are in general appropriately used catalysts. For esterification reactions mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid are usually used, and other acids can also be used for this purpose, such as p-toluenesulfonic acid or benzenesulfonic acid. As catalysts for alcoholysis in the production of esters

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furthermore, basic materials have already been used, such as in particular Alkali alkoxides or alkali or alkaline earth carbonates. The use of these acidic or basic catalysts is however, associated with two major problems, namely the fact that they cause side reactions to form undesirable Favor by-products and have to be neutralized after the reaction has ended.

Because of these disadvantages, titanium compounds containing alkoxy or acyl groups are increasingly used as catalysts in such processes, since these compounds do not have to be neutralized and only result in a minimum of troublesome side reactions. However, it is also known that these titanium catalysts hydrolyze in the presence of water, which leads to a corresponding loss of activity. This places limits on the use of such catalysts, and large amounts of catalyst are therefore often required for an esterification reaction to take place completely. Increase As a result, the costs, and also the production of catalyst-free esters wesentlieh difficult, what is more important is. Catalyst residues in the ester product are undesirable insofar as this makes the ester cloudy and discolored and at the same time increases the instability of the ester to oxidation, heat and hydrolysis.

In US Pat. No. 2,689,858 and German Pat. No. 1,142,868, condensed polytitanates derived from organic polyhydroxy compounds are disclosed various degrees of hydrolysis as well as polymer orthotitenates described. These catalysts give a clear one Improvement of the hydrolytic stability towards alkyl orthotitanates or titanium acylates, but here again the amount of catalyst remaining in the ester product is always still too high, especially for critical applications in which you get very clear ester products with good stability needs.

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. η.

An improved process and catalysts have now been found which overcome the disadvantages mentioned above permit. Quite surprisingly, it was found that in the present process, the presence of water for Carrying out the reaction is essential and therefore not, as would have been expected according to the prior art, disadvantageous proves. The supported catalysts obtained by this process are highly active and good in the presence of water stable, and they are free-flowing powders. In them, the transition metal compound is stronger than just monomeric bound so that more than just one transition metal atom is bound per hydroxyl group available on the surface and the present catalysts contain up to 60% or more of bound transition metal. The invention Transition metal catalysts are particularly suitable in esterification processes.

The present process for producing a supported transition metal catalyst consists in heating a support containing hydroxyl groups with a molar excess (based on the hydroxyl groups present) of the transition metal alkoxide with thorough mixing at temperatures of 100 to 300 ^° C. in an aliphatic hydrocarbon and in the presence of water . In addition to a reaction with the hydroxyl groups on the surface, there is also self-condensation of the transition metal alkoxide, as a result of which the carrier is coated with a cross-linked matrix of transition metal atoms with oxygen bridges (-0-) attached to it. Transition metal alkoxides suitable for this purpose have the formula

wherein

M stands for a transition metal from groups IVb, Vb or VIb of the Periodic Table of the Elements,

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OR is an alkoxy radical with 1 to 18 carbon atoms,

η is an integer from 2 up to the valence of the Metal M represents

Q is an inert radical which does not react with the hydroxyl groups of the carrier, an alkoxide radical -OR or a Alcohol means ROH and

m is such an integer that the sum of η + m corresponds to the valence of the metal M.

All common carrier materials can be used as a carrier, on the surface of which there are a number of hydroxyl groups.

The process according to the invention is generally carried out at temperatures from 120 to 250 ^° C. in a saturated aliphatic hydrocarbon, for example in mineral oils. Transition metal alkoxides in which the radical -OR stands for a saturated branched or straight-chain alkoxy radical with 2 to 8 carbon atoms and the metal denotes titanium, zirconium, hafnium or vanadium, in which titanium tetraalkoxides are particularly preferred, are particularly suitable for this process. When the reaction is carried out, water can be present, either in the form of water added at the beginning or absorbed on the carrier, or it can also be water added later or formed in situ by dehydration of the alcohols formed as by-products. To achieve a bond above a monomeric bond, namely a bond in which more than one titanium atom is bonded per hydroxyl group available on the surface, an excess of transition metal alkoxide is required. The ratio of transition metal alkoxide molecules per converted hydroxyl group should therefore be above 1: 1, and it can range up to 10: 1.

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The present catalysts are free-flowing powders with a transition metal content bound to the carrier of about 3 percent by weight up to about 60 percent by weight or higher. The immobilized catalysts are the result a highly cross-linked matrix of transition metal atoms with linking oxygen bridges (-0-) on the carrier is bound and covers it. This rigid polymeric metal oxide assembly with multiple attachments of the polymer on the support still contains a sufficient amount of alkoxide groups for catalytic activity.

According to the invention, a method for producing Esters created in which the problems encountered in the usual ester production are avoided. The present Process is suitable for a batch, semi-continuous or continuous operation, and then the products obtained are esters including simple esters or polyesters either by direct esterification or by any known ester interchange reaction. Because of the hydrolytic The present process can be applied to the production of esters with the stability of the catalyst used which is produced as a by-product, water. In the process according to the invention, no side reactions occur and it leads with the use of small amounts of catalyst at sufficient reaction rates. Because of the small amount required Amount of catalyst and the fact that this catalyst is immobilized on a support and is sufficient has hydrolytic stability, one arrives at extremely valuable esters, which are only very small and in a row in some cases even contain negligible amounts of catalyst residue. As a result one arrives at ester products, which are in fact colorless (water white) and stable in storage.

Another feature of this process that is extremely important in batch production is the fact that the heterogeneous catalysts can be easily separated off from the ester products obtained by filtration and again

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let use. Finally, it is also important for technical processes that the present process is also using an impure charge of acid, anhydride, alcohol or ester which is normally ketonic, Contains aldehydic and olefinic functional groups without the need for costly and time-consuming cleaning beforehand were. Such impurities normally interfere with ester production and / or lead to highly discolored products, which can only be used for purposes where you only need materials of the lowest quality. In the process of the invention, these contaminated feeds can be removed can be used directly, resulting in products with improved color and stability.

To carry out the process according to the invention, the respective reactants are heated in the liquid state in the presence a heterogeneous transition metal catalyst at elevated temperature. This can be done at temperatures of about 100 to 300.degree can be worked, and the process can be carried out at atmospheric or reduced pressure. The formation of esters or polyesters through direct esterification or ester interchange can be carried out batchwise, continuously or semicontinuously by this process. It can be aliphatic, aromatic or use alicyclic mono- and polyfunctional acids or alcohols. The method is also suitable for an ester interchange of synthetic or naturally occurring ester products (such as triglycerides). The process is carried out in the presence of the present immobilized supported transition metal catalyst (metals of group IVb, Vb and VIb of the Periodic Table of the Elements), where a catalyst is preferably used which contains titanium, zirconium, hafnium or vanadium as transition metals.

The supported catalyst can be used in this ester process in amounts of only 0.0005 percent by weight, based on the Reactants, are used, and it can go up to very large amounts, for example amounts of catalyst where the reactants are passed through a heated column packed with the catalyst.

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The present improved process is concerned with the preparation of supported transition metal catalysts by Implementation of a carrier material containing hydroxyl groups a transition metal alkoxide. Transition metal compounds suitable for this process have the general formula

wherein M is a transition metal from groups IVb, Vb and VIb of the periodic table, the radical -OR means an alkoxy radical with 1 to 18 carbon atoms, such as ethoxy, n-propoxy, Isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-octoxy, 2-ethylhex1oxy, n-decyloxy, allyloxy, tridecyloxy, stearyloxy, Isotridecyloxy, cyclopentyloxy or cyclohexyloxy, η a represents an integer from 2 up to the valence of the metal M, Q is an inert group associated with the hydroxyl groups of the carrier does not react, an alkoxide radical of the formula -OR or an alcohol of the formula ROH formed therefrom and m is an integer such that the sum of η + m corresponds to the valence of the transition metal M. The designation of the metal groups given above comes from the Handbook of Chemistry and Physics, 56th edition, 1975-76, CRC Press, Cleveland, Ohio, referenced Table of the Periodic Table of the Elements. Particularly suitable transition metal compounds are those in which the radical -OR is a saturated branched or straight-chain alkoxy radical with 2 to 8 carbon atoms and the transition metal is titanium, zirconium, hafnium or vanadium. Examples of suitable ones Transition metal compounds are tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetraisobutoxytitanium, Dimethoxydibutoxytitan, Methoxybutoxydiisopropoxytitan, Methoxyisopropoxydibutoxytitan, Tetrabutoxyvanadine, tetrabutoxyzirconium, tetraisopropoxyzirconium, pentamethoxyvanadine, pentaisopropoxyvanadine, Triisopropyl vanadate, tributyl vanadate, tetraisopropoxyhafnium, Chromium (II) isopropoxide, chromium (III) dodecyloxide, chromium (IV) isopropoxide or chromium (VI) ethoxide. In the inventive method

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-A

Metalloketone groups (such as —V = O) can also be driven Use containing transition metal compounds, and it can also be used other compounds that are inert Contain groups that do not interfere with the reaction. In the case of transition metal compounds which are particularly suitable for the process according to the invention all available valencies are saturated by saturated alkoxide radicals, and are particularly preferred Compounds of this type are the titanium tetraalkoxides.

