DE3002318A1 - METHOD FOR PRODUCING 1 OR MORE COMPLEX BONDED METALS CONTAINING POLYMERS - Google Patents

Description

DR. 6TEPHAN G. BESZfDES PATENT ADVOCATE

AUTHORIZED REPRESENTATIVE AT THE EUROPEAN PATENT OFFICE

PROFESSIONAL REPRESENTATIVE ALSO BEFORE THE EUROPEAN PATENT OFFICE

C060 CACIIAU 3El MDNCHEN

1 8

N 8

MDNCHENER STRASSE 8OA Federal Republic of Germany TELEPHONE: DACHAU 4371 Postal checking account Munich (BLZ 700 100 80)

Account no. 1 368 71

Bank account no. 906 370 at the district and city

parking bank Dachau-Indersdorf (BLZ 700 515 40)

(VIA Bayerische Undesbank

Girozentrale. Munich)

P 1 296

Describes! η

for patent application

MAGiAR TUDCMANYOS AKAL ¹ EMIA KÖZPONTI HIVATALA

Budapest, Hungary

concerning

Method of making 1 or more Polymers containing complexed metals

The invention relates to a process for the production of 1 or more complexed metals containing Polymers from solutions of metal ions or complexes.

030031/0801

The invention is based on the object of a simple method for the production of substances that as a result of metals bound by complex bonds to the framework of an organic polymer and the chemical and physical properties of the metal complex macromolecule in various fields, in particular as catalysts or as for the production of magnetic sound tapes suitable substances or as semiconductors, can be used advantageously, and their Use to create.

The above has surprisingly been achieved by the invention.

The invention is based on the surprising finding that in an organic base material (Katrix) embedded solid metal complexes can be obtained when metal complexes of organic substances which also have functional groups or sites suitable for polymerization, are formed and after Complex formation the complex is polymerized. In this way, a wide range of the most varied can be fixed Metal complexes are produced.

The invention therefore relates to a process for the production of 1 or more complexed Polymers containing metals by reacting ions and / or a complex or complexes of at least 1 metal with at least 1 compound which has a connection with this metal or these metals Complex or complex forms or form or for incorporation in his or her

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Ligand space is or are, in solution, which is characterized by the fact that the connection (s) for reacting with the ions and / or the complex (s) of the metal or metals a those or those with polymerizable sites and / or at least 2 polymerizable functional Groups {polymerizable [r] organic [r] Complexing agent] is or are used and the complex compound (s) thus obtained, in the or the at least 1 place in the ligand space of the metal or metals from the polymerizable Organic complexing agents or taken from the polymerizable organic complexing agents is, is or will be polymerized.

In the polymers containing complex bonded metals produced according to the invention, there is also at the same time at least 1 complexing agent part.

The term "polymerization" is used in the broadest sense than apart from polymerization by splitting and saturation of double or triple bonds of such compounds also the polycondensation and polyaddition and other conversions for formation used extensively by larger molecules. The same applies mutatis mutandis to the expressions "polymerizable" and "Polymer".

A solution of 1 or more salt (s) and / or complex (s) of the in the polymer base material is expediently used as the starting material metal to be incorporated or the metals to be incorporated into the polymer base material

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used. The metal complex used as starting material must of course be an exchangeable complex, that is, a compound in whose ligand space the complex-forming polymerizable organic compound can be incorporated.

As a complex-forming polymerizable organic compound, any organic compound, which on the one hand has complex-forming functional groups and, on the other hand, by polymerization including polycondensation, Polyaddition or other polymerization variants can be implemented into a polymer, used will.

Thus aniline and / or phenol and / or a derivative or derivatives of one or both of these and / or urea can advantageously be used as polymerizable organic complexing agents and the polymerization of the complex compounds obtained with .1 or more aldehyde (s) , especially formaldehyde. For example, as aniline derivatives, K-Akylanilines _t N-Arylanilines, K-Aralkylanilines, K-Cycloalkylanilines, toluidines, xylidines, haloanilines, liitranilines, phenylenediamines, alkoxyanilines, aryloxyanilines, aralkoxy & nilines, cycloalkoxy & nilines, cycloalkoxy & nilines and esters, cycloalkoxyanides, and aminobenzyl acids, aminobenzenes, and aminobenzenes, acoxyanides, toluidines, and aminoxyanides, toluidines and / or halides can be used, the use of the phenylenediamines being particularly preferred. For example, alkylphenols such as! [Resoles and xylenols, arylphenols,

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Aralkylphenols, cycloalkylphenols, halophenols, nitrophenols, aminophenols, alkoxyphenols, aryloxyphenols, Aralkoxyphenols and / or Cycloelkoxyphenols used , the use of aminophenols being particularly preferred. In the case of using more than 1, for example 2, polymerizable organic complexing agents the one advantageously phenol can be. Further examples of usable aldehydes are acetaldehyde, propionaldehyde, Butyraldehyde and benzaldehyde.

Furthermore, 1 or more di- and / or Polycarboxylic acids) and / or derivative (s) of such or of such used and the polymerization of the complex compound (s) obtained with 1 or more di- and / or Polyalcohol (s) and / or diamine (s) are carried out. Examples of di- or polycarboxylic acid derivatives that can be used are their esters, amides, halides, anhydrides, nitriles, hydrazides, azides, oximes and / or hydrazones.

Furthermore, can or can advantageously be used as polymerizable organic complexing agents 1 or more unsaturated bonds, optionally with initiators, polymerizable organic compounds) be used. The polymerization is after the complex formation, if necessary with the addition of Initiators carried out.

In the method according to the invention, as ions and / or complexes of ketals, advantageously those of metals from the platinum group of the periodic table, such as Palladium, platinum, rhodium, and / or rhenium, silver,

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BATH ORIGINAL

Nickel, cobalt, copper, iron, molybdenum, vanadium and / or Unrom can be used.

The complex formation can take place in any suitable solvent be made. Water is expediently used as the solvent, but water can also be used Miscible and water-immiscible organic solvents, mixtures of several organic solvents as well as mixtures of water and organic solvents are suitable. The output connections, that is, the Metal compound (s) and the polymerizable organic Complexing agents or the polyaerizable organic complexing agents can be used in the same solvent can be used dissolved, but it is also possible to combine their solutions in different solvents.

The polymer base material can be obtained by adding a further monomer or further monomers, that does or does not participate in the complex formation, but in the Polymer base material is or will be incorporated, to the complex-forming monomer or monomer mixture can be varied within wide limits. According to an advantageous embodiment of the method according to the invention is or are therefore also 1 or more no complex-forming [r] for the polymerization, but for Incorporation into the polymer capable constituent (s) jjmodifying [s] comonomer (s)] with used »For example can be used as such melamine.

