GB2047258A

GB2047258A - Polymers Containing Metals in Complex Form and a Process for the Preparation Thereof

Info

Publication number: GB2047258A
Application number: GB8002084A
Authority: GB
Original assignee: Magyar Tudomanyos Akademia
Current assignee: Magyar Tudomanyos Akademia
Priority date: 1979-01-23
Filing date: 1980-01-22
Publication date: 1980-11-26
Also published as: NL8000390A; DE3002318A1; FR2453191A1; HU186349B; JPS5599901A; LU82106A1; BE881253A

Abstract

The invention relates to a process for the preparation of polymers containing metals in complex form. The new polymers prepared according to the invention, which also form the subject matter of the invention, can be applied to advantage as hydrogenation catalysts, furthermore in the production of magnetic tapes and semiconductors. According to the invention the ions and/or a complex of at least one metal in one solution are/is contacted with at least one compound which is able to form a complex with the above metal(s) or to enter its (their) ligand field and which contains functional groups or sites capable of polymerization, and the resulting complex, in which at least one position of the ligand field of the metal is occupied by the polymerizable organic complexing substance, is subjected to condensation or addition polymerization.

Description

SPECIFICATION Polymers Containing Metals in Complex Form and a Process for the Preparation Thereof The invention relates to a process for the preparation of polymers containing metals in complex form from solutions of metal ions or complexes. More particularly the invention relates to a process for the preparation of polymers containing metals in complex forms, in which at least one of the complexing agents is also a constituent of the polymer. The invention also relates to the resulting polymers.

The aim of the invention is to provide a simple process for the preparation of substances which can be used to advantage in various fields owing to the chemical and physical properties of the metals bonded to the organic polymer chain by complex bonds and the properties of the macromolecule-metal complex. Thus, for instance, by means of the process according to the invention catalysts can be prepared which have the advantageous properties of homogeneous and heterogeneous catalysts without their main disadvantages. One can also prepare ferromagnetic iron-complex macromolecules which contain finely distributed metal, applied to advantage for the preparation of magnetic tapes.The process of the invention can also be used to prepare products which have different electric conductance properties from those of the organic polymers with the same matrix but containing the metal in other than complexed form, and thus they can be applied to particular advantage as semiconductors.

The invention is based on the recognition that when a metal complex is formed with an organic substance which has functional groups or sites capable of polymerization, and after complex formation the complex is polymerized, solid metal complexes embedded into the organic matrix are obtained. In such a way a wide variety of novel solid metal complexes can be prepared.

According to the invention the polymer containing metals in complex form is prepared by contacting the ions and/or complexes of at least one metal in one solution with at least one compound which is able to form a complex with the above metal(s) or to enter its ligand field, and which contains functional groups or sites capable of polymerization, and by polymerizing the resulting complex in which at least one position of the ligand field of the metal is occupied by the polymerizable organic complexing substance.

As starting substance it is preferred to use a solution of a soluble salt or complex of the metal to be built into the polymer matrix. Of course, if a complex of the metal is used, it should be an exchangeable complex, i.e. the polymerizable organic complexing compound should be able to enter the ligand field of the starting complex.

As polymerizable organic complexing compound an organic compound can be used which on the one hand contains functional groups able to form complexes, and on the other hand can be converted into polymer by polymerization, such as polycondensation, polyaddition or any other known polymerization processes. As an example, aniline and aniline derivatives, phenol and phenol derivatives are mentioned, which are polymerized preferably with an aldehyde, e.g.

formaldehyde. As polymerizable organic complexing compound a di- or polycarboxylic acid or a derivative thereof can also be used, and in this case the polymer is formed preferably with a di- or polyalcohol or a di- or polyamine derivative.

According to another method of polymer formation, as organic complexing agent a compound containing unsaturated bond is applied which, after complex formation, is polymerized in the usual manner, optionally after addition of appropriate initiators.

The complexes can be formed in any suitable solvent. Water is a preferred solvent, but water miscible or water immiscible organic solvents, multi-component organic solvent systems or mixtures of water and one or more water miscible organic solvent(s) can be applied as well. The starting metal compound and the polymerizable organic complexing agent can be reacted by dissolving the reactants in the same solvent, but they can be dissolved in different solvents also, and then the solutions can be admixed.

It is noted that when the other components used for polymerization do not influence complex formation and are inert with respect to the starting metal compound, they can be added to the system prior to complex formation.

After the above operations a complex is formed in which at least one polymerizable organic complexing substance occupies the ligand field of the metal.

It is not necessary that all sites of the ligand field are occupied by the polymerizable organic complexing substance. The remaining ligand sites may contain various other ligands, such as ammonia or organic complexing agents, optionally compounds with centre(s) of asymmetry, e.g. phenylethylamine.

The complex obtained in the above manner is then polymerized. Polymerization can be performed by any known method, with the use of the commonly used initiators, polycondensation co-monomers, polymerization auxiliary agents and, if desired, additives. The polymer matrix can be varied within wide limits by adding to tne monomer or monomer mixture to be polymerized other monomers which do not take part in complex formation, but build into the polymer matrix. Such modifying co-monomers are, for instance, phenol and melamine.