The process of the invention consists in reacting the transition metal compounds described above with any one of them conventional and commonly used carrier material, on the surface of which there are hydroxyl groups, and thus a material with a number of hydroxyl groups attached to its surface matrix. Those located on the surface Hydroxyl groups provide points of attachment for the transition metal on the support, and these points of attachment can be expressed by the following general formula

where Z stands for the support matrix, M stands for a tetravalent transition metal and χ _{indicates the number of%} linking sites present on the support, which corresponds to the number of available hydroxyl groups. The carriers can be either synthetically produced or naturally occurring materials and these carriers can be anhydrous or contain moisture. The particle size of the carrier can also be varied within a wide range, and the carrier material suitable for the process according to the invention can therefore be in the form of spheres, cavities, rings, rods, fibers or platelets. However, the present process can be applied in particular to finely divided supports, the potential reactivity of the support with the transition metal compound being greater, the larger the support surface and the larger the number of hydroxyl groups present on the surface.

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How large and varied the type of carrier which can be used in the process according to the invention is shown by the fact that even carbon black that contains hydroxyl groups on its surface, such as sewer black or flame black, is successful lets use. In a similar way, inorganic oxides of silicon, magnesium, aluminum, Zinc or mixtures thereof. It can also organic polymers that have a hydroxyl functionality or have a functionality that can be converted into hydroxyl groups. Matrix materials of Silicon dioxide and aluminum oxide or mixtures thereof, which also contain small amounts of alkali and alkaline earth oxides, May contain iron oxide or zinc oxide as these materials are available from natural sources. Bearer of this kind can be used as such or after a further activation, for example by an acid treatment.

Individual examples of suitable inorganic solid supports are aluminum oxide, silicon dioxide, pyrogenic silicon dioxide, Silica gel, naturally occurring clays such as kaolinite, smectite, especially montmorillonite, vermiculite, palygorskite, Chlorite, mica, zeolite, zirconium dioxide, titanium dioxide, thorium dioxide, Magnesium oxide, aluminates such as bauxite or corundum, or silicates such as chrysotile or actinolite.

Since, according to the process according to the invention, there is a highly crosslinked transition metal-containing polymeric coating layer on the surface of the carrier can be formed by condensation of the transition metal alkoxide, the carrier does not necessarily have to have a high concentration Contain hydroxyl groups to make an effective catalyst with a high percentage by weight of bound transition metal results. This situation is in contrast to the teaching given by the prior art, according to which the Transition metal content is proportional to the amount of converted hydroxyl groups on the surface. The

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The method according to the invention can theoretically even be applied to a catalyst support in which the polymeric transition metal the carrier is completely covered and! mobilized, although it only has a single hydroxyl group on the Carrier matrix is bound. However, having a larger number of surface hydroxyl groups makes it easier of course, the reaction and enables a more complete, more uniform and effective coating of the Carrier. For this reason, the carrier should therefore preferably have a number of hydroxyl groups. For the There is of course no upper limit to the amount of hydroxyl groups present on the carrier matrix.

The method according to the invention enables production of supported catalysts with higher activity and a significantly higher content of bound to the support, and thus immobilized transition metal, so that the transition metal during the use of the catalyst for any reaction does not fall off the catalyst. If the present catalysts are used in the esterification reaction, then result In addition to increased catalytic activity, there are also improvements in terms of color and stability obtained esters, with esters with only a very low content of residual transition metal being produced at the same time permit. The improvement according to the invention consists in heating the carrier containing hydroxyl groups with excess Transition metal alkoxide in an inert carbon medium in the presence of water at an elevated temperature with appropriate mixing, which leads to condensation of the transition metal alkoxide and a reaction comes with the hydroxyl groups on the surface.

The reaction between the carrier and the transition metal alkoxide should proceed as follows:

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CI) Z - (- OH) _χ + XMCOR) _n (^ _n > Z-fO M (OR) _n .! ^ + X ROH

Here, Z, M, R, Q, Χ / η and m have those given above Meanings. The above equation also describes the state of the art, according to which these reactions take place under anhydrous or practically anhydrous conditions can be carried out. In the present process, in which in a suitable Reaction medium and in the presence of water and with an excess of transition metal alkoxide (based on the On the other hand, a polycondensation of the transition metal alkoxide occurs forming a cross-linked transition metal oxide polymer, which is bound to the support surface. From the above equation it is also clear that under an excess of transition metal alkoxide is to be understood as meaning an amount in moles which is greater than χ or more than one molecule converted transition metal alkoxide per hydroxyl group available on the surface. ^ Theoretically Although all the hydroxyl groups present on the surface can react in the above manner, this is not practical necessary. Since the transition metal alkoxide polymerizes (self-condenses) , all of the transition metal present can be absorbed into the carrier while achieving a high concentration incorporated transition metal bound thereon, and as a result, extremely effective and valuable catalysts are obtained.

If a titanium alkoxide of the formula Ti (OR) _{4 is} used as the transition metal alkoxide and the reaction at a single hydroxyl group is considered, the process proceeds according to the following equation:

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OR - I (IT) Z-OH + TiCOR) ₄ -> 2-0-Ti-OR + ROH

OR '(a)

If, on the other hand, there is still more transition metal compound and if the equilibrium of the reaction is shifted by the presence of water, then it can be at any or all Groups -OR of the remainder (a) above come to a condensation. If one looks at this reaction in only one group -OR, then it works like this:

OR
I.
(III) Z-Ti-OR + y Ti (OR) _4. + Y

OR / OR QR \

/ UK UK \

4-Ti-O — Ti — j—

ZV-Ti-O-Ti-f- OR + 2y ROH OR OR 'γ

Of course, all other -OR radicals can also enter into the same reaction, and condensation can occur Different hydroxyl groups come with adjacent radicals -OR, which means they are attached to the support surface results in a highly complex cross-linked titanate polymer. Before the reaction shown in equation (II) above with hydroxyl groups on the surface can do it

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a certain amount of condensation (polymerization) can also occur. The extent of the condensation is primarily dependent on the amount of transition metal alkoxide, the amount of water available to shift the reaction equilibrium and the respective reaction conditions, while the extent of the crosslinking that occurs also includes a puncture of the is the transition metal alkoxide used in each case, namely the number of alkoxide substituents available for the reaction. The above equations are only intended to show the overall reaction, with the possible gradual process a particular response is not specified.

The process for the preparation of the supported catalysts according to the invention is carried out at elevated temperatures of about 100 to 300.degree. The temperature to be used in each case is determined by the transition metal alkoxide used in each case, the amount of water present in the reaction mixture at the end of the reaction and the rate and extent of the desired reaction. Although the process according to the invention can be carried out at a temperature of 100 ° C., the reaction rate at this temperature can then be so low that the process becomes uneconomical. In such a case, it is therefore advisable to increase the reaction temperature, since practically the same reaction products are obtained. The inventive reaction is best carried out in general at temperatures of 120 bid 250 ⁰ C. It can be at atmospheric pressure or in one

closed reaction vessel at pressures up to about

2 2

70.3 kg / cm, preferably up to about 35.2 kg / cm will. To some extent, the particular temperature used also determines the question of whether the implementation in an open or a closed reaction vessel. If the process is carried out at atmospheric pressure, then can you work under an inert gas atmosphere, such as under nitrogen or argon. Absolutely necessary

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however, this measure does not. The removal of alcohol and other by-products created during the reaction can be facilitated by using a carrier gas. You get particularly good results when you look at the present Reaction at atmospheric pressure in the presence of. Air carries out and at the same time also the as a by-product released gases into the open and the alcohol formed condenses and in a suitable trap catches.

It is not absolutely necessary to use a suitable hydrocarbon as the reaction medium to produce an immobilized transition metal catalyst. It is not entirely clear what role the use of such a hydrocarbon plays. In addition to the normal function of such a reaction medium of uniform distribution of heat, and thus better control of the reaction rate, such a hydrocarbon should also contribute to a solution of the transition metal alkoxide and a coating of the support surface while preventing agglomeration of the finely divided catalyst particles. The use of a hydrocarbon also makes it easier to obtain the finished immobilized catalyst. Aliphatic hydrocarbons suitable for this purpose are normal paraffins (C _n H _{2n + 2} ), isoparaffins (C _n H _{2n + 2} ), olefins (C _n H _2n ), diolefins (CH ₂ ) and cycloparaffins (CH) and mixtures thereof. Aromatic hydrocarbons can also be present in the mixture. In general, it is expedient to use predominantly saturated hydrocarbons, since the presence of large amounts of olefinic unsaturation leads to undesired discoloration of the product, which is particularly the case when working in the presence of air. If, on the other hand, a predominantly aliphatically saturated hydrocarbon is used, then these problems do not arise.

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The aliphatic hydrocarbons used as the reaction medium can be normal paraffins, isoparaffins, cycloparaffins or mixtures thereof with small amounts of olefins. These hydrocarbons can contain from about 8 to 40 carbon atoms and are usually obtained by fractional distillation of paraffinic petroleum fractions. They generally consist of mixtures of oily liquid hydrocarbons with a carbon range from C ₁₄ to C ₃₃ . According to the invention, in particular, an aliphatic hydrocarbon is used which is liquid at a temperature of about 30 ° C. or below and has a boiling point of about 140 ° C. Examples of suitable aliphatic hydrocarbons are liquid petrolatum, liquid paraffin and a wide variety of commercially available mineral oils and mineral sealing oils. The ratio of hydrocarbon oil to carrier is, on a weight basis, usually about 0.5: 1 to 50: 1, and preferably about 2: 1 to 25: 1.