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BATH ORIGINAL

If the other ingredients used to form the polymer do not or do not interfere with the complex formation are indifferent to the metal compound or the metal compounds, these components can be added before the complex formation.

In the manner described, complexes in which in the ligand space of the metal or the Metals at least 1 polymerizable organic complex-forming compound is incorporated.

It is not necessary to have every site in the ligand space from the polymerizable organic complexing agent or from the polymerizable organic Complexing agents is taken, but as already mentioned only at least 1. At the other points of the Ligand space can be various other ligands, for example ammonium and organic complexing agents, for example Kexoses, such as glucose, hexites, such as sorbitol, polyalkylene glycols, such as polyethylene glycols, glyoxal, Glycolic acid, oxyquinolines, such as 8-oxyquinoline, and / or aromatic oxyaldoximes, such as saücylaldoxime, and optionally compounds having an asymmetry center, such as 1-Fhenyläthylamin are located. These can also be used in the inventive Process "in situ" are formed.

The polymerization of the complex compounds thus obtained) can in any known manner, if necessary using customary initiators or polycondensation comonomers and optionally Polymerization auxiliaries and / or modifiers, be performed.

030031/0801

It can be polymerized according to the usual process engineering or technology. The polymerization temperature depends on the type of monomer or monomers and the reaction medium. A polymerization temperature of 350 to 420 ^° K is preferred, but it is also possible to work at higher or lower temperatures. The polymerization is generally carried out under atmospheric pressure or elevated pressure.

After the end of the polymerization, the product can be separated off from the reaction mixture in a customary manner. The product obtained can be codified in such a way that components which can be removed thermally or chemically are removed from it and, if necessary, Λ or more other substance (s) are incorporated into the ligand space. According to an advantageous embodiment of the method according to the invention, the unpolymerized organic complexing agent (s) is (are) removed thermally or chemically after the polymerization and, if necessary, replaced by another or different complexing agent. An example of the removal of the unpolymerized organic complexing agent is treatment with alkali sulfides, such as sodium sulfide, to form insoluble sulfides.

The inventive method is expedient as follows carried out.

The metal salt or the metal salts is or will be in a solvent, in the simplest way Trap in water, dissolved and with stirring is refer-

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that is, the polymerizable sites and / or functional groups with the metal or metals form a complex or complexes or, if a metal complex solution is assumed, capable of being incorporated into the ligand space of the complex or complexes (n) organic compound (s) added. Optionally, 1 or more complex-forming but no polymerizable sites or compound (s) containing polymerizable functional groups and / or compound (s) not forming complexes but participating in the polymerization can be added in a suitable solvent will. In the case of aniline and phenol or their derivatives, it is often expedient to use water with an optimally adjusted pH as the solvent. After stirring for a few minutes, the polymerizing constituent or constituents are added. In the case of aniline and phenol or their derivatives, an aqueous solution of an aldehyde is expediently used as the polymerizing component, in the simplest case an aqueous formaldehyde solution such as one with a concentration of 35 to 40% by weight (formalin). The resulting suspension is stirred for 30 to 60 minutes at 250 to 400 ⁰ C, during which time Expires polymerization. The product is filtered off, washed to remove the accompanying substances and then dried. A similar procedure is followed in the production of polyesters, for example the polymer of diaminotetraacetic acid with ethylene glycol, or in the production of polyamides, for example the polymer of triethylenetetramine with terephthalic acid.

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First, the solution of the complexing agent or the complexing agent in water or an organic solvent is reacted with the solution containing metal ions and / or 1 or more metal complexes or the same, reacted = As Eeaktionstemperatur be applied advantageously over 36O ⁰ K, so that the resulting water can escape from the reaction mixture _e in the polymerization of, for example, p-aminostyrene is also produced first, the complex and the latter was then dissolved in a solvent and mixed with an organic peroxide «The mixture is heated for several hours, then the solvent is filtered off and the product is dried under vacuum =

If necessary, the polymerization can then be carried out by thermal treatment or by chemical means non-participating ligands wholly or partially removed or by impregnation, sorption or be exchanged for other ligands in another way »

According to the invention, the 1 or more complex bound Polymers containing metals or, in other words, metal-containing polymer complexes also on the surface of Porters formed xverden »As porters, for example Activated carbon, aluminum oxide (AIqOz) and silica gel in question, First and foremost, the carriers widely used for the production of catalysts = the Impregnated carrier “For example, the carrier can first

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Θ30031 / 0801

with the polymerizable organic complexing agent or the polymerizable organic complexing agents and then with the solution of the metal salt respectively the metal salts and / or the metal complex or the metal complexes are impregnated, then can or can the polymerizing component or the polymerizing components, for example an aqueous formaldehyde solution, added, heated and finally the product separated and getting washed.

A special case of application to a carrier is when the carrier is also a polymer, which also has further sites suitable for polymerization. According to an expedient embodiment the process according to the invention therefore involves the production of the polymers containing complexed metals the surface of other polymers "which are still to Polymerization have suitable vacancies and optionally also contain complex-bound metals, carried out and the 2 or more polymers become polymerizing and polymerizing by means of 1 or more, respectively Components [s] connected to one another. The carrier polymer can be composed of the same components as the complex Polymer base material containing bonded metals exist, but its composition can also be from the latter differ. The carrier polymer or the carrier polymers can also be 1 or more contain complexly bound metals. A polymer base material composition containing different metals in its individual layers can as one through one on

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the surface of the carrier polymer or the Carrier polymers produced 1 or more polymer base material containing more complex bonded metals formed sandwich structure can be realized. These Eigenart can also be advantageous for catalytic purposes. For the production of such sandwich structures necessary For example, the polymer used as the carrier or the polymers used as the carrier become first with the polymerizable organic complexing agent or the polymerizable organic complexing agents impregnated, then treated with the metal salt or metal complex solution (s) and finally the polymerizing second ingredient respectively the polymerizing second constituents added, the one or the one hand the polymer base material forms on the surface and on the other hand the carrier with that located on its surface Polymer base material connects "

By the method according to the invention, 1 or more Complex-bonded metal (s) containing polymers, which can be used in numerous fields, produced! - / ground » Thus, for example, catalysts which have the advantages of homogeneous and combine heterogeneous catalysts, but do not have their significant disadvantages will. In this case, relation: becomes wise as Starting material 1 or more containing metal ions and / or consisting of 1 or more metal complex (s) Salt (s) and / or complex (s) of at least 1 catalytically active metal used. Furthermore, ferromagnetic

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Iron complex macromolecules, which make the iron finer Distribution contain and can be used advantageously for the production of Kagnetton tapes will. Furthermore, products which have different properties than those with a similar polymer base material, however, do not have complex-bonded metal-containing polymers and, for example, as semiconductors are suitable to be produced.