Polymerization is performed by commonly used techniques. The temperature of polymerization is determined by the nature of the monomers and the reaction medium.

Polymerization is carried out preferably in the temperature range of 3500 to 4200 K, but lower or higher temperatures may be applied as well.

Polymerization may be carried out at atmospheric pressure or at higher pressures.

After the end of polymerization the product can be separated from the reaction mixture by known methods. If desired, the product can be modified by removing from it the components removable by thermal or chemical treatment and, if desired, by introducing into the product further substances capable of entering the ligand field.

According to a preferred method of the invention, the salts of the metal are dissolved in a suitable solvent, in the simplest case in water, and the organic compound with functional groups or sites capable of polymerization which is able to form a complex with the ions of the given metal or, if starting from a solution of metal complex, it is able to enter the ligand field of the metal, is added to this solution under stirring, preferably in a common solution formed with an appropriate solvent, in the case of aniline and phenol derivatives preferably in water with optimum pH, optionally together with complexing substances containing no functional groups capable of polymerization, and optionally with noncomplexing substances which take part in polymerization.After some minutes of stirring the polymerizing component is added; in the case of aniline and phenol derivatives this may be an aqueous solution of an aldehyde, in the simplest case formaldehyde. In order to complete polymerization, the resulting suspension is stirred optionally for 30 to 60 minutes at 3500 to 4000 K, filtered, washed to remove accompanying substances, and dried. If a polyester-type polymer, e.g. the polymer of diaminotetraacetic acid and ethylene glycol, or if a polyamide-type polymer, e.g. the polymer of triethylene tetramine and terephthalic acid is to be formed, the process is similar to the above. First the aqueous or organic solution of the complexing agent is reacted with the solution of the metal ion or metal complex.The precipitate is filtered, and then reacted with polymerizing component or preferably with its non-aqueous solution, preferably at a temperature above 3600K in order to remove water formed in the reaction. In the case of polymerization, starting e.g. from paminostyrene, first the complex is formed again, and then it is dissolved in an appropriate solvent, organic peroxide is added, heated for some hours, then the solvent is removed by filtering and the product is dried in vacuo.

If neccesary, the ligands not taking part in polymerization are then removed partly or completely by thermal or chemical treatment and, if desired, they can be replaced with other ligands by impregnation, sorption or other appropriate methods.

The metal polymer complexes can also be prepared on the surface of carriers by means of the process of the invention. Such carrier can be active carbon, Al2O3, silica gel and the like, in particular substances widely used in the preparation of catalysts. The substance is deposited on the support preferably by impregnation. One can proceed by impregnating the support first with the organic complexing agent, and then with a solution of a salt or a complex of the metal. Then the polymerizing component (e.g. formaldehyde) is added, the system is heated, and finally the product is separated and washed.

As a special case of carrier, it may also be a polymer which contains sites for further polymerization. The carrier polymer may contain the same components as the polymer matrix holding the complexed metal, but it may be different as well. The carrier polymer itself may also contain complexed metal. In this case a sandwich structure may be formed with the metal containing polymer matrix deposited on the carrier when the various layers of the matrix contain different complexed metals. This property may also be advantageous in the application as catalyst.In such cases one may proceed preferably by first impregnating the polymer used as carrier e.g. with the polymerizable organic complexing component, then adding the solution of metal salt and finally the other polymerizing component which on the one hand forms the surface polymer matrix and on the other hand links the two polymer systems.

As mentioned, the product prepared according to the invention can be used in various fields, including the use as catalysts. The process according to the invention is very important since it enables one to prepare hitherto unknown types of catalysts with completely new properties.

These catalysts show the advantages of metal complex catalysts as well as those of heterogeneous metal catalysts.

An advantage of metal complex catalysts is high selectivity. They have, however, several disadvantages, such as relatively complicated and expensive preparation methods, occasional sensitivity towards moisture and poor separability from the reaction mixture. The preparation of heterogeneous metal catalysts is often simpler, cheaper and less vulnerable than that of the corresponding metal complexes. Their activities are usually higher, they can be separated easily from the reaction mixture, and simply regenerated, but their selectivity is often inferior to that of metal complexes. Recently much attention has been devoted to the combination of the advantages of metal complex and metal catalysts. With this aim, for instance, the surfaces of various solid substances were transformed chemically so as to enable metal complexes to be bound by chemical bonds to the resulting chemical groups on the surface. These operations are, however, very complicated, precarious and the catalysts formed are frequently sensitive even to atmospheric humidity.

By means of the process according to the invention catalysts can be prepared that show the advantages of both catalyst types discussed above, and are devoid of several disadvantages characteristic of these catalysts. According to the process of the invention many, hitherto un studied metal complex-metal catalysts can be prepared.

The number of variations is very large, various metal combinations can be applied. The complexing agents may also be varied, even optically active substances are usable and the ligand field influences the catalytic properties. The composition of the polymer matrix holding the complex can also be influenced by noncomplexing substances built into the polymer matrix which also effect the properties of solid metal-complex catalysts. Consequently, from one metal, such as palladium alone, a whole family of catalysts can be produced.