The presence of water, as already indicated, is essential for the formation of the highly active immobilized according to the invention Catalyst essential. The hydroxyl groups on the surface can indeed with the titanium alkoxide without water react, but the desired subsequent reaction (condensation) does not occur under anhydrous conditions be maintained. After 1 mol of water is required for each oxygen bridge to be formed (see Equation III), at least 1 mole of water per mole of transition metal alkoxide must be condensed for a polycondensation. The presence of larger amounts of water (and even amounts up to a ten-fold molar excess) makes the reaction or, however, does not adversely affect the activity of the subsequently obtained catalyst. That for the invention Process required water can be added at the beginning of the reaction, in the course of the reaction continuously or be introduced intermittently or arise in situ. To create the for the expiry of the

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The amount of water required for the condensation reaction can also be used with combinations of these measures. Using of a titanium alkoxide, the overall reaction can be explained in terms of a formula as follows:

(IV) -Ti-OR + RO-Ti- + H ₉ O -> - Ti-O-Ti- + 2R0H II ² II

If you add water at the beginning of the reaction, this can take shape a direct addition to the reaction mixture or in the form of the water present on the carrier. The latter working method is particularly useful for introducing water into the system, and it is particularly useful for promoting condensation if all or part of the water required is present on the support surface at the start of the reaction has available. If the reaction is to be carried out continuously or semi-continuously, then it is advisable to either meter the required water continuously into the reaction system or add it in several partial amounts.

Another interesting embodiment of the method according to the invention is that part of the required Water in situ, namely during the reaction, by dehydration of the alcohols formed by the condensation is formed in the reactor. From the above equation (IV) it becomes clear that the formation of an oxygen bridge each time carries two molecules of alcohol, creating a more than adequate continued source of water for the drainage of the water Condensation results when the alcohol becomes dehydrated. If, for example, titanium isopropoxide is used as the transition metal alkoxide, then the following results for the overall reaction the condensation of the two isopropoxide residues and the dehydration The formula of the alcohol obtained is as follows:

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CH _x -te / * cH _x 26b385Q-

i ³ i I ι ³

2-Ti-OCH + H ₂ O - ^ - Ti-O-Ti- + 2 HO-CH

CH ₃

CH ₃ CH,

1-5 Il *

QTI) HO-CH ^Tr * ffir * r, _), HC +

^Δ CH ₇

Oi ₃ . '-

To make dehydration easier (Equation VI) one can do that Add a small amount of an acid, such as sulfuric acid, to the reaction mixture; such acid catalysts are absolutely necessary However not. It is generally advantageous if at the beginning of the reaction to start the condensation there is already one small amount of water is present, for example absorption water on the support, with increasing reaction temperature and amount of alcohol in the reactor to terminate the condensation, further water is formed in situ by dehydration of the alcohol will. However, this is not absolutely necessary. Furthermore, one does not necessarily have to remove the dehydration product. However, if the process is carried out under atmospheric conditions, these products can generally be removed easily, by venting the reaction vessel if the product is a gas (e.g. propene), or by removing the material condensed and collected in a suitable trap if the product is a low-boiling liquid.

The amount by weight of the transition metal bound to the support matrix depends on the amount and type of transition used metal alkoxide and the extent of condensation. In general makes the transition metal about 3 percent by weight up to about 60 percent by weight or more of the immobilized Catalyst off. Preferably about 5 to 50 percent by weight transition metal is bound to the support. To improve education Immobilized catalysts should have the ratio of transition metal alkoxide molecules per available hydroxyl group be greater than 1: 1 and range up to about 10: 1, and preferably

4th
wisely between 1.5: 1 and 10: 1. In the case of carriers with

-4-3 moderately high hydroxyl content, for example 10-10 This ratio is equivalent to hydroxyl groups per g of support

2 generally between about 2: 1 and 10: 1.

709823/0993 ORIGINAL INSPECTED -

The catalysts of the invention are typical free-flowing powders that are easy to handle and because of their hydrolytic properties Let the stability be stored for a long time without loss of catalytic activity. You can simply through standard filtration methods recovered and reused.

The immobilized catalysts of the present invention have a complex structure of a highly cross-linked transition metal-containing polymer network, which as a result of the condensation of the transition metal alkoxide with the hydroxyl groups on the surface and a polycondensation of the transition metal alkoxide is bound to the support surface. The polymeric surface coating provides a cross-linked matrix of transition metal atoms which are bonded to each other as well as via oxygen bridges (-O-) on the carrier. By however, the specific guidance of the present process still contains the rigid matrix for a high catalytic one Effectiveness Sufficient amount of unreacted alkoxide groups. These alkoxide groups are likely to be on the surface of the polymer Transition metal oxide may also be present within the matrix. The inventive method enables a complete Coating of carrier materials with even a low hydroxyl content as well as carrier materials with very irregular surfaces, so that then only polymeric transition metal oxide and alkoxide groups on the surface of the immobilized catalyst are present to quite a depth.

The catalysts of the invention can generally be used wherever catalysts have already been used Transition metals from groups IVb, Vb or VIb of the periodic table used. Examples of such uses are metatheses and polymerizations of olefins, Cyclooligomerizations of alkynes and alkenes, Ziegler-Natta polymerizations or hydrogenations = they are particularly suitable for esterifications and ester interchange reactions with inclusion of transesterifications. The present immobilized catalysts

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offer a number of advantages, predominantly in their hydrolytic properties Stability, the possibility of their complete removal after the end of the reaction by simple filtration and reside in the fact that virtually all of the transition metal is bound to the support and not in the reaction mixture is resolved.

The present immobilized catalysts can in particular use for the production of esters, which can be used as plasticizers, lubricants, including base materials and additives, polymer additives or intermediates are suitable. Since the present catalysts are the catalytically effective Transition metal is bound to the support surface and is therefore not dissolved in the reaction mixture, thereby all The resulting metal-containing color bodies are trapped on the catalyst surface, so that they are at the end of the reaction remove by filtration.

Since practically the entire catalyst can be separated from the esters prepared using these supported catalysts, the practically metal-free esters and polyesters prepared in this way have more favorable hydrolytic, oxidative and thermal stability. This is particularly important in the case of esters with regard to their metal content must satisfy certain conditions, and for this purpose is for example made to the turbine nests lubricating oils with viscosities of 3 centistokes (99 ⁰ C) and 1 centistoke (260 ⁰ C) that meet the strict requirements of MIL-L-7808 G and MIL-L-27502 must comply.

As already stated, the invention also relates to batch, continuous or semi-continuous production of esters including simple esters and polyesters. The method according to the invention can be used in. Reactions apply, in which it is with direct reactions of a carboxylic acid or a carboxylic acid anhydride with a mono- or to do polyfunctional alcohol with formation of an ester

703823/09 9-3

Has. Furthermore, this method can also be used just as well for the known ester exchange reactions in which it to a mutual exchange of an acyl and / or alkoxy radical of an existing ester by another acyl and / or alkoxy radical. As already stated, the present process is suitable for the preparation of simple esters, wherein at least one of the reactants (acid, anhydride or alcohol) is monofunctional. However, this simple ester can also contain more than one ester residue within the molecule, as is the case, for example, for the conversion of glycerol with of a fatty acid applies. The present process can also be used for the production of polyesters, namely of polymeric materials with repeating ester groups.

The process of the invention can be applied to any mono- or polycarboxylic acids or anhydrides, including aliphatic, aromatic or alicyclic acids or mixtures thereof, which also include others May contain substituents. The acids can be saturated or olefinically unsaturated. Individual examples of suitable acids are acetic acid, vinyl acetic acid, phenylacetic acid, triphenylacetic acid, propionic acid, acrylic acid, methacrylic acid, ß-phenylacrylic acid, η-butyric acid, isobutyric acid, valeric acid, isovaleric acid, 5-phenyl-n-valeric acid, hexanoic acid, 2-ethylhexanoic acid, Heptanoic acid, caproic acid, octanoic acid, pelargonic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Erucic acid, linoleic acid, linolenic acid, eleostearic acid, lignostearic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid, Pentadecane-1,15-dicarboxylic acid, pentacosane-1,25-dicarboxylic acid, 1,2,3-propane tricarboxylic acid, crotonic acid, maleic acid, Fumaric acid, mesaconic acid, citraconic acid, itaconic acid, muconic acid or aconitic acid.

709823/0993

Examples of suitable alicyclic acids are cyclopropanecarboxylic acid, Cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, Cycloheptanecarboxylic acid, cyclohexanecarboxylic acid, cyclopropanedicarboxylic acid, Cyclohexanedicarboxylic acid, cyclohexane-1, 2,3,4,5,6-hexacarboxylic acid, Cyclopenten-2-carboxylic acid, 1-cyclohexene-1-carboxylic acid, Cyclohexadiene-1,2-dicarboxylic acid, 1,3-cyclohexane-1,4-dicarboxylic acid or the dicarboxylic acid formed by the Diels-Alder addition of acrylic acid to linoleic acid.

Examples of aromatic compounds suitable for the process according to the invention Acids are the toluic acids, alpha-naphthoic acid, ß-naphthoic acid, o-, m- and p-Ethy! benzoic acid, p-phenylbenzoic acid, Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyromellitic acid.