The invention therefore also relates to the use of the 1 or obtained by the process according to the invention Polymers containing more complex bound metals as catalysts, for Kagnetton tapes or as semiconductors.

The particular importance of the method according to the invention lies in the fact that it produces catalysts which have previously unknown, completely new properties can be.

As already mentioned, for example catalysts which have the advantages of metal complex catalysts those of the heterogeneous metal catalysts combine in themselves, can be used.

Metal complex catalysts are known to have the The advantage of high selectivity, but at the same time the disadvantage that their production is relatively complicated is, they are often sensitive to moisture and difficult to separate from the reaction mixture and with they generally involve a lot of effort.

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The production of heterogeneous metal catalysts is usually easier and involves less effort than that of the corresponding metal complexes . Their activity is generally higher, they can be easily separated from the reaction mixture and can also be regenerated, but they have the disadvantage that their selectivity is often lower than that of the metal complexes *

Efforts have been underway lately that are beneficial Properties of metal complex catalysts and the metal catalysts to unite with each other »To this end, the surfaces of various become more solid Substances are chemically activated in such a way that those located there Groups can enter into chemical bonds with metal complexes. These operations are general complicated and in many cases the catalyst obtained is already against the moisture content of the air sensitive"

With the method according to the invention, it is against succeeded in catalysts which combine the advantages of the two mentioned Eatalysatorty ^ en in itself, their disadvantages but do not have to obtain »By the invention Processes can produce numerous previously unexplored solid complex metal catalysts

The possibilities for variation are extremely numerous: Different metals or metal combinations can be used and also various complexing agents, including optically active substances, are used and also the

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Q30031 / 0801

-y-

Ligament space influences the catalytic properties. Also, the composition of the embedding the complex Serving polymer base material can by not participating in the complex formation, but polymerized into the product Substances are changed, which also changes the catalytic properties of the product. In this sense, a whole family of catalysts can be formed from a single metal, for example palladium will.

The solid ketal complexes containing polymers containing 1 or more complexed metals and prepared according to the invention can be in the form of powders and their heat and complex resistance and their resistance to solvents is good ^{up to 460 to 600 ° K.} Due to their low specific weight, they can easily be mixed into liquids and fill the volume of the liquid phase well. They are also extremely easy to filter.

It is easy to manufacture. The production of catalysts based on aniline, phenol or their Derivatives is "simpler than that of the simplest, for example Metal catalysts. In many cases it can be in aqueous Medium to be worked. The operations are simple and easy to carry out and the manufacturing time is short.

The devices required for manufacture are the simplest imaginable, that is, when the products are introduced into the practice of technology, respectively Industry hardly any investments are required.

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Some of the products made according to the invention, for Example of a palladium complex catalyst produced with phenol derivatives as complexing agents are already included in Room temperature and active and under atmospheric pressure selective hydrogenation catalysts and yet have no pyrophoric properties. This especially for the industry a particularly advantageous feature is characteristic of most of the catalysts prepared according to the invention. The noble metal complexes are active in, among other things, catalytic hydrogenation and in relation to oxidations Complexes of transition metals with respect to oxidations and Reductions with carbon isonoxide

The metal complex catalysts prepared according to the invention are less sensitive to catalyst poisons than the corresponding metal catalysts ₀

The following are the measuring methods or devices with which the activity and the physical Properties of the catalysts have been checked, specified.

Catalytic hydrogenation in the liquid phase at room temperature and below Atmospheric pressure

In a 250 cur round bottom flask, 20 cur ethyl alcohol, 0.1 g of the catalyst to be examined and 0.5 cm of eugenol, benzyl cyanide or acetophenone as well

7th

0.1? cm nitrobenzene introduced. The flask was

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- opened up and first with nitrogen and then with hydrogen flushed through. It was hydrogenated on a shaker table at a frequency of 160 minutes and the hydrogen consumption was measured as volume. The activity is equal to that measured from the start of the reaction Hydrogen uptake expressed in cm / minute. 0.1 g Catalyst.

Oxidation activity in the liquid phase

3 3

There were 20 cm in a 80 cm glass flask

10% ascorbic acid solution and 0.1 g of the catalyst to be investigated were introduced. The flask was flushed through first with nitrogen and then with oxygen and its temperature was kept constant ^{with a thermostat with a tolerance of ± 0.2 ° C.} The magnetic stirrer was turned on and stirring was carried out at a speed of about 120 minutes. The activity is equal to the oxygen uptake measured from the start of the reaction, expressed in cur / minute · 0.1 g of catalyst.

Magnetic properties

They were measured with a Faraday device between 20 and 35O ⁰ C.

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BATH ORIGINAL

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la

Thermogravimetric measurements

The products of Examples 1, 34 and 38 were also analyzed thermogravimetrically. It was found that the samples containing m-aminophenol showed a ^{greater change in weight and decomposition by about 30O 0} C, while the samples containing o ~ aminophenol already ^{showed similar phenomena at 170 to 300 0} C. The measurements were made with a derivatograph made according to Erdey-Paulik-Paulik.

Activity related to the hydrogenation of carbon dioxide

She was using in a flow tube reactor about 0.1 to 0.2 g of catalyst and a gas mixture 12 cnr hydrogen and 3 cnr carbon oxide under atmospheric pressure measured. The reaction apparatus was connected to a gas chromatograph, the one given in the examples The temperature is the so-called ignition temperature, i.e. the lowest temperature at which the reaction begins.

The invention is illustrated by the following examples explained.

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030031/0801

example 1

A solution of 1.78 g of palladium (II) chloride [PdCl ₂ J in 50 cm * water and then a solution at room temperature with vigorous stirring were placed in a 250 cm beaker

7th

of 4.4 g of m-aminophenol introduced into 20 cnr of water · Zum The precipitate formed was added 20 cm of water

7th

and then, with stirring, 12 cm of concentrated

aqueous formaldehyde solution (formalin solution) was added dropwise. The mixture was kept 30 minutes under stirring at 90 to 95 ° C, the dark brown precipitate was filtered through a glass filter, washed to achieve a neutral reaction and dried at 80 ⁰ C in air. 6.7 g of product were thus obtained.

With this catalyst, cinnamaldehyde could be reduced to hydrocinnamaldehyde with a selectivity of 95 to 98 # (Yield: 95 to 98 # of theory). Hydrogenation activity: in terms of eugenol 11 cnr / minute x 0.1 g Catalyst and in terms of nitrobenzene 12 cnr / minute. 0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced, Carbon dioxide reduction: 110 ° C. Thermogravimetric analysis [jDTG analysis] with "the one given in front of the examples Result.