The solid metal-complex powders prepared according to the invention have high thermal and complex stabilities up to at least 4600 to 6000K, and their solvent resistance is also good. Owing to their low specific weight they are easily miscible and volume-filling in liquid phase. They also have excellent filtering properties.

The preparation techniques are simple; in the case of aniline, aniline derivatives, phenol or phenol derivatives as complexing component, for instance, the preparation method is simpler than that of the simplest metal catalysts. In many instances aqueous media can be used, the preparation steps are simple, not precarious, and take very short time.

The method requires the simplest apparatus possible, and thus the investment costs are very low, which is most advantageous in industrial realization.

Some of the catalysts, such as the solid palladium complex catalyst prepared with phenol derivatives as complexing agent, are active and selective hydrogenation catalysts already at room temperature and atmospheric pressure, without being pyrophoric. This latter property, which is particularly advantageous in industrial applications, is generally characteristic of the catalysts prepared according to the invention. The complexes of noble metals are usually active in catalytic hydrogenation and oxidation; those of transition metals in oxidation and carbon monoxide reduction. These examples are only for illustrating the catalytic properties of the catalysts according to the invention; the field of application of these catalysts is much wider than mentioned here.

The sensitivity to poisoning of the metal complex catalysts prepared according to the invention is lower than that of the corresponding metal catalysts.

Owing to the large number of possible combinations, the catalytic properties of the catalysts prepared according to the invention have been tested only in some simple cases.

These examples do not limit the scope of applicability.

Liquid phase catalytic hydrogenation at room temperature and atmospheric pressure was carried out as follows. 20 cm3 of ethanol, 0.1 g of the catalyst to be tested, 0.5 cm3 of eugenol, benzylcyanide or acetophenone or 0.17 cm3 of nitrobenzene were placed into a 250 cm3 round bottom flask. After closing the flask it was flushed with nitrogen and then with hydrogen. Thereafter the mixture was shaken at 160 r.p.m., and the amount of hydrogen consumed was measured volumetrically. The activity was calculated from the initial consumption rate of hydrogen in Cm3/min. related to 0.1 g of catalyst.

Liquid phase oxidation activity was determined as follows. 20 cm3 of 10% ascorbic acid and 0.1 g of the catalyst to be tested were introduced into a 80 cm3 glass flask. The flask was flushed with nitrogen and then with oxygen, and the temperature was set with an accuracy of +0.2 C by means of a thermostat. The magnetic stirring was started at approx. 120 r.p.m. The activity was calculated from the initial rate of oxygen consumption in cm3/min. related to 0.1 g of catalyst.

The magnetic measurements were carried out with a Faraday type instrument at temperatures between room temperature and 6230K. For the substances prepared according to Examples 1,34 and 38 thermogravimetric measurements were also performed. They indicated that in the samples containing m-aminophenol strong weight change and decomposition can be observed at approx. 5730K, whereas in the samples containing o-aminophenol this phenomenon occurs at approx. 4430 and 5730K.

The measurements were carried out with an Erdey-Paulik-Paulik derivatograph. In the thermogravimetric measurements 35 to 45 mg samples were investigated in a quartz crucible, under nitrogen atmosphere.

Activities in the hydrogenation of carbon monoxide were determined in a flowing tube reactor, using about 0.1 to 0.2 g of catalyst, and a gas mixture of 12 cm3 of hydrogen and 3 cm3 of carbon monoxide, at atmospheric pressure. The reactor was connected to a gas chromatograph.

In the Examples the ignition temperature is given, i.e. the lowest temperature at which the reaction sets in.

The invention is elucidated in detail with the aid of the following non-limiting Examples.

Example 1 A solution of 1.78 g of PdCi2 in 50 cm3 of water is introduced into a 250 cm3 cylindrical flask, and a solution of 4.4 g of m-aminophenol in 20 cm3 of water is then added at room temperature under vigorous stirring. Further 20 cm3 of water are added to the resulting suspension, and then 12 cm3 of concentrated aqueous formaldehyde solution are introduced under stirring. The mixture is stirred then at 3630 to 3680K for 30 minutes. The dark brown precipitate is filtered off on a sintered glass filter, washed until neutral, and dried in air at 3530K.

6.7 g of a palladium-containing catalyst are obtained. Using this catalyst, cinnamic aldehyde can be reduced into hydrocinnamic aldehyde with a selectivity and yield of 95 to 98%. The hydrogenation activity of the catalyst is 11 on eugenol and 12 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. Carbon monoxide reduction: 3830K (DTG analysis).

Example 2 One proceeds as described in Example 1 with the difference that 0.58 of CuCl2.H2O are also introduced with PdCl2. 6.6 g of a Pd/Cu catalyst are obtined. The hydrogenation activity of the catalyst is 1 on eugenol and 3 on nitrobenzene; it does not reduce acetophene and benzyl cyanide.

Carbon monoxide reduction: 4230K.

Example 3 One proceeds as described in Example 1 with the difference that 2 g of D-glucose are also dissolved in the aqueous solution of PdCl2. 0.2 g of aluminium scrapings are also introduced into the reaction mixture simultaneously with the addition of formaldehyde, whereupon hydrogen evolves in the acidic medium. After 10 to 15 minutes of heating the pH of the mixture is adjusted to about 8 with aqueous sodium hydroxide solution. 6.8 g of Pd catalyst are obtained. The hydrogenation activity of the catalyst is 11 on eugenol and 11 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.3.