Various substituted acids can also be used, and examples of these are hydroxyacetic acid, chloroacetic acid, bromoacetic acid, cyanoacetic acid, lactic acid, alpha- or ß-hydroxypropionic acid, citric acid, ricinoleic acid, alpha- or ß-chloroacrylic acid, ß-bromoacrylic acid, 2-hydroxycyclohexanecarboxylic acid, o-, m- or p-chloro- or -bromobenzoic acid, o-, m- or p-hydroxybenzoic acid, o-, m- or p-nitrobenzoic acid, o-, m- or p-methoxybenzoic acid or hydroxyphthalic acid. Finally, a wide variety of mixed acids of natural origin can also be used, such as tall oil fatty acids, lanolin fatty acids, coconut fatty acids or mountain wax acids. High molecular weight acids, including dimeric, trimeric and higher polymeric acids, such as are obtained by polymerization of olefinically unsaturated fatty acids, are also suitable, and examples of these are oleic acid, linoleic acid or mixtures thereof, and other high molecular weight acid products can also be used, such as alpha -alkyl- or alpha, -alpha-dialkyl-branched acids, which are obtained by free radical addition of short-chain monobasic acids, such as propionic acids, to higher molecular weight alpha-olefins, or one can also

709823/09 93

Use higher molecular weight mixed acid products, which can be added by ozonization or oxidation of higher molecular weight olefins got. Examples of anhydrides of monobasic and dibasic acids used in the process according to the invention are acetic anhydride, Adipic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride or benzoic anhydride.

Alcohols which can be reacted with the above-mentioned carboxylic acids and carboxylic acid anhydrides are monoalcohols or di-, tri- or higher polyfunctional alcohols. They include aliphatic, alicyclic or aromatic alcohols, which can contain further substituents, as well as ether alcohols, namely intermolecular ethers formed by the condensation of two or more molecules of a polyol with elimination of water. Individual examples of suitable monohydric alcohols are ethanol, chloroethanol, cyanoethanol, n-proponal, sec-propanol, n-butanol, tert-butanol, isoamyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, n-decanol, isodecanol, Caprylic alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol, oxo alcohols such as tridecyl alcohol, which is predominantly tetramethyl-1-nonanol and hexadecyl alcohol, which are a complex mixture of 2,2-dialkylethanols called primary alcohols Alkyl radicals are predominantly methyl-branched C _ß and Cg radicals, cyclohexanol, benzyl alcohol, o-, m- or p-methoxybenzyl alcohol, o-, m- or p-methylbenzyl alcohol, phenylethyl alcohol or triphenylethyl alcohol. Examples of polyols suitable according to the invention are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 3-methyl-1, 5-pentanediol, 2,3-dirnethy1-2,3-butanediol, trimethylolpropane, mannitol, sorbitol, glycerin, pentaerythritol, 1,4-cyclohexanedimethanol, xylenol or bisphenols, such as bisphenol A. Ether alcohols that can be used in the process according to the invention, are, for example, diethylene glycol, triethylene glycol, tetraethylene glycol , polyoxyethylene or polyoxypropylene glycols with molecular weights

709823/09 & 3

of up to about 4000, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Triethylene glycol monomethyl seams, butoxyethanol, butylene glycol monobutyl ether, dipentaerythritol, tripentaerythritol, Tetrapentaerythritol, diglycerin, triglycerin, tetraglycerin, Pentaglycerin, hexaglycerin, heptaglycerin or octaglycerin.

In addition to the acids, acid anhydrides and alcohols specified above, the resulting process can also be used Use esters. These esters can be subjected to appropriate exchange reactions, such as, for example Acidolysis, alcoholysis or transesterification. Both synthetic esters and esters of natural origin are suitable for this purpose. The ester content of such naturally occurring products is usually quite high, but it can also be Products with less than 50% ester compounds are used. Advantageously in the method according to the invention naturally occurring fats or oils of animal or vegetable origin are used, and these compounds leave modify themselves many times to produce other valuable ester products. The above fats and oils contain predominantly Triglycerides, but other esters can also be present.

To carry out the process according to the invention, a wide variety of reaction conditions can be used, each of which is dependent on the particular reaction temperature, the reactants used and the desired result. In general, temperatures of about 100 to 300 ^° C., preferably about 125 to 250 ^° C., are used. If corresponding reactions are carried out at temperatures significantly below ^100.degree. C., the reaction rate is inadequate, and working at temperatures significantly above 300.degree. C. is generally not associated with any advantage. The temperature and other reaction conditions used in each case are of course also dependent on the particular one

709823/09

How the procedure is carried out, and thus the question of whether batch, continuous or semi-continuous is carried out. In a continuous process, for example at Carrying out the reaction in a column packed with the catalyst in a suitable form, with very short contact times has to do, the temperatures to be used are of course generally higher than, for example, a batch Work. Furthermore, if the product runs through a series of reaction vessels in a particular process, then so can it be useful here if the reactors at the end of the reaction chain are operated at a higher vacuum and / or higher temperatures is working. A wide variety of process variations are possible according to the invention.

The reaction can be carried out at atmospheric pressure, reduced pressure or superatmospheric pressure. In general the same criteria apply to the pressure as have been mentioned above for the various reaction temperatures. To facilitate the complete process of the reaction by removing water or other volatile products, such as for example from Glcolen, the process steps lying at the end of the reaction chain are generally reduced Pressure carried out. This is particularly recommended where you have esters with low acid numbers and high molecular weight Want to manufacture polyester.

The process according to the invention does not necessarily have to be carried out in an inert solvent or diluent, provided the reactants remain liquid. The use of a solvent or diluent can, however to facilitate the handling of the reactants or the contact of the reactants with the catalyst recommend in order to make the reaction rates more uniform. The one used for this purpose Solvent or diluent is not critical as long as it does not react with the reactants and the catalyst

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or otherwise interferes with the reaction. Aliphatic or aromatic solvents are particularly suitable for this purpose Hydrocarbons. Above all, those hydrocarbons are used that form an azeotrope with water, that boils lower than the constituents present in the reaction mixture, so that all of the water formed is incorporated Shifting the equilibrium towards the desired product can be removed azeotropically from the reaction mixture.

Depending on the variables given above, a wide range of reaction times can be used, but even when the process according to the invention is carried out batchwise, the reaction rates are so high that that the desired conversion is usually practically complete within a few hours.

Due to the particularly favorable activity of the present immobilized catalyst, sufficient reaction rates are obtained even with very small amounts thereof. However, once the transition metal has been bound to the support, working with large amounts of catalyst does not do any harm, since practically all of the catalyst present can be separated off from the ester product simply by filtration after the reaction has ended. It is possible to work with catalyst amounts of only about 0.0005 percent by weight up to very high amounts, since corresponding esters can also be prepared, for example, by continuously passing the required reactants through a column packed with the transition metal supported catalyst. Usually, however, amounts of catalyst from about 0.001 to about 10 percent by weight, based on the total reactants present, are used. Batchwise or semi-continuous process for producing esters or polyesters by direct esterification or by Esteraustausch are usually carried out using 0.01 to 1 weight percent catalyst.

709823 / 099-3

- 3Θ -

The advantages of the process of the invention, that of the present immobilized transition metal catalysts Uses are numerous. Because the catalyzically active metal is bound on the support and not in the reaction mixture is dissolved, the resulting metal-containing color bodies remain trapped on the surface of the heterogeneous catalyst and can therefore be removed by filtration at the end of the reaction. The esters produced by this process or Polyesters therefore generally have one compared to esters made using homogeneous catalysts much better color. Precisely because of this, the process according to the invention can also be successfully applied to reaction participants who are ketonic, aldehydic or olefinic Contain impurities, as they are present in commercial starting materials, without one such materials must be cleaned beforehand in a complex and time-consuming manner.

Another major advantage of the method according to the invention can be seen in the fact that at the end of the reaction practically all of the catalyst present simply dissolves can be filtered off. For example, esters or polyesters with a content of less than Produce 1 ppm titanium, and these are practically metal-free esters or polyesters, compared to those below Ester products obtained using known catalysts, also better hydrolytically, oxidatively and thermally stable. Just in this way ester products can be produced on a large scale for certain applications in which earlier It was not possible or inexpedient to reduce the remaining metal content to acceptable levels. Examples of such uses are in the food field or in other critical areas where appropriate esters or polyesters are needed, such as plasticizers for polyvinyl chloride or other polymers that are used as packaging materials for, for example, foodstuffs or blood bags

709823/09 & 3

will. The inventive method also allows the manufacture of turbine nests lubricating oils with viscosities of 3 centistokes (99 ⁰ C) or 1 centistoke (260 ⁰ C), with respect to their metal content-L-27402 MIL meet the strict requirements of MIL-L-78O8G or or these even over meet.

According to the invention, hydroxyl-terminated polyesters can also be produced in an advantageous manner, which are polymeric Intermediate products can be used to react with diisocyanates to form flexible polyurethanes. In present residual metal catalysts would form undesirable by-products (such as biurets, ureas or allophanes), which would lead to crosslinking or an impairment of the flexibility of the polyurethane.