Example 2

The procedure described in Example 1 was followed, with the difference that, in addition to the falladium (II) chloride, 0.58 g of copper (II) chloride monohydrate [CuCl ₂ . H ₂ O] was used. So there was 6.6 g of a palladium / copper catalyst

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obtained »hydrogenation activity in relation to eugenol 1 cnr / minute. 0.1 g of catalyst and in relation to nitrobenzene 3 cnr / minute »0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced carbon oxide reduction:

Example 3

The procedure was as described in Example 1 of 35 $ aqueous solution of formaldehyde were dissolved, however, with the difference that in the palladium (II) chloride solution for a further 2 g of D-glucose _o Upon addition iirurden 0.2 g of aluminum shavings in the reaction mixture interspersed developed _o After 10 whereby hydrogen in an acidic medium to stirring for 15 minutes the pH was adjusted with a sodium hydroxide solution to about 8., Thus, 6.8 g catalyst = he were observed. Hydrogenation activity in relation to eugenol 11 cnr / minute. 0.1 g of catalyst and, in terms of nitrobenzene, 11 cnr / minute _β 0.1 g of catalyst, acetophenone and benzyl cyanide were not reduced
Oxidizing activity! O ₉ J cnr / minute _o 0.1 g catalyst »

Example 4

The procedure was as described in Example 1, but with the difference that instead of the m-aminophenol 4.4 g of o-aminophenol were used »So were 5? 7 g of product obtain. Hydrogenation activity in relation to eugenol 9 cnr / minute. 0.1 g of catalyst and in terms of nitrobenzene

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10 cnr / mimite. 0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced.
Oxydationsaktivität: 0.2 cnr / Mmite "0 ₉ 1 g of catalyst.

Example 5

The procedure described in Example 1 was followed, with the difference that 4.4 g of p-aminophenol were used became. 4.7 g of product were thus obtained. Hydrogenation activity: in terms of eugenol 21 cnr / ^ inute x 0.1 g Catalyst and with respect to nitrobenzene 15 cm / minute. 0.1 g Catalyst; Acetophenone and benzyl cyanide were not reduced. Oxidation activity: 0.35 emv minute. 0.1 g Catalyst.

Example 6

The procedure was as described in Example 1, but with the difference that instead of the m-aminophenole one Solution of 4 cm aniline and 4 cm concentrated hydrochloric acid in 20 cur V / water was used. While heating the pH \ vert was adjusted to neutral with sodium hydroxide solution. 5 ES of product were obtained in this way.

Hydrogenation activity: in terms of eugenol 6 cnr / minute x 0.1 g Catalyst and in relation to nitrobenzene 12 cmvmin. 0.1 g Catalyst; Acetophenone and benzyl cyanide were not reduced. Oxidation activity: 0.3 cmvmin. 0.1 g catalyst.

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300231

Bei Piel 7

The procedure was as described in Example 1, but with the difference that the m = aminophenol was dissolved in 40 cnr water and a solution of 9 g phenol in 50 cnr water was added _o It i-jurden 23 cnr a 35 $ = used is ^en aqueous solution of formaldehyde So were 7? 9 g product obtained "Hydrieraktivitätg regarding eugenol 9 emvMinute = 0.1 g catalyst and in terms of nitrobenzene 12 cnr / minute ° 0.1 g of catalyst ^ acetophenone and benzyl cyanide were not reduced .

Example 8

The procedure was as described in Example 1, but with the difference that in place of the _t m-Aminophenoles a solution of 5 cm m-chloroaniline and H- cnr concentrated hydrochloric acid in 10 cm of water used was _o To 6.7 g of catalyst was obtained

Hydrogenation activity§ in relation to eugenol 1 cnr / minute ° 0.1 g catalyst and in relation to nitrobenzene 2 cm / minute _o 0.1 g catalyst; Acetophenone and benzyl cyanide were not reduced,

Example 9

The procedure was as described in Example 1, but with the difference that instead of the m-arainophenol one Solution of 6.9 g of p-aminobenzenesulfonic acid amide and 1 car of concentrated hydrochloric acid in $ 0 cnr of water was used

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10.8 g of product were thus obtained.

Hydrogenation activity: with respect to eugenol 3 cnr / minute. 0.1 g catalyst and in terms of nitrobenzene 5 cnr / minute # 0.1 g Catalyst; Acetophenone and benzyl cyanide were not reduced, oxidation activity: 0.25 cnr / minute. 0.1 g catalyst.

Example 10

The procedure was as described in Example 1, but with the difference that instead of the m-aminophenole one Solution of 5 »76 g of m-phenylenediamine in 30 cm of hydrochloric acid water was used. 6.5 g of product were thus obtained.

Hydrogenation activity: in terms of eugenol 5 cnr / minute x 0.1 g

■ j. Catalyst and in terms of nitrobenzene 4 cnr / minute. 0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced. Oxidation activity: 0.3 cnry minute. 0.1 g catalyst.

Example 11

The procedure was as described in Example 1, but with the difference that instead of the m-aminophenole one Solution of 5 »76 g of o-phenylenediamine and 1 cnr of concentrated Hydrochloric acid in 35 cnr water was used. Thus 1.2 g of product were obtained.

Hydrogenation activity: with respect to eugenol 9 cnr / minute x 0.1 g catalyst and with respect to nitrobenzene 8 cnr / minute x 0.1 g Catalyst; Oxidation activity: 0.06 emv minute x 0.1 g Catalyst.

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Example 12

The procedure was as described in Example 11, but with the difference that was used in place of m-Phenyldiamines a solution of 59 76 gp ~ phenylenediamine and 1 cm of concentrated hydrochloric acid in 35 cm of water _o To 7.8 g of product were obtained

Example 13

The procedure was as described in Example 1, with the difference that instead of the m-aminophenol, a solution of 4.28 g of m-toluidine and 4 cn of concentrated hydrochloric acid in 20 cn of water was used. Thus, 6.8 g Product received. Hydrogenation activity? in terms of eugenol 14- cnr / minute. 0.1 g of catalyst and 11 cnr / minute in terms of nitrobenzene. 0.1 g catalyst?
Oxidation activity% 0.1 emv minute ° 0.1 g catalyst »

Example 14

The procedure was as described in Example 1, with the difference that 4 cm of polyethylene glycol with a molecular weight of 400 were added to the palladium (II) chloride solution. 7-3 g of product were thus obtained »hydrogenation activity in relation to eugenol 7 emv minutes ° 0.1 g catalyst and in relation to nitrobenzene 10 emv minute« 0.1 g catalyst; Oxidation activity ι 0.3 cnr / minute “0.1 g catalyst.