Example 4 One proceeds as described in Example 1 with the difference that o-aminophenol is substituted for m-aminophenol. 5.7 g of Pd catalyst are obtained. The hydrogenation activity of the catalyst is 9 on eugenol and 10 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.2.

Example 5 One proceeds as described in Example 1 with the difference that p-aminophenol is substituted for m-aminophenol. 4.7 g of Pd catalyst are obtained. The hydrogenation activity of the catalyst is 21 on eugenol and 15 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.35.

Example 6 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced by a solution of 4 cm3 of aniline and 4 cm3 of conc.

hydrochloric acid in 20 cm3 of water, and during heating the pH of the acidic mixture is adjusted to neutral with NaOH. 5 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 6 on eugenol and 12 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.3.

Example 7 One proceeds as described in Example 1 with - the difference that m-aminophenol is dissolved in 40 cm3 of water, and a solution of 9.4 g of phenol in 50 cm3 of water is added to it. 23 cm3 of a concentrated aqueous solution of formaldehyde are applied. 7.9 g of a Pd catalyst are obtained.

The hydrogenation activity of the catalyst is 9 on eugenol and 12 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide.

Example 8 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced by a solution of 5 cm3 of m-chloroaniline and 4 cm3 of conc. hydrochloric acid in 10 cm3 of water. 6.7 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 1 on eugenol and 2 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide.

Example 9 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced by a solution of 6.9 g of p-amino-benzenesulfonamide and 1 cm3 of conc. hydrochloric acid in 50 cm3 of water.10.8 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 3 on eugenol and 5 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.25.

Example 10 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced by a solution of 5.76 g of m-phenylenediamine hydrochloride in 30 cm3 of water. 6.5 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 5 on eugenol and 4 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.3.

Example 11 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced by a solution of 5.76 g of o-phenylenediamine and 1 cm3 of conc. hydrochloric acid in 35 cm3 of water.

4.2 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 9 on eugenol and 8 on nitrobenzene; its oxidation activity is 0.06.

Example 12 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced by a solution of 5.76 g of p-phenylenediamine and 1 cm3 of conc. hydrochloric acid in 35 cm3 of water.

7.8 g of a Pd catalyst are obtained. The resulting catalyst has no measurable hydrogenation and oxidation activities at room temperature.

Example 13 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced with a solution of 4.28 g of m-toluidine and 4 cm3 of conc. hydrochloric acid in 20 cm3 of water. 6.8 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 14 on eugenol and 11 on nitrobenzene; its oxidation activity is 0.1.

Example 14 One proceeds as described in Example 1 with the difference that 4 cm3 of polyethylene glycol (molecular weight: 400) are also added to the PdC13 solution. 7.3 g of a Pd catalyst are obtained.

The hydrogenation activity of the catalyst is 7 on eugenol and 10 on nitrobenzene; its oxidation activity is 0.3.

Example 15 One proceeds as described in Example 1 with the difference that a solution of 2.2 g of maminophenol, 2.4 g of urea and 2.5 g of melamine in 75cm3 of water (pH=8) is applied. 13.4 g of a Pd catalyst are obtained. This catalyst has no detectable hydrogenation activity at room temperature.

Example 16 One proceeds as described in Example 1 with the difference that m-aminophenol is replaced with a solution of 2.4 g of urea and 5 g of melamine in 130 cm3 of water. 14.6 g of a Pd catalyst are obtained. This catalyst has no detectable hydrogenation activity at room temperature.

Example 17 6.6 g of urea are dissolved with stirring in 10 cm3 of a 30% aqueous solution of glyoxal. A solution of 1.78 g of PdCI2 in 10 cm3 of water is added, followed immediately by a solution of 4.4 g of maminophenol in 20 cm3 of water. 30 cm3 of water and then 12 cm3 of a 35% aqueous formaldehyde solution are added to the resulting suspension.

Thereafter the pH of the acidic mixture is adjusted to about 9 with NaOH, and the mixture is heated at 3530K for 20 to 30 minutes. The precipitate is filtered off, washed until neutral, and dried in air at 3530K. 12.4 g of a Pd catalyst are obtained.

The hydrogenation activity of the catalyst is 1 on eugenol; it does not reduce nitrobenzene, acetophenone and benzyl cyanide.

Example 18 One proceeds as described in Example 1 with the difference that a solution of 3.3 g of maminophenol and 1.21 gof(+)-1- phenylethylamine in 12 cm3 of 35% aqueous ethanol is applied. 6.5 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 12 on eugenol and 20 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide.

Example 19 One proceeds as described in Example 1 with the difference that a solution of 3.3 g of maminophenol and 12.1 gof(-)-1- phenylethylamine in 12 cm3 of 50% aqueous ethanol is applied. 6.8 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 12 on eugenol and 8 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide.