The invention is further illustrated by the following examples. All parts and percentages contained therein are based on weight, unless otherwise stated. To the In the preparation of the catalysts, the supports used were not dried before use, and no measures were taken which would ensure the exclusion of moisture from the system, if not specifically stated.

example 1

In a jacketed stainless steel reaction vessel with a stirrer, thermocouple and condenser with a collecting vessel a supported titanium catalyst is produced. The reactor is filled with 90 parts of mineral oil (white oil No. 70) and 10 parts of natural added acid montmorillonite clay, which adsorbed about 4% Contains water. Then one begins with the heating and stirring of the reactor contents and leads in these below the Surface a solution of 33.5 parts of tetraisopropyl titanate (Tyzor TPT from E. I. du Pont de Nemours and Company) and 27.5 parts Divide mineral oil. This material is added via

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a period of 1.25 hours / and during this time you raise the reaction temperature to 110 ⁰ C. As soon as the temperature has reached 120 ^° C., the further addition of a solution of 21 parts of mineral oil and 34 parts of tetraisopropyl titanate is started. As soon as the reaction temperature has reached 140 C, distillate begins to collect in the collecting vessel. In the course of time, the temperature rises to 170 ^° C., this second addition (addition time 1.25 hours) having ended and the rate of distillate accumulation having increased significantly. One then further heated up to a temperature of about 200 ° to 210 ⁰ C and leaves the whole further 5 hours under these conditions to give distillate is withdrawn and propene, as well as other volatile components that do not condense discharges to the outside. The reaction mixture foams somewhat, but this does not interfere with the reaction or the collection of the distillate. The reaction mixture is then cooled to a temperature of about 70 ^° C., the supported catalyst is collected on a filter, washed several times with isopropanol until the filtrate is clear and finally dried in air. The weight of the wearer increases by 205%. Analysis (atomic absorption) of the product shows that it contains 37.8% by weight of titanium. The supported catalyst is a free-flowing grayish powder that appears almost like a liquid.

Example 2

A corresponding glass reactor is provided with a stirrer, a thermometer and a condenser equipped with a trap. A ventilation line arranged at the top of the condenser leads to a dry ice trap. The reactor is then charged with 20.1 g of the natural acidic montmorillonite clay from Example 1, 180 g of mineral oil and 50.3 g of tetraisopropyl titanate. The reaction mixture is then heated with stirring over a period of one hour to a temperature of about 200 ^° C., with 27 ml of isopropanol being withdrawn at the same time. 10 g of propene also collect in the dry ice trap. The reaction mixture is then cooled, keeping that on the filter

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2653S50

washes the material present with isopropanol until a colorless filtrate is obtained. After subsequent drying on the Air leads to 44.2 g of catalyst, which is 21.8 percent by weight Contains titanium.

Example 3

Using a method similar to Example 2, a supported vanadium catalyst is prepared by converting 10 g of the natural acidic monmorillonite clay and 15 g of tributyl vanadate in 160 g of mineral oil, and while stirring the reaction mixture from room temperature to 250 ° over a period of 1.2 to 5 hours ⁰ C heated. At a temperature of about 200 ^° C., a distillate begins to form, and a total of 6.2 ml of butanol is collected. Butene also condenses in the dry ice trap. The resulting reaction mixture is then cooled and filtered, whereupon the product obtained is washed with isopropanol until the filtrate is only completely pale yellow in color. Subsequent drying of the material obtained in the air gives 14.8 g of product. The supported catalyst produced in this way contains 16.1 percent by weight vanadium.

Example 4

An immobilized zirconium catalyst is also produced in the same way as described above. A synthesis carrier made of silicon dioxide and aluminum oxide (13% Al ₂ Ot) is used as the carrier for this reaction. The alumina / silica support (10.8 g) is placed in a reactor filled with 120 g of mineral oil (70 SUS) and 10.1 g of tetrabutyl zirconate. Subsequently heating the reaction mixture over a period of about 3 hours gradually to a temperature of about 22Q ⁰ C to obtain the same butanol and exhaust

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26B3850

removed. The resulting reaction mixture is then cooled and filtered, followed by washing and air drying the material obtained in this way leads to 13.25 g of a carrier catalyst (7.3 percent by weight zircon).

Example5

To demonstrate the versatility of the invention and the The possibility of producing suitable immobilized catalysts from a wide variety of supports is used in a number of ways hydroxylic carrier materials with tetraisopropyl titanate (TPT) in a mineral oil (70 SUS). The applied for this Apart from slight changes in the reaction temperature and the reaction time, the process is similar to those already described Working methods. The details of the respective experiments can be found in Table I below. Specified in this table are also the carriers used, the feeds from the respective reactants and mineral oil, the maximum reaction temperatures, the reaction times, the percentage weight increases of the support

. Final weight - initial weight e ₁ _ ^K initial ^{weight 'x IUJ}

and the percentage by weight of the titanium bound to the carrier. The data listed in this Table I can it can be seen that the most varied of carrier matrices are used for the production of the immobilized catalysts according to the invention let pull. It can also be seen that this process allows the production of catalysts with extremely high Transition metal content allows.

709823/09 9 3

Tabel

CD OO N>

Example 5a 5b 5c 5d

5e 5f 5g

5h 5i 5y

5k 51

carrier

Activated soot

2 potassium montmorillonite

Southern bentonite

Silicon dioxide / aluminum oxide (13% Al O)

Montmorillonite treated with HCl "Subbentonite Clay

Montmorillonite treated with H SO

Natural acidic montmorillonite

Calcium silicate

Pyrogenically produced silicon dioxide

Diatomaceous earth (containing water)

10

Sulfonated polystyrene resin

11

Added parts
(TPT / carrier / oil) reaction time
(Hours) Maximum
temperature (C) Percentage
Weight to
taking the
Carrier Weight pro
cent titanium
the carrier 59 / 11.9 / 160 4th 250 238 21.5 68 / 10.1 / 154 7th 250 20th 9.7 68 / 10.7 / 162 3.75 200 225 27.7 68.8 / 10/165 2 200 214 31.4 68.2 / 10.6 / 170 2.5 180 236 22.5 170/25/325 1.5 220 209 41.0 81.4 / 10.1 / 178 3.75 181 299 33.7 81.4 / 10.4 / 160 3 195 278 33.3J. 50.8 / 10.3 / 140 4.75 250 170 39.6? 30.2 / 6.0 / 170 4.5 240 560 13.5 35.4 / 5.1 / 140 4th 242 204 36.9 22.5 / 10/170 5.5 140 90 18.3

Darco KB; Atlas Chemical Co.

"

KOH treated montmorillonite (KOH excess) Panther Creek Clay; American Colloid Co, Silica-alumina 135 from Davison

Tonsil FF Optimum; Southern chemistry Clarolite BC; Georgia Kaolin Co.

10

11

Filtrol Grade 1; Filtrol Corporation

Microcell C, - Johns-Manville
Cabosil (M-5); Cabot Corporation

Diatomaceous earth is mixed with water, filtered and
air dried; the carrier contains over 50 percent by weight water

Amberlyst 15 Dry, Rohm and Haas (grain size = 0.25 mm)

-χ-

cn cn CO CO cn O

Example 6

10.25 g of the above-mentioned natural acidic montmorillonite clay, 68.5 g of tetraisopropyl titanate and 170 g of mineral oil (50 SUS) are placed in a reactor and then ^{heated to a temperature of about 220 °} C. for 1.5 hours, with 32.5 g ml of isopropanol and 12 g of propene are removed. The immobilized catalyst prepared in this way contains 35 weight percent titanium. Similar results are obtained if the conversion is carried out in a 100 SUS mineral sealing oil. When working with this more viscous oil, however, there is greater foaming of the reaction mixture, and at the same time the filtering time is somewhat longer.

Example7

To demonstrate the usability of various titanium alkoxides, namely tetrabutyl titanate. (7a), tetraoctyl titanate (7b) and a partially condensed tetrabutyl titanate (7c), which is obtained by the controlled addition of an amount of water calculated in this way, that a condensation product of 2 to 3 moles of tetrabutyl titanate results, as described in US Pat. No. 2,689,858 you go through a series of reactions. Each of these reactions is made with natural acidic montmorillonite clay as well as mineral oil 7O SUS worked. The reaction conditions used in each case and the percentage of titanium content of the immobilized products obtained therefrom Catalysts are shown in Table II below.

Table II

7a 7b 7g_ Added parts
(Ti compound / carrier / oil)

Max. Reaction ^{temperature (0} C) Reaction time (hours) Percentage weight increase

of the carrier 191 39

Weight percent on the

Supported Titanium 25.7 4.9 29.6

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68/11/1 53 24/27/1 75 73 / 10.5 / 1 60 250 210 235 6th 2 1/4 10

Example 8

For the production of an immobilized zirconium catalyst uses 21.3 g of natural acid montmorillonite clay and 84 g of tetrabutyl zirconate in 140 g of mineral oil (70 SUS). The reaction time is 8.5 hours, and during this time 40 ml Butanol and 13.5 g of butene collected. During the last The reaction temperature is kept at 250 to 265 ° C. for two hours of the reaction. Finally, after appropriate drying The catalyst obtained (51 g) contains 13.5 percent by weight of Sirkon.

Example 9

The following experiments are carried out to demonstrate the versatility of the invention. A diatomaceous earth (dicalite) dried at a temperature of 90 ° C. for a period of about two days is used as the carrier. About 10.5 g of this dry carrier are then combined with 60 g of tetraisopropyl titanate in 160 g of mineral oil (70 SUS) and the mixture is then heated to a temperature of 250 ^° C. with stirring over a period of over two hours Reaction, since neither isopropanol nor butene are formed. Repeating this experiment with the same charge indicated above, but adding 3 drops of 95 percent sulfuric acid at the beginning of the reaction _f leads to a vigorous development of isopropanol and butene at a temperature of 250 C and to the formation of an immobilized catalyst, the Contains 39.1 percent by weight bound titanium. If this experiment is repeated with the addition of 0.5% (based on the reactants) water at the beginning of the reaction, there is again a lively reaction with the formation of isopropanol and propene, with an immobilized catalyst with a titanium content again in a similar manner of 42.3 percent by weight arises.