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BATH ORIGINAL

Example 15

The procedure described in Example 1 was followed, with the difference that from a solution of 2.2 g m-aminophenol, 2.4 g urea (carbamide) and 2.5 g melamine

7th

in 75 cnr water with a pH of 8 was assumed. 13 * 4 g of product were obtained in this way.

Hydrogenation activity: in terms of eugenol, 1 cnr / minute x 0.1 g Catalyst and in terms of nitrobenzene 0.5 cnr / minute x 0.1 g Catalyst.

Example 16

The procedure was as described in Example 1, but with the difference that instead of the m-aminophenole one

7th

Solution of 2.4 g urea and 5 g melamine in 130 cnr water were used. 14.6 g of product were thus obtained.

Example 17

It was submerged in 10 cnr 30-3 strength aqueous glyoxal Stir 6.6 g of urea dissolved. A solution of 1.78% palladium (II) chloride in 10 cnr water and the same was used for the solution then a solution of 4.4 g of m-aminophenol in 20 cnr Water added. To the suspension obtained there were added 30 cubic meters of water and then 12 cubic meters of a 35% lormaldehyde solution admitted. The pH was adjusted to about 9 with sodium hydroxide solution. The mixture was heated to 80 ° C for 20 to 30 minutes held, then the product was filtered off and until

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BATH ORIGINAL

Achieving the neutral reaction, after drying in the air at 80 ^° C., 12.4 g of product were obtained. Hydrogenation activity: with respect to eugenol, 1 cmV minute. 0.1 g of catalyst; Nitrobenzene, acetophenone and benzyl cyanide were not reduced. It should be noted that, compared with the prior art, this fact that the hydrogenation of the double bond of eugenol is catalyzed by the catalyst prepared according to the invention, whereas the hydrogenation of nitrobenzene, acetophenone and benzyl cyanide is not, is particularly surprising.

Example 18

The procedure was as described in Example 1, but with the difference that instead of the solution given there a solution of 3 »3 g of m-aminophenol and 1.21 g of (+) - 1-phenylethylamine in 12 cnr 35 # aqueous ethanol was used. 6.5 g of product were thus obtained. Hydrogenation activity: in relation to eugenol 12 cmVmin. 0.1 g Catalyst and in relation to nitrobenzene 20 cmVmin. 0.1 g Catalyst; Acetophenone and benzyl cyanide were not reduced.

Example 19

The procedure was as described in Example 1, but with the difference that from a solution of 3 »3 g m-Arainophenol and 1.21 g (-) - i-Phenylethylamine in 12 cnr 5O # ethanol was assumed. This made 6.8 g of product

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obtain. Hydrogenation activity: with respect to eugenol 12 cnr / minute x 0.1 g catalyst and with respect to nitrobenzene 8 cur / minute. 0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced.

Example 20

13 g of activated carbon (Carbo C extra) were carefully homogenized with a solution of 1.78 g of palladium (II) chloride in 15 cnr of water. A mixture of 4 cm aniline, 4 cm concentrated hydrochloric acid, 2 g D-glucose and 5 cnr v / water was added to the moist mass, which was also homogenized. Finally, the mixture was homogenized with 12 cnr of a 35 # iS ^en aqueous formaldehyde solution and then placed in a drying cabinet (at 100 ^° C.) for 1 hour. Then 60 cnr of water were poured in and the pH was adjusted to about 8 with sodium hydroxide solution. The mixture was kept at 80 to 90 ° C. for a further 20 minutes, then filtered and washed until a neutral reaction was achieved. After drying in the air at 80 ° C., 20 g of product were obtained. Hydrogenation activity: with respect to eugenol 6 cm / minute. 0.1 g of catalyst and, in terms of nitrobenzene, 1 cnr / minute x 0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced.

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030031/0801

Example 21

A solution of 1.28 g of tetrachloroplatinic acid (HoPtC1) and 2 were added to a solution of 1.6 g of m-aminophenol and 2 cpm of 40% sodium hydroxide solution in 20% of water at room temperature g of D-glucose poured into 10 cnr of water. While stirring, 4- ⁵ cm a 35 # ~ iE ^en formaldehyde solution was added to give a white precipitate, which changed color to lemon yellow. The mixture was kept at 80 to 90 ^° C. for 50 to 40 minutes with stirring and its pH value was kept at about 9 by adding lye. Then the product was filtered off, washed until a neutral reaction was reached and at 60 to Air-dried at 80 ° C. This gave 3.1 g of catalyst.

Hydrogenation activity: in relation to eugenol 7 cnr / I ^v -minute. 0.1 g of catalyst and, in terms of nitrobenzene, 4 cnr / minute x 0.1 g of catalyst; Acetophenone and benzyl cyanide were not reduced. Oxidation activity: 0.7 cnr / minute. 0.1 g catalyst »

Example 22

The procedure described in Example 21 was followed, with the difference that from 5i5 S

5 "5 3

m-aminophenol in 20 cm of water and 1.5 cm of aniline + 1.5 cm concentrated hydrochloric acid in 5 cnr water.

12 g of product were thus obtained.

Hydrogenation activity: with respect to eugenol, 2 cnr / minute. 0.1 g Catalyst and in terms of nitrobenzene 0.4 cnr / minute. 0.1 g Catalyst; Acetophenone and benzyl cyanide were not reduced,

Oxidation activity: 0.04 cm ^ / minute. 0.1 g catalyst.

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Zh

Example 23

1.038 g of potassium tetrachloroplatinum (II )ate (KoPtCl ^) were dissolved in 20 cubic centimeters of boiling water. To the still boiling solution, a solution of 1.6 g of m-aminophenol and 1 enr of 40 # sodium hydroxide solution in 5 cnr water was added with stirring. The mixture was stirred for 5 minutes and then 3 »7 cm of a 35 # aqueous formaldehyde solution were added dropwise. The mixture was stirred for a further 10 minutes. The coffee-brown precipitate was stirred for about 50 minutes at 80 to 90 ⁰ C, then filtered, washed to achieve a neutral reaction and dried in the air at 80 ⁰ C. 2.3 g of product were obtained in this way. Hydrogenation activityϊ in relation to eugenol 7 cmvmin. 0.1 g of catalyst and, in terms of nitrobenzene, 5 cnr / minute x 0.1 g of catalyst} acetophenone and benzyl cyanide were not reduced.