Example 20 13 g of activated carbon (Carbo C extra) are thoroughly homogenized with a solution of 1.78 g of PdCI2 in 1 5 cm3 of water. A solution of 4 cm3 of aniline, 4 cm3 of conc. hydro-chloric acid and 2 g of D-glucose in 5 cm3 of water is added to the wet mass under thorough blending. The resulting mass is homogenized with 12 cm3 of a 35% aqueous formaldehyde solution, and then it is heated at 3730K in a drying oven for one hour. 60 cm3 of water are poured onto the mass, and the pH of the liquid phase is adjusted to about 8 with NaOH under stirring. The resulting suspension is heated for additional 20 minutes at 3530 to 3630K, thereafter the solids are filtered off, washed until neutral, and dried in air at 3530K.

20 g of a Pd catalyst are obtained. The hydrogenation activity of the catalyst is 6 on eugenol and 1 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide.

Example 21 A solution of 1.28 g of H2PtCI4 and 2 g of Dglucose in 10 cm3 of water is poured at room temperature into a stirred solution of 1.6 g of maminophenol and 2 cm3 of 40% aqueous NaOH in 20 cm3 of water. 4 cm3 of a 35% aqueous solution of formaldehyde are added to the resulting solution with stirring, whereupon a white precipitate appears. The precipitate turns lemon yellow or darkens, respectively. The suspension is stirred at 3530 to 3630K for 30 to 40 minutes, and the pH of the mixture is maintained at about 9 by introducing an alkali.

Thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3330 to 3530K.

3.1 g of a Pt catalyst are obtained. The hydrogenation activity of the catalyst is 7 on eugenol and 4 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.7.

Example 22 One proceeds as described in Example 21 with the difference that a solution of 5.5 g of maminophenol in 20 cm3 of water and a solution of 1.5 cm3 of aniline and 1.5 cm3 of conc.

hydrochloric acid in 5 cm3 of water are applied.

12 g of a Pt catalyst are obtained. The hydrogenation activity of the catalyst is 2 on eugenol and 0.4 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.04.

Example 23 1.038 g of K2PtCl4 are dissolved in 20 cm3 of hot water, and a solution of 1.6 g of maminophenol and 1 cm3 of 40% aqueous NaOH in 5 cm3 of water is added with stirring to the still hot solution. The mixture is stirred for about 5 minutes, then 3.7 cm3 of a 35% aqueous formaldehyde solution are added dropwise, and the resulting mixture is stirred for additional 10 minutes. The separated coffee-brown precipitate is stirred for about 50 minutes at 3530 to 3630K, thereafter it is filtered off, washed until neutral, and dried in air at about 3530K. 2.3 g of a Pt catalyst are obtained. The hydrogenation activity of the catalyst is 7 on eugenol and 5 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide.

Example 24 1.32 g of RhCl3.6H20 are dissolved in 40 cm3 of water. A solution of 3.3 cm3 of aniline and 3.3 cm3 of conc. hydrochloric acid in 5 cm3 of water is added with stirring at room temperature, whereupon a pink precipitate separates. 8 cm3 of a 35% aqueous formaldehyde solution and 8 cm3 of water are added to the resulting suspension, and the pH of the mixture is adjusted to about 8 to 9 with NaOH. The mixture is stirred at 3530 to 3630K for 30 to 40 minutes, and the pH is maintained between about 8 and 9 by introducing an alkali. The precipitate is filtered off, washed until neutral, and dried in air at 3530K. 4.8 g of a Rh catalyst are obtained. The hydrogenation activity of the catalyst is 1 5 on eugenol; it does not reduce nitrobenzene, acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.4.Carbon monoxide activity: 5030K.

Example 25 One proceeds as described in Example 24 with the difference that a solution of 3.3 cm3 of aniline and 2.7 g of glycolic acid in 5 cm3 of water is applied. 4.8 g of a Rh catalyst are obtained. The hydrogenation activity of the catalyst is 1 5 on eugenol and 0.4 on nitrobenzene; it does not reduce acetophenone and benzyl cyanide. The oxidation activity of the catalyst is 0.4.

Example 26 A solution of 4.4 g of o-aminophenol and 1.5 cm3 of conc. nitric acid in 30 cm3 of water is added at room temperature to a stirred solution of 1.7 g of AgNO3 in 40 cm3 of water. Thereafter 12 cm3 of a 35% aqueous formaldehyde solution are added, the pH of the mixture is adjusted to 8 to 9 with caustic soda and the resulting mixture is heated for 30 minutes. The mixture is cooled, the precipitate is washed by decanting, and then dried in air at about 3530K. 6 g of a silver catalyst are obtained. The catalyst has no detectable oxidation activity at room temperature.

Example 27 A solution of 1.7 g of AgNO3 in 40 cm3 of water is added to a stirred solution of 1.5 g of 8 oxyquinoline and 1 cm3 of conc. nitric acid in 40 cm3 of water. The pH of the resulting mixture is adjusted to neutral with caustic soda. Thereafter a solution of 4.4 g of m-aminophenol in 40 cm3 of water is introduced, followed by 12 cm3 of a35% aqueous formaldehyde solution. The mixture is heated at 3530 to 3630K for 30 to 40 minutes, and the pH is maintained at about 9 by introducing caustic soda. The precipitate is filtered, washed until neutral and dried. 7.9 g of silver catalyst are obtained, which has no detectable oxidation activity at room temperature.