70 9823/09 S3

Example 10

A corresponding reactor is charged with 10.5 g of activated granular carbon black (Witcarb 517), 2 3.6 g of tetraisopropyl titanate and 140 g of mineral oil and the reaction mixture is then heated to a temperature of 200 ^° C. for one hour. There is no reaction. After adding 3 drops of concentrated sulfuric acid, however, isopropanol and propene quickly pass over. The catalyst obtained in this way (23 g) contains 19.6 percent by weight of titanium.

Example 11

The suitability of the catalysts of the invention for hydrogenation processes is shown on the basis of the following investigation. A 1 liter stainless steel autoclave is charged in a dryer Nitrogen atmosphere with 500 ml deoxygenated xylene, 50.5 ml (0.5 mole) of cyclohexenes, 26.5 ml (0.25 mole) of toluene, 32 moles of 24.8 percent diisobutylaluminum hydride (0.04 mole) in heptane and 3.0 g (0.01 mol Ti) of the immobilized titanium catalyst from Example 1. The autoclave is then placed Heating and stirring (500 revolutions per minute) to a pressure of 35.2 kg / cm. As soon as a temperature of 87 ° C has been reached the pressure of the reaction vessel is set by releasing it

2
to 35.2 kg / cm and then heated the whole thing further. At a

The hydrogen uptake begins at a temperature of 180 ^° C. (39.7 kg / cm). Once the temperature has reached 200 C, the reaction is interrupted and leaves the reactor along with its contents slowly to 180 ⁰ C (4O, 4 kg / cm) and then allowed to cool to room temperature. The subsequent analysis of the reaction mixture by gas-liquid chromatography shows an almost complete conversion of cyclohexene into cyclohexane.

Example 12

To further illustrate the invention, a hydroxyl-terminated terminal suitable for the production of urethane polymers is provided Polyester is made by adding 364 parts of 1,4-butanediol and 1,076 parts a 1010 dimer acid with 97% dibasic C ,, .- acid and 3%

JD

tribasic C ₅₄ acid. The reaction mixture is

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- 3fr -

together with 0.05 parts of HUPO ^ solution with removal of water heated to a temperature of 225 C. A moderate vacuum is applied to the system to facilitate water removal. As soon the acid number has reached about 2, 1 g of the catalyst from Example 1 is added to the reaction mixture and this is increased Vacuum while maintaining the temperature. The polymerization is then continued for a further 20 minutes, until there is no longer any distillate catches. The polyester produced in this way is extremely clear and of excellent color, contains less than 3 ppm titanium and can easily be reacted with diisocyanates to form polyurethanes.

Example 13

Using the immobilized titanium catalyst obtained in Example 1, a mixed ester product is prepared, which is suitable as an industrial lubricant for metal processing, for example as rolling oil, and easily in water lets emulsify. Add 288 g (1.0 equivalent) refined palm oil, 60 g (0.3 equivalent) polyoxyethylene glycol with an average molecular weight of 400 and 85.8 g (0.3 equivalent) Empol 1014 dimer acid with 95% dibasic

C - ,, - acid together with 0.01 weight percent (based on the

entire charge) of the immobilized titanium catalyst in a reactor and then heated the reaction mixture with simultaneous removal of water for about 5 hours to a temperature of 220 ^° C. After cooling, the reaction mixture is filtered using 0.5% diatomaceous earth as a filter aid. The product obtained in this way has an acid number of less than 20, can be easily emulsified in cold tap water with gentle stirring and gives an aqueous emulsion with good stability. The triglyceride modified in this way has good heat stability, has good lubricating properties and contains less than 1 ppm of titanium.

709823/09 ^ 3

Example 14

The following experiment serves as a comparative experiment to further demonstrate the advantages obtained using the catalysts according to the invention. For this purpose, a polymeric orthotitanic acid ester catalyst similar to the heterogeneous catalysts described in DT-PS 1 142 868 is first prepared from ethylene glycol and tetrabutyl titanate. This catalyst is prepared by reacting 62 g of pure polymer ethylene glycol (previously dried) with 83.6 g of tetrabutyl titanate by heating to a temperature of about 130 to 150 C. Within a very short period of time, a white suspension forms, and 30 ml Butanol collected. The reaction mixture is then cooled and filtered, followed by washing the catalyst thus obtained with hot xylene and then dried in a vacuum oven at a temperature of 110 ⁰ C. The heterogeneous polymeric catalyst prepared in this way contains 35.5 percent by weight of titanium.

To further evaluate this catalyst, a mixed ester is prepared by adding azelaic acid, phthalic anhydride and a mixture of saturated aliphatic monobasic and dibasic acids (75:25) with excess propylene glycol (equivalent ratio of the respective reactants 0.625: 0.222: 0.150: 1.25) esterified by heating to a temperature of up to 230 ° C. for a period of 9 hours in the absence of the catalyst with removal of water. The Mischester thereby obtained as a product has an acid number of 5.4 and a kinematic viscosity at a temperature of 38 ⁰ C of 430 centistokes. The color of this product (as measured by the percent transmission determined by spectrophotometric analysis at 440 and 5550 millimicrons -% T) is 35/82.

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- vr-

2653350

1000 g of the above mixed ester are then admixed with 0.031 percent by weight of that prepared in the above manner heterogeneous catalyst (110 ppm Ti). The reaction mixture it is then heated under high vacuum (1 to 2 mm Hg) for 2 hours to a temperature of 225 ° C., the reaction mixture being removed at the same time removes glycol. After this two-hour reaction time, the acid number of the material is below a corresponding level Viscosity increase decreased to 0.4. The color of the product has become darker, so that the percentage permeability only has a very unsatisfactory value of 4/48. Except The polyester obtained also exhibits this poor color (after filtering to remove the heterogeneous catalyst) still has a content of 86 ppm titanium.

The process described above is repeated using 1000 g of the mixed ester, and repeated for two hours, heating at a temperature of 225 ⁰ C at a pressure of 1 to 2 mm Hg. In contrast to this, however, 0.057 percent by weight of an immobilized titanium catalyst (186 ppm Ti) similar to Example 5g is used in this reaction. The polyester obtained in this way has a higher viscosity, has an acid number of 0.5 and has a better color (% T = 19/75). Although in the reaction mixture more titanium is substantially present, the polyester finally obtained contains only 2 _r 4 ppm Ti by filtering off the immobilized catalyst.

Example 15

To further demonstrate the superior effectiveness of the present immobilized catalysts, one provides using the procedure customary for this, starting from tetraisopropylitanate, natural acidic montmorillonite carrier and mineral oil (70 SUS) those in the following

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-ASr-

^T able catalysts specified III forth. The details of the reaction used for this purpose and the analysis of the products obtained are shown in Table III below.

Table III

15a 15b 15c

Added parts
(Ti compound / carrier / oil) 20.3 / 40.4 / 150 45.6 / 30.5 / 160 67.5 / 10 / 138.5

TPT / carrier 0.50 1.5 6.75

Max. Reaction temperature

185 200 210 ° C

Response time (hours) 1 11

Percentage weight gain

of the carrier 32 57 205

Weight percent on the

Supported Titanium 7.9 20.3 37.8

For comparison with the immobilized ones produced in the above manner Titanium catalysts are also made into a heterogeneous catalyst (namely catalyst 15d) by adding tetraisopropyl titanate with the same natural acidic montmorillonite clay as described in US Pat. No. 3,817,931. The reaction is carried out under anhydrous conditions. The one used for this Clay (9.69 g) is added to the reaction to remove water under nitrogen for two hours at a temperature of Calcined at 350 C, whereupon it is mixed with 70.18 g of tetraisopropyl titanate and introducing 160 g of anhydrous toluene into a reactor.

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The reaction mixture is then heated to a temperature of 25 ° C. over a period of about 19 hours with stirring and finally filter it. After washing and appropriate drying, 10.2 g of catalyst are obtained. This catalyst contains only 2.9 weight percent bound titanium, although the ratio of tetraisopropyl titanate to support is the same as in the preparation of the immobilized catalyst 15c.

To further evaluate the above catalysts, a mixed ester is prepared. The preparation of this mixed ester is made by reacting adipic acid, 1,3-butylene glycol and 2-ethylhexanol (equivalent ratio of 1.0: 1.125: 0.125) at a temperature of 225 ⁰ C with removal of water. To facilitate the removal of water, the last reaction stages are carried out under vacuum. As soon as the acid number has reached a value of about 25, the reaction is interrupted. The ester obtained in this way has an acid number of 25.4, a viscosity at a temperature of 38 ^° C. of 197 cSt and a percentage permeability of 98/100.

1000 g of the above product are used for the following tests to assess the effectiveness of the products according to the invention Catalysts.