example

1.32 g of rhodium (III) trichloride hexahydrate [. 6 HoOj dissolved in 40 cnr water. A solution of 3.3 cubic centimeters of aniline and 3.3 cubic centimeters of concentrated hydrochloric acid in 5 cubic centimeters of water was added to the solution at room temperature with stirring. A strawberry-colored precipitate separated out. To this, a solution of 8 cubic meters of a 35% formaldehyde solution in 8 cubic meters of water was added and the pH was adjusted to 8 to 9 with sodium hydroxide solution. The mixture was heated to 80 to 90 ° C. for 30 to 40 minutes, the pH being kept constant by the occasional addition of sodium hydroxide solution

- 30 030031/0801

Z2>

became. The product was filtered off, washed until a neutral reaction was achieved and air-dried at 80.degree. 4.8 g of product were thus obtained. Hydrogenation activity: with respect to eugenol, 15 cnr / minute. 0.1 g of catalyst; Nitrobenzene, acetophenone and benzyl cyanide were not reduced. Oxidation activity: 0.4 cnr / minute. 0.1 g of catalyst; Carbon Oxide Reduction: 130 ⁰ C.

Example 25

The procedure described in Example 24 was repeated, with the difference that a solution of 3.3 cnr aniline, 2.7 g glycolic acid and 5 cnr water was used. 4.8 g of product were thus obtained. Hydrogenation activity: with respect to eugenol 15 cm / minute. 0.1 g of catalyst and, in relation to nitrobenzene, 0.4 cnr / minute · 0 * 1 S catalyst; Acetophenone and benzyl cyanide were not reduced, oxidation activity: 0.4 cnr / minute. 0.1 g catalyst.

Example 26

1.7 g of silver nitrate (AgNO,) were dissolved in 40 cnr of water . While stirring, a solution of 4.4 g of o-aminophenol and 1.5 cm ^{5 of} concentrated nitric oxide was added at room temperature.

X Z

acid in 30 cnr water added. After 12 cm of a 35 # aqueous formaldehyde solution had been added , the pH was adjusted to 8 to 9 with a soda solution. The mixture was heated for 30 minutes. After cooling down, the

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Washed precipitate with decanting and ^{dried at 80 0} C in the air. 6 g of product were thus obtained.

example 27

1.7 g of silver nitrate (AgNO *) were dissolved in 40 cnr of water. The solution was added with stirring to a solution of 1.5 g of 8-oxyquinoline and 1 cn of concentrated nitric acid in 40 cm of water, and then the solution was adjusted to neutral pH with soda solution. Thereupon 4.4 g of m-aminophenol in 40 cnr water and then 12 cnr of a 35 # aqueous formaldehyde solution were added. The mixture was heated for 30 to 40 minutes at 80 to 9O ⁰ C, the pH was maintained with sodium carbonate solution. 9 The product was filtered off and washed until the reaction was neutral. 7.9 g of product were thus obtained.

Example 28

There were 1.7 S of silver nitrate (AgNO ^) in 40 cm of water solved. While stirring, the solution became a solution of 37 g of salicylaldoxime and 2 cpm of a 20% soda solution added in 50 cnr water. Then 2.2 g of m-aminophenol in 20 cnr of water and then 6 cm of a 35 # aqueous formaldehyde solution and enough soda solution were added that the pH was 9. The mixture lasted for 30 minutes

030031/0801

BATH ORIGINAL

to 80 bit 9O ° C, and then held the Rieder was filtered off, washed to achieve a neutral reaction, and dried at 80 to 90 ° C. 4.3 g of product were thus obtained.

Example 29

A solution of 4.4 g of m-aminophenol in 15 ml of water was added to a solution of 1.34 "6 ammonium perrhenate ReQ ^,)> in 40 cnP of water with stirring. The mixture was then for 5 to 10 minutes stirred for a long time and mixed with 12 cnr of a 35 # iS ^en aqueous formaldehyde solution. The pH value was kept at 8 by adding a little soda solution. The mixture was ^{heated to 80 to 90 °} C. for 30 minutes and then the product was filtered off, washed to achieve a neutral reaction and at 80 C in air dried "yield: 7 61 Oxydationsaktivität: O 0.1 g of catalyst ₁ ^ cm / minute..

Example 30

2.4 g of Kickel (II) chloride hexahydrate ο 6 HoCQ were dissolved in 45 cm ^ of water and made into a solution

10 cm of 25 ^ ammonia were added. First 4.4 g of m-aminophenol in 40 ml of water and then 12 ml of a 35/6 strength aqueous formaldehyde solution were added to the ammonium complex with stirring. The mixture was held at 80 to 90 ^° C. for 30 minutes and then the product became

- 33 030031/0801

filtered off, washed until a neutral reaction is reached and be
Yields 7 »8 g.

washed and dried in the air at 80 C.

Example 51

It was worked in the manner described in Example 30, but with the difference that after the end of the heating a solution of 3 g sodium sulfide _{nonahydrate (Na 2} S.9 HoO) in 10 cnr water was added, the pH with hydrochloric acid to about 4 and the mixture was left to stand at room temperature for 15 I ^{v for} 5 minutes. The black precipitate was filtered off, washed until a neutral reaction was achieved and air-dried at 80.degree. Yield: 6.4 g.

Example $ 2

A solution of 9 »6 g of cobalt (II) chloride hexahydrate [CoCl ₂ . 6 H ₂ OJ in 20 cnr water 40 cnr concentrated ammonia added. The solution was filtered. While stirring, 4.4 g of m-aminophenol in 20 cm of water and then a mixture of 30 cm ⁵ a 35 # -iS ^en aqueous formaldehyde solution and added 6 cnr a # 20 strength sodium hydroxide solution. A dark brown precipitate formed. The pH was adjusted to about 9 with sodium hydroxide solution. The mixture was kept at 80 ^° C. for 30 minutes and then the product was filtered off,

- 34-030031/0801

3?

washed until a neutral reaction is reached and dried ^{at 80 ° C.} Yield: 8.6 g;

Oxidation activity: 0.04 cmV minute. 0.1 g catalyst.

Example 33

It became a solution of 2.4 g of cobalt (II) chloride hexahydrate [CoGl ₂ . 6 H ₂ CQ in 25 cnP of water with stirring a mixture of 4.4 g of o-aminophenol, 15 cm of concentrated ammonia, 2 cm of 40 # sodium hydroxide solution and 40 cm of water. Then 12 cm of a 33% aqueous formaldehyde solution were added. The mixture was heated to 80 ° C. for 30 minutes and then the product was filtered off, washed until a neutral reaction was achieved and air-dried ^{at 80 ° C.} Yield: 5 »1 SJ Oxidizing activity: 0.1 cnr / minute x 0.1 g catalyst.