Example 28 A solution of 1.7 g of AgNO3 in 40 cm3 of water is added to a stirred solution of 1.37 g of salicylaldoxime, 2 cm3 of 20% soda lye and 50 cm3 of water. Thereafter a solution of 2.2 g of maminophenol in 20 cm3 of water is added, followed by 6 cm3 of 35% aqueous formaldehyde solution. During this operation the pH of the mixture is maintained at about 9 by introducing caustic soda. The mixture is heated at 3530 to 3630K for 30 minutes, thereafter the precipitate is filtered off, washed until neutral and dried at 3530 to 3630K 4.3 g of a silver catalyst are obtained. The catalyst has no detectable oxidation activity at room temperature.

Example 29 A solution of 4.4 9 of m-aminophenol in 15 cm3 of water is added to a stirred solution of 1.34 g of NH4ReO4 in 40 cm3 of water. After 5 to 10 minutes of stirring, 12 cm3 of a 35% aqueous formaldehyde solution are introduced. If necessary, a small amount of caustic soda is added to the mixture in order to maintain the pH at about 8, and the mixture is heated at 3530 to 3630K for 30 minutes. The precipitate is filtered off, washed until neutral, and dried in air at 353JK. 7 g of a Re catalyst are obtained.

Example 30 2.4 of NiCl2.6H20 are dissolved in 45 cm3 of water, and 10 cm3 of 25% aqueous ammonia are added. A solution of 4.4 g of m-aminophenol in 40 cm3 of water is added with stirring to the resulting ammonium complex, followed by 12 cm3 ofa 35% aqueous formaldehyde solution. The mixture is heated at 3530 to 3630K for 30 minutes, thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3530K.

7.8 g of a Ni catalyst are obtained. The catalyst has no detectable hydrogenation and oxidation activities at room temperature.

Example 31 One proceeds as described in Example 30 with the difference that after heating a solution of 3 g of Na2S.9H20 in 10 cm3 of water is added to the suspension. The pH of the mixture is adjusted to about 4 with hydrochloric acid, and the resulting ~ mixture is allowed to stand at room temperature for about 15 minutes. The resulting black precipitate is filtered off, washed until neutral, and dried in air at 3530K. 6.4 g of a Ni catalyst are obtained. This catalyst has no detectable hydrogenation and oxidation activities at room temperature.

Example 32 40 cm3 of conc. aqueous ammonia are added to a solution of 9.6 g of CoCl2.6H20 in 20 cm3 of water, and the resulting solution is filtered. A solution of 4.4 g of m-aminophenol in 20 cm3 of water is added to the stirred filtrate, followed by a mixture of 30 cm3 of a 35% aqueous formaldehyde solution and 6 om3 of a 20% aqueous sodium hydroxide solution, whereupon a dark brown precipitate separates. The pH of the suspension is adjusted to about 9 by introducing a lye, and the mixture is heated at about 3530K for about 30 minutes. The precipitate is filtered off, washed until neutral, and dried at about 3530K.

8.6 g of a Co catalyst are obtained. The oxidation activity of the catalyst is 0.04.

Example 33 A solution of 4.4 g of o-aminophenol, 1 5 cm3 of cc. aqueous ammonia, 2 cm3 of 40% aqueous sodium hydroxide solution in 40 cm3 of water is added to a stirred solution of 2.4 g of CoCl2.6H20 in 25 cm3 of water. Thereafter 12 cm3 of a 33% aqueous formaldehyde solution are added dropwise into the mixture. The mixture is heated at about 3530K for 30 minutes, thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3530K. 5.1 g of a Co catalyst are obtained. The oxidation activity of the catalyst is 0.1.

Example 34 A solution of 8.7 g of o-aminophenol and 5 cm3 of 40% aqueous NaOH solution in 60 cm3 of water is added to a stirred solution of 3.4 g of CuCI2.2HzO in 40 cm3 of water. A brownish precipitate forms immediately, which is diluted with 60 cm3 of water. Thereafter 20 cm3 of a 35% aqueous formaldehyde solution are introduced, and the pH of the mixture is adjusted to about 8 with hydrochloric acid. The mixture is heated at 3530 to 3630K for about 30 minutes, thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3530K. 10.5 g of a copper catalyst are obtained. The oxidation activity of the catalyst is 1.4 DTG analysis.

Example 35 One proceeds as described in Example 34 with the difference that 15 cm3 of conc. aqueous ammonia are also added to the solution containing o-aminophenol. 5.2 g of a copper catalyst are obtained. The oxidation activity of the catalyst is 0.4.

Example 36 A solution of 4.4 g of p-aminophenol, 1 5 cm3 of conc. aqueous ammonia, 3 cm3 of 40% aqueous NaOH in 40 cm3 of water is added at 3330K to a stirred solution of 2.67 g of CoCl3.6H20 in 50 cm3 of water. Thereafter a mixture of 12 cm3 of a 35% aqueous formaldehyde solution and 12 cm3 of water is added dropwise to the resulting mixture. The mixture is heated at 3530K for about 30 minutes; during this operation the pH of the mixture is maintained at about 9. The precipitate is filtered off, washed until neutral, and dried in air at about 3530K. 4.0 g of a Co catalyst are obtained. The catalyst has no detectable oxidation activity at room temperature.