1000 g of the above ester are mixed with 0.01 percent by weight of catalyst and the whole is then heated to a temperature of 225 ^° C. under a nitrogen atmosphere. A vacuum (123 mm Hg) is then applied to the system and the temperature is maintained at 225 ^° C. As soon as 9.5 ml of water has been collected, the vacuum is lowered to 0.8 mm Hg and the reaction is continued for exactly 30 minutes. At this point the heating is turned off and the vacuum is broken by introducing nitrogen. After the reaction mixture has cooled to a temperature of 195 ° C., a 1.5 percent by weight filter aid is added

709823/09 93

- 4-r -

Add diatomaceous earth and filter the whole thing. Each ester obtained in this way is then examined with regard to its Acid number, its kematic viscosity and its color. The results obtained here are shown in the following Table IV.

Table IV

Under the use of
Catalyst produced

Polyester 15a 15b 15c 15d

Acid number 1.1 0.8 0.6 1.4

Viscosity at 38 ⁰ C 994 1440 1740 876 (cSt)

Color (% T at 440/550 m, u) 95/97 93/97 92/96 93/98

From the above-mentioned higher kematic viscosity values for the products 15a, 15b and 15c it is clear that the inventive Catalyst works more efficiently and effectively.

The catalysts are analyzed by Auger electron spectroscopy by pressing the respective powdered catalyst onto a stainless steel sieve which is arranged at an angle of about 30 to the electron beam. The Auger standard reference spectra are obtained when working with a radiation energy of over 6500 electron volts and a radiation current of 1 to 4 milliamperes when analyzing the L ₃ M _{3 3} M _{2 3} ~ Auger electron for Ti (387 EV) and the KL ₂ L ₂ -auger electrons for Si (1619 EV). Each titanium and silicon maximum is measured at least 10 times, after which one

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determines the mean value for the distance from maximum to maximum and calculates the ratio of the heights of the maxima. That for the Catalyst 15d here obtained maximum height ratio for Ti / Si is 0.13, while values of 1.3 and 10.5 result for the catalysts 15a and 15b. At the catalytic converter 15c is the amount of silicon that may be present on the surface, namely the first pair of layers of the support below the observation limit of the device. The results obtained here are not quantitative, they however, qualitatively show that there is a greater surface area of the immobilized catalysts according to the invention Amount of titanium is present. Furthermore, it can be seen from these values that a acidic sound carrier can be coated practically completely.

To demonstrate the improved hydrolytic stability of the immobilized catalysts according to the invention, the catalysts 15c and 15d are treated with aqueous isopropanol. For this purpose, combined 54 g of the particular catalyst with 76 g isopropyl! Alcohol (91 percent) and 135 g of water and then heating the resulting mixture for 2 hours under reflux to a temperature of 84 ⁰ C. Thereafter, the mixture is filtered and washes the catalyst with isopropanol, and the catalysts so prepared are referred to as Catalysts 15cH and 15dH. After the above treatment, the 15cH catalyst contains 38.2 percent by weight of bound titanium, while the 15dH catalyst contains only 2.8 percent by weight of bound titanium. Both catalysts (0.01 percent by weight) are then examined for their activity on the mixed ester prepared in the above manner by the method already described. This leads to the results shown in Table V below.

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Table V

Under the use of
Catalyst produced

Polyester 15cH 15dH

Acid number 0.8 1.3

Viscosity at 38 ^° C
(cSt) 1540 822

The above results show that the catalyst 15c retains most of its activity after the water treatment indicated and the catalyst 15cH has about the same activity as the untreated natural acidic sound carrier using which a polyester with a Acid value of 1.7 and a viscosity at 38 ⁰ C of 802 cSt.

Example 16

20 g of the natural acidic Mon tmorxllonitton s from Example 1 *, 361 g of mineral oil are placed in an autoclave with a capacity of 1 liter (70 SUS) and 137 g of tetraxsopropyl titanate. Then stir the reaction mixture (400 rpm) and starts heating. The temperature is kept at a value of 200 ° C for 4.5 hours, and during this time the pressure rises from 9.84 kg / cm and finally stabilizes at 31.6 kg / cm. In connection this is used to cool the reactor and its contents to room temperature

2
door (2.11 kg / cm) and slowly ventilate the whole thing into two connected dry ice traps. In this way, 18.25 g of propene are obtained. The catalyst obtained after washing and drying weighs 54.9 g and contains 40.7 percent by weight of titanium.

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Example 17

The supported titanium catalyst of Example 1 is also used to promote the exchange reaction (alcoholysis) between the methyl esters of short-chain dibasic acids and a so-called oxo alcohol. For this reaction, 2585 g of tridecyl alcohol and 915 g of dimethyl ester of mixed dibasic acids (predominantly glutaric acid and succinic acid) are added together with 3.5 g of activated carbon, 0.70 g of 50 percent H ₃ PO ₂ and 0.35 g of the immobilized supported titanium catalyst into an esterification reactor. The reaction mixture is stirred with heating. The accumulation of methanol begins at a temperature of about 180 ^° C., and a vacuum is then applied to the system as soon as the rate of methanol formation has become almost negligible. Excess tridecyl alcohol is then distilled off from the resulting reaction mixture by increasing the vacuum to 3 Torr. The ester finally obtained after filtration has an acid number of 0.1, a hydroxyl number of 1.2 and a tridecyl alcohol diester content of 94%. The ester contains only 0.6 ppm residual titanium and has an excellent color value of 96/98 as shown by the percent transmittance (% T) of a spectrophotometric analysis performed at 440 and 550 millimicrons.

Example 18

Triethylene glycol (413 g, 5.5 equivalents) and heptanoic acid are used (787 g, 6.05 equivalent) by heating the mixture up to 225 ° C. in the presence of 0.12 g of the supported catalyst according to Example 1 with the simultaneous removal of the water formed as a by-product. During the final stages of the reaction, the is lowered

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Pressure to facilitate water removal. After virtually complete removal of water (6 hours), cool the reaction mixture to 100 ° C and puts then high vacuum (2 to 5 Torr), while heating the whole over a period of 50 minutes to a temperature of 200 ⁰ C. The diester obtained in this way has an acid number of 0.1, a hydroxyl number of 11.8, a viscosity at 38 ^° C. of 82 cSt, a residual titanium content of less than 0.5 ppm and a color (% T) from 100/100.

Using the catalyst of Example 1, others are carried out similar esterifications through. The reaction of 2-ethylhexanol and phthalic anhydride results in a diester with a Less than 1ppm titanium content and excellent color. Also the esterification product of 1,3-butylene glycol and pelargonic acid contains less than 1 ppm titanium.

Example 19

For producing a polyester is heated (225 ⁰ C) 595 g of adipic acid, 449 g of propylene glycol, 39 g of pelargonic acid and 217 g of mono- and zweibbasische (75:25) mixed acids with removal of water with 0.13 g of H ₃ PO. ₃ As soon as the acid number has fallen to about 20, 0.13 g of catalyst from Example 1 is added to the reaction mixture. To facilitate the removal of water, which is necessary for complete esterification, a low vacuum is applied to the reaction system. As soon as the theoretical amount of water has been collected, the reaction system is brought under high vacuum (3 Torr) in order to effect the ester exchange and transesterification by removing volatile products. The polyester product obtained after filtering the reaction mixture has a temperature of 38 ^° C. Viscosity of 1017 cSt and contains 0.7 ppm residual titanium.

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ZGDJSb

Example 20

802 g of adipic acid, 813 g of phthalic anhydride, 695 g of propylene glycol and 1190 g of 2-ethylhexanol are reacted with one another according to the method described in Example 19. The case, after filtering obtained polyester (residual titanium content 0.7 ppm) has an acid number of 0.3 and at a temperature of 38 ⁰ C, a kinematic viscosity of 531 cSt.

Example 21

To demonstrate the recyclability of the present supported catalysts for reuse, an immobilized catalyst is prepared using preformed beads (4 to 5 mm) of acidic montmorillonite clay. For this purpose, combined 10.7 g of the clay balls, and 11.1 g of tetraisopropyl titanate in 200 g of mineral oil and then the whole is heated under collecting the formed as a by-product isopropanol and propene over a period of 3 hours to a temperature of 200 ⁰ C. The in this Supported catalyst produced in this manner weighs 5.3 g after drying and contains about 10 percent by weight of titanium.

The above catalyst (10 g) and 1000 g of the starting material of Example 14 is then combined and the whole is heated to this high pressure for PoIyveresterung exactly 2 hours at a temperature of 225 C. Thereafter, the product at 190 ⁰ C is cooled, and filtered, whereupon the catalyst beads are recovered and used again for the conversion of a further 1000 g of starting material under identical reaction conditions. The results obtained in the manufacture of the polyester products in two experiments are shown in Table VI below.

709823/0993 ORIGfMAL [MSPECTED

Acid number Hydroxyl number

Kinematic viscosity at 38 ⁰ C (cSt)

e 26th VI polyester 53850 T a b e 1 1 Try second ' First 4 0, 8 16, attempt 2 0, 9 16,

1351

1407

Example 22

To further demonstrate the versatility of the process according to the invention, a number of different ones are produced in the usual way Carried out catalysts by changing the ratio of tetraisopropyl titanate to carrier. As a hydrocarbon a mineral oil is used here and montmorillonite clay is used as a carrier. After that, the from the following Table VII prepared catalysts.

Tabel

VII

Catalysts

22a 22b 22c 22d

TPT / tone

0 , 25 0, 50 1, 0 1, 5

Percent bound Ti

5.2

13.4 20.3

Using the above catalysts, the base material of Example 14 is esterified by the same procedure. The polyester in this case obtained as products are at a temperature of 38 ⁰ C respectively viscosities of 1Ο3Ο, 994, 1330 and 1440 cSt.