Example 34-

A solution of 3 »^ g copper (II) chloride dihydrate PCuCl ₂ . 2 H ₂ O] in 40 cubic centimeters of water, with stirring, 8.7 S o-aminophenol and 5 cubic centimeters of a 40 cubic centimeter sodium hydroxide solution in 60 cubic centimeters of water were added. A brown precipitate formed immediately, which was diluted with 60 cnr water. The mixture was then treated with 20 cm of a 35% aqueous formaldehyde solution and the pH was adjusted to about 8 by adding hydrochloric acid. The mixture was kept at 80 to 90 ^° C. for 30 minutes and then the product was filtered off until the temperature was reached

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washed neutral reaction and dried at 80 C in the air. Yield: 10.5 S »

Oxidation activity: 1.4 cnr / minute x 0.1 g catalyst. Thermogravimetric analysis [DTG analysis] with the before the Examples given result.

Example 35

The procedure described in Example 34 was followed, with the difference that the o-aminophenol solution 15 cnr more concentrated ammonia was added. Yield: 5 »2 g; Oxidation activity: 0.4 cnr / minute. 0.1 g Catalyst.

Example 36

A solution of 2.67 g of chromium (III) chloride hexahydrate JTcrCl,. 6 H ₂ O] in 50 cm * of water at -60 ° C with stirring initially a mixture of 4.4 g of p-aminophenol, 15 cm of concentrated ammonia, 3 cm of 40% sodium bicarbonate

• 5 3

Lye and 40 cm V / water were added and then Λ2 cm of a 35 / ·? -ϊε ^Θη aqueous formaldehyde solution were added dropwise. The mixture was heated for 30 minutes at 8O ⁰ C, its pH was maintained at. 9 Then, the product was filtered off, washed to achieve a neutral reaction and dried in air at 8O ⁰ C. Yield: 4.0 g.

- $ 6 030031/0801

Example 57

There were a solution of 2.8 g of iron (II) sulfate heptahydrate [FeSO ^. 7 H ₂ O] and 2 g D-glucose in 50 cnr ⁵ water at room temperature with stirring initially a mixture of 4.4 g m-phenylenediamine, 15 cnr concentrated ammonia, 2 cnr 40 # sodium hydroxide solution and 40 cnr water and then 12 cm ^ of a 35 # strength aqueous formaldehyde solution was added. ^{The mixture was stirred at 80 °} C. for 30 to 40 minutes. The product was filtered off, washed until a neutral reaction was achieved and ^{dried at 80 °} C. in the air. Thus 7 »8 S substance were obtained» The product was paramagnetic (K = 757 · 10 "/ g iron). Carbon oxide reduction: 250 ° C.

Example 38

A solution of 5> 6 S iron (II) sulfate heptanydrate JHFeSQ ^. 7 Ηρ ^ 3 · * " ^η - ^ ^c water with stirring 20 cb of a 35% aqueous formaldehyde solution and 4 cm of a 40% sodium hydroxide solution were added. A blue-green precipitate immediately fell out. The mixture was 1 cnr made alkaline with a 40 # strength sodium hydroxide solution and then heated to 80 to 90 C and treated with 8.8 g of m-aminophenol

χ ο

added in 30 cnr water. The temperature from 80 to 90 C. was held for 30 minutes. Then the product became cooled, washed until a neutral reaction was achieved and dried in the air at 100.degree. So were

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12.8 6 of a ferromagnetic (o '= 70.3 / g Fe) substance was obtained. Thermogravimetric analysis [DTG analysis] with the result given in front of the examples.

Example 39

There were a solution of 12.35 S ammonium

molybdate tetrahydrate in 50 cnr water while stirring initially

3 ζ

4 ×, 4- g of m-aminophenol in 15 cm of water and then 15 cm of a 35 # aqueous formaldehyde solution were added. A milk coffee-brown precipitate formed. The pH of the mixture was 3 and was adjusted to 8 to 9 with sodium hydroxide solution. The mixture was stirred at 80 to 90 ° C. for 30 minutes and then the product was filtered off, washed until the reaction was neutral
dries. Yield: 10.5 g «

neutral reaction and washed at 100 ⁰ C in the air

Example 40

It resulted in a solution of 1.1? g of ammonium vanadate [^ VO ~ j cnr in 10 of water with stirring 4.4 g of m-aminophenol was added in 15 cnr water and then 24 cnr a 18 # aqueous formaldehyde solution. The mixture was stirred at 80 to 90 ^{° C. for about 30 minutes.} The product was then filtered off, washed until a neutral reaction was achieved and ^{dried at 100 °} C. in the air. Yield: 51 g; Oxidation activity: 0.02 cnr / minute. 0.1 g catalyst.

030031/0801

Example 41

It imrde to an aqueous solution of 0.85 g of copper (II) chloride dihydrate £ CuCl ₂ ο 2 H ₂ O]] and 1.34 g of chromium (III) = chloride hexahydrate jjCrClz ο 6 HpOl in 50 cm of water while stirring a mixture from 4.4 g of o-aminophenol, 15 cnr concentrated ammonia, 2 cnr of a 40 # strength sodium hydroxide solution and 40 cnr water and then 12 cm ^{5 of} a 35 # strength aqueous formaldehyde solution added C stirred »Then the product was filtered off, washed until a neutral reaction was achieved and dried in the air at 100 ° C. Yield? 4.45 oxidation activity % 0.5 cm / minute "0.1 g catalyst"

Example 42

The procedure described in Example 41 was followed, with the difference that instead of the m-aminophenol, a solution of 4.4 g of aminophenol and 4 cm of concentrated hydrochloric acid in 25 cw of water was used. This solution was added 4 cnr of a 40 # sodium hydroxide solution added, yield? 4.25 g? Oxidation activity s 0.9 emv minute ° 0.1 g catalyst =,

Example 43

There were added to a solution of 7 _S 4 g of nickel (II) chloride hexanydrate JJJiCl _{2 o} 6 H ₂ Oj, 1.2 g of ammonium molybdate hydrate [CNH ^) ₂ MoO _{4 o} 4 H ₂ O], 0.2 g of copper ( II) ~ chloridehexa ~

- 39 630031/0801

hydrate [CuOl ₂ . 6 H ₂ Oj and 0.14 g of cobalt (II) chloride hexahydrate [CoCl ₂ · 6 H ₂ 0 ~ | in 50 cm of water with stirring first a solution of 8.8 g of o-aminophenol, 30 cm of concentrated ammonia and 4 cm of 40 # sodium hydroxide solution in 80 cm of water and then 24 cm of 35 # aqueous formaldehyde solution. The mixture was stirred at 80 to 90 ^{° C. for about 50 minutes.} The product was then filtered off, washed until a neutral reaction was achieved and ^{dried at 100 °} C. in the air. Yield: 11.6 g; Oxidation activity: 0.08 cnr / minute x 0.1 g catalyst.