Example 37 A solution of 4.4 g of m-phenylenadiamine, 1 5 cm3 of cc. aqueous ammonia and 2 cm3 of 40% aqueous NaOH in 40 cm3 of water is added at room temperature to a stirred solution of 2.8 g of FeSO4.7H20 and 2 g of D-glucose in 50 cm3 of water. Thereafter 12 cm3 of a 35% aqueous formaldehyde solution are introduced, and the mixture is stirred at about 3530K for 30 to 40 minutes. The precipitate is filtered off, washed until neutral, and dried in air at 353 OK. 7.8 g of a paramagnetic iron catalyst are obtained; X=757x 10-6/g of iron. The catalyst has no oxidation activity at room temperature; its carbon monoxide activity is 5230K.

Example 38 A mixture of 20 cm3 of a 35% aqueous formaldehyde solution and 4 cm3 of a 40% aqueous NaOH solution is added to a stirred solution of 5.6 g of FeSO4.7H2O in 50 cm3 of water. A blueish-green precipitate forms immediately. The pH of the mixture is neutral; it turns alkaline upon introducing 1 cm3 of a 40% aqueous NdOH solution. The suspension is heated to 3530 to 3630K, and a solution of 8.8 g of m- aminophenol in 30 cm3 of water is added. The mixture is heated at 3530 to 3630K for about 30 minutes, thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3730K.

12.8 g of a ferromagnetic iron catalyst are obtained (cur=70.3 g/Fe). The catalyst has no oxidation activity at room temperature. DTG analysis.

Example 39 A solution of 4.4 g of m-aminophenol in 1 5 cm3 of water is added to a stirred solution of 12.35 g of ammonium molybdate tetrahydrate in 50 cm3 of water, followed by 1 5 cm3 of a 35% aqueous formaldehyde solution. A light brownish precipitate separates from the acidic mixture (pH=3). The pH of the mixture is adjusted to about 8 to 9 with NaOH solution, and the mixture is stirred at 3530 to 3630K for 30 minutes. The precipitate is filtered off, washed until neutral, and dried in air at 3730K. 10.5 g of a Mo catalyst are obtained. The catalyst has no oxidation activity at morn temperature.

Example 40 A solution of 4.4 g of m-aminophenol in 15 cm3 of water is added to a stirred solution of 1.17 g of NH4VO3 in 10 cm3 of water, followed by 24 cm3 of a 18% aqueous formaldehyde solution.

The mixture is stirred at 3530 to 3630K for about 30 minutes, thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3730K. 5.3 g of a vanadium catalyst are obtained.

The oxidation activity of the catalyst is 0.02.

Example 41 A mixture of 4.4 g of o-aminophenol, 1 5 cm3 of conc. aqueous ammonia, 2 cm3 of 40% aqueous NaOH and 40 cm3 of water is added to a stirred solution of 0.85 g of CuCl2.2H20 and 1.34 g of CrCl3.6H20 in 50 cm3 of water, followed by 12 cm3 of a 35% aqueous formaldehyde solution.

The mixture is stirred at 3530 to 3630K for about 30 minutes, thereafter the precipitate is filtered off, washed until neutral, and dried in air at 3730K. 4.45 g of a Cu/Cr catalyst are obtained.

The oxidation activity of the catalyst is 0.5.

Example 42 One proceeds as described in Example 41 with the difference that solution of 4.4 g of paminophenol and 4 cm3 of cc. hydrochloric acid in 25 cm3 of water is applied, and after introducing this solution 4 cm3 of a 40% aqueous NaOH solution is added to the mixture. 4.25 g of a Cu/Cr catalyst are obtained. The oxidation activity of the catalyst is 0.9.

Example 43 A mixture of 8.8 g of o-aminophenol, 30 cm3 of conc. aqueous ammonia, 4 cm3 of 40% aqueous NaOH solution and 80 cm3 of water is added to a solution of 7.4 g of NiCl2.6H20, 1.2 g of ammonium molybdate tetrahydrate, 0.2 g of CuCI2.6H20 and 0.14 g of CoCl2.6H20 in 50 cm3 of water under stirring. Thereafter 24 cm3 of a 35% aqueous formaldehyde solution are introduced, and the mixture is stirred at 3530 to 3630K for about 30 minutes. The precipitate is filtered off, washed until neutral, and dried in air at 3730K. 11.6 g of a Ni/Mo/Cu/Co catalyst are obtained. The oxidation activity of the catalyst is 0.08.

Example 44 30 cm3 of water and a small amount of a wetting agent are introduced into a 150 cm3 cylindrical flask, and 2 g of a silica gel with high surface area (such as Aerosil R 972) are added.