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Example 23

90 parts of aluminum oxide-silicon dioxide pellets (3.175 mm) are reacted with 45 parts of tetraisopropyl titanate in white oil (70 SUS) at a temperature of 200 ^° C. over a period of 1.5 hours. The washed and dried catalyst pellets (50 parts) form a fixed bed catalyst in a reactor designed for a continuous process. The reactor is operated at a temperature of 225 ^° C. and a pressure of 1.0 mm Hg at a rate varying from about 2 to 5 ml per minute and at the same time removing the resulting polyester at a comparable rate to produce an ester with adipic acid, 1.3- Butylene glycol and 2-ethylhexanol are charged continuously according to the procedure described in Example 14, but the reaction is carried out up to an acid number of 2.2 (a viscosity at a temperature of 38 ^° C. of 270 cSt). After a reaction time of two hours, the viscosity (38 ° C.) of the product removed here has risen to 1300 cSt. At this point the process is continued for an additional hour so that the viscosity of the resulting polyester never drops below 1300 cSt. In this way, about 250 g of polyester are obtained per hour.

Example 24

10 g of a natural acidic montmorillonite clay and 15g Tributylvanadat comprises reacting 160 grams of mineral oil for the production of a vanadium-supported catalyst to each other by heating the reaction mixture with stirring over a period of 1.25 hours from room temperature to 50 ⁰ C 2. At a temperature of about 200 ° C., a distillate begins to pass over, and a total of 6.2 ml of butanol is collected. Butene also accumulates in the dry ice trap. After cooling and filtering the reaction mixture

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the product obtained is washed with isopropanol until the filtrate is only very slightly yellow in color. That product finally obtained after drying in air weighs 14.8 g. The supported catalyst produced in this way contains 16.1 weight percent vanadium.

An immobilized zirconium catalyst is also prepared in the same way. Synthetic silicon dioxide / aluminum oxide (13% Al ₃ O ₃ ) is used as the carrier for this reaction Reactor. ^{The reaction mixture is then gradually heated to 220 °} C. over a period of about 3 hours while removing butanol and exhaust gas. After filtering the reaction mixture, washing and air-drying the material obtained, 13.25 g of a supported catalyst (7 , 3 percent by weight zircon),

Both products obtained in the above manner are effective esterification catalysts.

Example 25

The procedure for preparing methyl oleate is as follows: 500 g of oleic acid, 58 g of methanol and 5 percent by weight (based on the oleic acid) of the catalyst from Example 1 are placed in a reactor. The reaction mixture is then gradually heated to a temperature of 140 ⁰ C, wherein distill off a mixture of water and methanol at a temperature of about 8O ⁰ C begins. Subsequently, methanol (29 g per hour) is introduced into the reaction mixture below the surface with heating to a temperature of 170 ^° C. As soon as the acid number of the reaction mixture has reached a value of about 1, the

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Reaction interrupted. The methyl oleate obtained after filtering with diatomaceous earth as a filter aid has an acid number of 0.9 and contains less than 1 ppm titanium.

Example 26

1000 g of the ester feed from Example 14 (% T = 98/100) is used to prepare corresponding polyesters with (a) 0.58 g of the supported catalyst from Example 1 and (b) 1.30 g of tetraisopropyl titanate around. Both reaction systems contain 219 ppm Ti. With heating to a temperature of 225 ° C., a vacuum (160 mm Hg) is then applied to each reaction system, up to 9.5 ml Water are collected, at which point the pressure is lowered to 19.6 mm Hg and the individual reactions are carried out then continue for 2 hours until the end. About the same amount of distillate is obtained in both reactions. To Filtering with 1.5 percent by weight diatomaceous earth as a filter aid indicates that using the immobilized Catalyst obtained polyester product (A.V. 0.5) a color of 95/100, while that using the homogeneous tetraisopropyl titanate catalyst obtained polyester (A.V. 0.4) has a color of 60/95. The inventive method under Use of the immobilized transition metal catalysts therefore clearly leads to a significant improvement in the Color of the polyester produced afterwards. In the polyester produced by the method (b), the amount of residual is Titanium is also about 10 times larger than that of the polyester obtained according to procedure (a).

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Claims (17)

Claims 1. Process for the preparation of a transition metal supported catalyst by reacting a support with hydroxyl groups containing surface with a transition metal alkoxide of the formula worm M for a transition metal from groups IVb ₇ Vb or
VIb of the Periodic Table of the Elements is OR is an alkoxy radical with 1 to 18 carbon atoms, η is an integer from 2 up to the valence of the
Metal M represents Q is an inert radical that does not react with the hydroxyl groups of the carrier, the alkoxy radical -OR or a
Alcohol means ROH and m is such an integer that the sum of η + m corresponds to the valence of the metal M, characterized in that the
Carrier and an excess of the hydroxyl groups available on the surface of the carrier. Transition metal alkoxide heated in an inert hydrocarbon and in the presence of water to a Tempeatur of 100 to 300 ⁰ C, thus causing a condensation of the transition metal alkoxide
and a reaction of the transition metal alkoxide or one
Oligomer comes from this with the hydroxyl groups located on the surface of the support. 7 0 9823/09 9-3 ORIGINAL INSPECTED 2 hb 3 H b Ü 2. The method according to claim 1, characterized that at a ratio of transition metal alkoxide molecules to on the support surface located hydroxyl groups of over 1; 1 up to 10: 1, preferably from 2: 1 to 10: 1, works, used as the inert hydrocarbon an aliphatic hydrocarbon and the reaction under a weight ratio from hydrocarbon to carrier of about 0.5: to 50: 1, preferably 2: 1 to 25: 1. 3. The method according to claim 2, characterized that all or part of the water required for the reaction is in the form of adsorption water is present on the surface of the hydroxyl-containing carrier. 4. The method according to claim 3, characterized that the hydroxyl-containing carrier is silicon dioxide, aluminum oxide or mixtures used hereof. 5. The method according to claim 2, characterized in that the whole or one Forms part of the water required for the reaction in situ by dehydrating alcohols. 6. The method according to claim 1 to 5, characterized in that the transition metal alkoxide Tetraisopropyl titanate or tetrabutyl titanate is used. 709823/09 ORIGINAL SUSPECTED - 56 - / 6b38SÜ 7. The method according to claim 2, characterized in that one with a transition metal alkoxide the formula mentioned in claim 1 works, in which M stands for titanium, zirconium, hafnium or vanadium and -OR is one means saturated branched or straight-chain alkoxy radical having 2 to 8 carbon atoms and the reaction in one Temperature from 120 to 250 C in a practically saturated liquid aliphatic hydrocarbon with a boiling point above about 140 ° C as well as below a ratio of transition metal alkoxide molecules to pre- existing hydroxyl groups of about 1.5: 1 to 10: 1 carries out. 8. Transition metal supported catalyst, producible according to one of claims 1 to 7, characterized in that that it contains about 3 to 60 percent by weight bound transition metal. 9. Transition metal supported catalyst according to claim 8, characterized in that it contains about 5 to 50 percent by weight of titanium bonded to the support. 10. Supported transition metal catalyst according to claim 8 or 9, characterized in that that it contains an acidic monmorillonite clay as a carrier. 11. Immobilized supported transition metal catalyst, characterized in that it is about 3 to 60 percent by weight of a supergum metal from the Contains groups IVb, Vb and VIb of the periodic table, where 7 098 2 3/09 9-3 "INSPECTED - 5-7 - this transition metal in on the carrier matrix via oxygen bridges exists as a polymeric cross-linked network in bound form, in which the transition metal atoms via oxygen bridges are tied together. 12. Immobilized supported transition metal catalyst according to claim 11, characterized in that that it is a hydrolytically stable, finely divided and free-flowing powder. 13. Immobilized supported transition metal catalyst according to Claim 11 or 12, characterized in that that its carrier matrix is almost completely covered with transition metal polymer, the carrier silicon dioxide, Represents aluminum oxide or mixtures thereof and the transition metal is titanium, zirconium, hafnium and / or vanadium. 14. Immobilized supported transition metal catalyst according to claim 13, characterized in that that it contains about 5 to 50 percent by weight bound transition metal and that the transition metal is titanium. 15. Process for the batchwise, continuous or semicontinuous preparation of carboxylic acid esters by direct esterification of a carboxylic acid or a carboxylic acid anhydride with an alcohol or by ester interchange of a carboxylic acid ester with another carboxylic acid ester, an alcohol or a carboxylic acid by heating the reactants in the liquid state to temperatures from 100 to 300 ⁰ C in the presence of a supported transition metal catalyst, characterized in that the reaction is carried out in the presence of at least 0.005 percent by weight, 709823/09 ^ 3 based on the reactants, of an immobilized transition metal supported catalyst carried out, the about 3 to 60 percent by weight of a transition metal from groups IVb, Vb and VIb of the periodic table contains, and in which the transition metal in on a carrier matrix via oxygen bridges as a polymer crosslinked network bonded form is present, the transition metal atoms are bound to each other by oxygen bridges. 16. The method according to claim 15, characterized that a catalyst obtained according to claims 1 to 7 is used. 17. The method according to claim 15, characterized that a catalyst obtained according to claims 8 to 14 is used. 709823/09 ^ 3