Example 44

50 cm of water, a little wetting agent and, with stirring, 2 g of silica gel (Aerosil R 972) were placed in a 150 cm beaker. A solution of 4 cm aniline, 4 cm concentrated hydrochloric acid and 10 cm water was added to the suspension. A weakly acidic solution of 1.78 g of palladium (II) chloride in 15 cm of water, in which 1 g of D-glucose had previously been dissolved, was then added. Finally, 12 cnr of a concentrated (35 #) "aqueous" formaldehyde solution were added dropwise. The acidic solution was adjusted to a pH of 9 to 10 with sodium hydroxide solution and then ^{stirred for 1} hour at 80 to 90 ° C. The product was stirred filtered off, washed until a neutral reaction and chlorine-free and then dried.

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Example 4-5

It turned out to be 14 g of alumina with great specificity

P ^ t

Surface area (about 2 ^ 0 m / g) in a 150 mm beaker a solution of 4 cm aniline, 4 cm concentrated hydrochloric acid and 10 cm water was added. The mixture was homogenized and then all at once with a solution of 1.78 g palladium ( II) chloride was added to 10 cm of weakly acidic water. Finally, 12 cnr of a concentrated

gen) aqueous formaldehyde solution added the acid The pH was neutralized with sodium hydroxide solution and the mixture was evaporated to dryness at 100 ° C. in a drying cabinet. The dry residue was suspended in water / water, filtered off until a neutral reaction was achieved and Washed chloride-free and finally dried hydrogenation activity 5 in relation to eugenol / minute 0.1 g Catalyst and in relation to nitrobenzene 0 enr / canoe ° 0.1 g Catalyst.

Example 46

2.5 hours of the product obtained according to Example 30 were obtained with a solution of 2.2 g of m-aminophenol in 5 cnr Impregnated with water, then triturated with a solution of 0.6 g of palladium (II) chloride in 5 enr weakly acidic water and finally with 6 enr one concentrated

ⁿ ) aqueous formaldehyde solution added = after homogenization, the mixture was kept at 90 to 95 ° C. for U hours. The product was filtered off ₉ until the reaction was neutral and free of chloride

and finally dried at 80 ⁰ C. Hydrogenation activity: in relation to eugenol M cnr / minute · 0.1 g catalyst and in relation to nitrobenzene 2 cnr / minute. 0.1 g catalyst.

Example 4-7

A solution of 2.2 g of m-Amir.ophenol,

Z Z

10 cnr water and 1 cm concentrated hydrochloric acid at $ 0 ° C for 2 cnr a concentrated Q5 # -ig ^s) aqueous formaldehyde solution in 2 cm v / ater was added dropwise. Then 1 cnr of a 40% sodium hydroxide solution was added dropwise with stirring and cooling. A loose, cheesy, light yellow precipitate formed. This was immediately followed by a

Solution of 2.2 g of m-aminophenol in 5 cnr water and added homogenized and then a solution of 0.6 g palladium (II) chloride in 5 cnr weakly acidic water was added.

puts. Finally, 6 cnr of a concentrated (35 # strength) aqueous formaldehyde solution were added dropwise with stirring. The thin liquid mass was held for 4 to 5 hours at 95 ° C up to the level of the neutral reaction and washed free of chloride and dried at 80 ⁰ C.

Hydrogenation activity: in relation to eugenol 4 cm / minute. 0.1 g Catalyst and with respect to nitrobenzene 2 cm / minute. 0.1 g catalyst.

Claims

030031/0801

BATH ORIGINAL

Claims (1)

Claims 1.) Method of making 1 or more complex - / 'bound metals containing polymers by Implementation of ions and / or a complex respectively of complexes of at least 1 metal with at least 1 compound, which with this Metal or these metals form or form a complex or complexes form or is or is suitable for incorporation into his or her ligand space are, in solution, characterized in that the compound (s) for reacting with the ions and / or the or the complex (s) of the metal or metals such or those with polymerizable sites and / or at least 2 polymerizable functional groups polymerizable [V] organic complexing agents} used and the complex compounds obtained in this way, in which or the at least 1 place in the ligament space of the metal respectively of metals from polymerizable orp / ariische-n Complexing agents or from the polyrr.eri: pi erbaren organic complexing agents are taken, polymerizes " 2 =) Process according to claim 1, characterized in that one or more none for the polymerization Complex forming], but to the Kiribau in the Polymer-capable component (s) are also used. 030031/0801 ORIGINAL 3.) Method according to claim 1 or 2, characterized in that that after the polymerization, the or not polymerize organic Complexing agents removed thermally or chemically and, if necessary, by a other or other complexing agents replaced. 4.) The method according to claim 1 to 3 »characterized in that the production of the complex Performs polymers containing bonded metals on supports. 5.) Method according to claim Ί to 4, characterized in that that one as polymerizable [n ~) organic complexing agents aniline and / or Phenol and / or a derivative or derivatives of one or both of the same and / or urea used and the polymerization of the complex compound (s) obtained with 1 or more Aldehyde (s), especially formaldehyde, performs. c.) Method according to claim 1 to 4, characterized in that that as poly ^ erisable ^ n "] organic jf} complexing agent 1 or more di- and / or polycarboxylic acid (s) and / or derivative (s) of such or of such used and the polymerization of the complex compounds obtained) with 1 or more di- and / or polyalcohol (s) and / or diamine (s) carried out » 030031/0801 ORlGiNAL 7.) Process according to Claim 1 to 4, characterized in that the polymerisable jjrfj organic ^ n] complexing agents 1 or more unsaturated Bonds having, optionally with initiators, polymerizable organic Connection (s) used. 8.) The method according to claim 1 to 7, characterized in that the production of the complex Polymers containing bonded metals on the surface of other polymers that are still have suitable vacancies for polymerization and possibly also complex bound ones Metals contain, carries out and the 2 or more polymers by means of 1 or more polymerizing or polymerising constituents ^ "> connects with each other. 9 ·) Process according to claim 1 to 8, characterized in that 1 or more salt (s) and / or complex (s) of at least 1 are used as starting material containing metal ions and / or consisting of Λ or more metal complex (s) active metal used. 10.) Use of the according to the method according to claim 1 to 9 obtained polymers containing 1 or more complexed metals as catalysts, for magenta tapes or as semiconductors » 030031/0801 BATH ORIGINAL