Therafter a solution of 4 cm3 of aniline and 4 cm3 of conc. hydrochloric acid in 10 cm3 of water is added to the mixture. A slightly acidic solution of 1.78 g of palladium chloride and 1 g of D-glucose in 1 5 cm3 of water is then introduced, followed by 12 cm3 of a concentrated aqueous formaldehyde solution. The pH of the acidic mixture is adjusted to 9 to 10 with sodium hydroxide solution, and the resulting mixture is heated at 3600K for 30 minutes. The precipitate is filtered off and washed until neutral and free of chloride ions. The hydrogenation activity of the resulting Pd catalyst is 8 on eugenol and 2 on nitrobenzene.

Example 45 14 g of aluminium oxide with high surface area (about 250 m2/g) are filled into a 150 cm3 cylindrical flask, and a solution of 4 cm3 of aniline and 4 cm3 of conc. hydrochloric acid in 10 cm3 of water is added. The suspension is homogenized, and a slightly acidic solution of 1.78 g of palladium chloride in 10 cm3 of water is added in one batch. Thereafter 12 cm3 of a concentrated aqueous formaldehyde solution is poured into the mixture. The pH of the acidic mixture is adjusted to neutral with sodium hydroxide solution, and the mixture is evaporated to dryness in a drying oven at 3800 K. The resulting solid substance is suspended in water, filtered, and then washed until neutral and free of chloride ions. The hydrogenation of the resulting Pd catalyst ia 1 on eugenol and 0 on nitrobenzene.

Example 46 2.5 g of the catalyst prepared according to Example 30 are impregnated with a solution of 2.2 g of m-aminophenol in 5 cm3 of water. The resulting mass is triturated evenly with a slightly acidic solution of 0.6 g of palladium chloride in 5 cm3 of water, and finally 6 cm3 of a concentrated aqueous formaldehyde solution are added. The mass is homogenized, heated at 2730K for 4 hours, thereafter the solid is washed until neutral and free of chloride ions and dried at 3500 K. The hydrogenation activity of the resulting catalyst is 4 on eugenol and 2 on nitrobenzene.

Example 47 A mixture of 2 cm3 of concentrated aqueous formaldehyde solution and 2 cm3 of water is added dropwise to a solution of 2.2 g of maminophenol and 1 cm3 of conc. hydrochloric acid in 10 cm3 of water at 3030K. Thereafter 1 cm3 of a 40% aqueous sodium hydroxide solution is added dropwise to the mixture under cooling. A loose, light yellow precipitate separates. A solution of 2.2 g of m-aminophenol in 5 cm3 of water is introduced immediately, the mixture is homogenized, and then a slightly acidic solution of 0.6 g of palladium chloride in 5 cm3 of water is added. The mixture is homogenized again, and 6 cm3 of a concentrated aqueous solution of formaldehyde are added dropwise to the stirred mixture. The thin, flowable mass is maintained at 3700K to 4 to 5 hours, thereafter the catalyst is washed until neutral and free of chloride ions and dried at 3500K. The hydrogenation activity of the resulting catalyst is 4 on eugenol and 2 on nitrobenzene.

Claims

1. A process for the preparation of a polymer containing a metal complex form, characterized in that the ions and/or complex of at least one metal in one solution are/is contacted with at least one compound which is able to form a complex with the above metal(s) or to enter its (their) ligand field and which contains functional groups or sites capable of polymerization, and the resulting complex, in which at least one position of the ligand field of the metal is occupied by the polymerizable organic complexing substance, is subjected to polymerization.

2. A process as claimed in claim 1 , wherein a non-complexing second component capable of being built into the polymer is also applied in the polymerization.

3. A process as claimed in claim 1 or claim 2 wherein the non-polymerized complexing agent is removed by thermal or chemical treatment from the product of polymerization and, if desired, it is exchanged for another complexing agent.

4. A process as claimed in any one of the preceding claims wherein the polymer containing a metal in complex form is formed on a carrier.

5. A process as claimed in any one of the preceding claims wherein aniline, an aniline derivative, phenol or phenol derivative is applied as polymerizable organic complexing substance, and the resulting complex is polymerized with an aldehyde.

6. A process as claimed in claim 5 wherein the aldehyde is formaldehyde.

7. A process as claimed in any one of claims 1 to 4 wherein a di- or polycarboxylic acid or a derivative thereof is applied as polymerizable organic complexing substance, and the resulting complex is polymerized with a dialcohol or a polyacohol.

8. A process as claimed in any one of claims 1 to 4 wherein an organic compound containing unsaturated bond, capable of polymerization upon the effect of an initiator, is applied as polymerizable organic complexing substance.

9. A process as claimed in any one of the preceding claims wherein polymer containing a metal in complex form is formed on the surface of a second polymer still containing free sites capable of polymerization, said second polymer containing optionally a metal in complex form, and then the two polymer matrixes are coupled with each other with a polymerizing component.

10. A process as claimed in any of the preceding claims for the preparation of solid complex catalysts, wherein the ions or complex of at least one catalytically active metal are (is) applied as starting substance.

11. A process for the preparation of a polymer containing a metal in a complex form as claimed in claim 1 substantially as hereinbefore described in any one of the Examples.

12. A polymer containing a metal in complex form, whenever prepared according to any of claims 1 to 9 and 11.

13. A solid complex catalyst, whenever prepared according to claim 10.