DE102021106741A1 - Mechanochemical synthesis process using a catalytically active shaped body - Google Patents

Abstract

The present invention relates to a mechanochemical process for the direct heterogeneous catalysis of a chemical reaction, comprising the following steps: (a) providing at least one starting material; (b) providing a shaped body, wherein the shaped body comprises at least one catalytically active material; and (c) direct grinding of the at least one starting material to form a product by bringing it into contact with the shaped body in an energy-transferring manner; wherein the shaped body has an inert core material and at least one outer layer which is formed from the catalytically active material (i.e. active component) and wherein the outer layer is arranged on the surface of the core material, and the use of a catalytically active shaped body in this chemical reaction.

Description

technical field

The present invention relates to a mechanochemical process for direct heterogeneous catalysis of a chemical reaction, a catalytically active shaped body, and the use of a catalytically active shaped body in this chemical reaction.

State of the art

About 90% of all chemical production processes are catalyzed nowadays. Catalysis allows raw materials to be processed into valuable chemicals and fuels either in the first place or in an economically more efficient and ecologically compatible way. It is therefore of crucial importance for a large number of chemical processes, for example in the food, automotive, chemical, petrochemical and pharmaceutical industries. In both heterogeneous and homogeneous catalysis, a catalyst is added to the reaction mixture and has to be separated from it again after the reaction. In classical heterogeneous catalysis, a gas flows through a fixed catalyst bed, with a gaseous product being formed from a gaseous starting material. The reaction itself usually takes place in reactors that are thermally heated. This heating is necessary to overcome the activation energy of the chemical reaction.

However, for homogeneous catalysis, both the reactants and the catalyst must be soluble in a solvent. After the chemical reaction, the catalyst has to be separated from the reaction mixture in a complicated manner.

Above all, heterogeneous catalysts therefore play a dominant role, as they can be easily separated from most fluid reaction products. Depending on the energy source used to overcome the activation energy, a distinction is made between thermal, electro and photocatalysis. In recent years, however, mechanocatalysis has also become increasingly important. Here, energy is introduced into the system in a locally limited manner (e.g. at the impact cross section of the balls in ball mills), whereby extreme pressures and temperatures are generated selectively and products are made accessible which cannot be synthesized in the classic way. So far, in mechanocatalysis, the catalyst was added to the reaction mixture as an additional solid phase (indirect mechanocatalysis) and the mill was used exclusively for energy input. In this context, indirect mechanocatalysis means that the catalyst is added as an additional powder [Hernandez et al.; Tetrahedron Letters, 56(29), 2015-07-15, 4253-4265].

WO 2007/023295 A2 describes one of the first mechanocatalytic processes for the production of organometallic compounds. For this purpose, the starting compounds (ie starting materials) are placed together with catalysts in a grinding device (eg a mill) which has an inert surface and are polymerized by being ground together.

In addition, for example in US 9,206,098 B2 proposed the production of organic compounds in a mechanocatalytic process with metal‐based catalysts. In this specific case, pre-treated cellulose is processed into sugar alcohols. As in the WO 2007/023295 A2 the catalyst is added to the starting compounds in the form of a dry powder.

The aforementioned processes have the disadvantage that the (inner) surfaces of the grinding device are not directly involved in the reaction, so that a catalyst always has to be added. After the chemical conversion of the educts, this must be laboriously separated from the product and purified.

At the in the US 9,701,542 B2 The process described is an inorganic mechanocatalysis in which hexagonal osmium boride is produced in a ball mill. In this case, no additional catalyst is added, which also does not have to be separated off or deposited after the chemical reaction. The chemical conversion is based on the reactivity of the inorganic starting compounds and can therefore not be transferred to the formation of organic compounds. The wall (ie the surface) of the grinding device is irrelevant for the reaction as long as it has sufficient hardness.

Furthermore, in Fulmer et al. (Green Chemistry 2009, 11(11):1821; DOI: 10.1039/B915669K) describe a process in which the grinding balls take on the role of the co-catalyst in a Sonogashira reaction. In this case, grinding balls and grinding vessels (beakers) made of copper were used, replacing the usual copper(I) iodide and regenerating the actual palladium catalyst (Pd(PPh ₃ ) ₄ ).

In another method by Cook et al. (Green Chemistry 15(3):617-619; 10.1039/C3GC36720G), the same copper beakers and grinding balls are used as in Fulmer et al. (2009) used in the catalysis of a click reaction coupling alkynes with azides. However, this catalytic process has the disadvantage that the copper, due to its low hardness (Mohs hardness 3.0), low strength (320 MPa) and the low bulk modulus (138 GPa), can only introduce a very small amount of energy into the reaction and also the metal abrasion and the associated input of particulate copper into the reaction mixture is very high. Due to the high level of metal abrasion, a downstream, complex separation process is required here, which is disadvantageous. In addition, the majority of the starting materials used must be in the form of liquids.

the DE 10 2019 117 437 discloses a mechanochemical process for the direct heterogeneous catalysis of a chemical reaction, in which the entire shaped body is formed from the catalytically active material and at least one of the starting materials in the heterogeneously catalyzed chemical reaction is used as a solid. However, this has the disadvantage that not all of the catalytically active material used is available for the reaction (ie it is chemically dead or inactive). This is very costly, particularly when using expensive catalysts.

task

It is therefore desirable to provide a mechanochemical process for directly catalyzing a chemical reaction heterogeneously which overcomes the aforementioned disadvantages.

The object of the present invention is therefore in particular to provide a mechanochemical process in which the catalytic properties of the shaped body and its bulk properties (e.g. density, deformability) are decoupled from one another.

solution

According to the invention, this object is achieved by a mechanochemical method for directly heterogeneously catalyzing a chemical reaction according to claim 1.

Further advantageous configurations are specified in the dependent claims.

1. a) Bereitstellen zumindest eines Edukts;
2. b) Bereitstellen eines Formkörpers, wobei der Formkörper zumindest ein katalytisch aktives Material (d.h. Aktivkomponente) umfasst; und
3. c) direktes Vermahlen (mechanochemisches Umsetzen) des zumindest einen Edukts zu einem Produkt durch energieübertragendes Inkontaktbringen, insbesondere wiederholtes energieübertragendes Inkontaktbringen dieser Edukte mit dem Formkörper;

wobei der Formkörper ein inertes Kernmaterial und zumindest eine Außenschicht aufweist, die aus dem katalytisch aktiven Material (d.h. Aktivkomponente) gebildet ist und wobei die Außenschicht auf der Oberfläche des Kernmaterials angeordnet ist.The mechanochemical method according to the invention for the direct heterogeneous catalysis of a chemical reaction comprises the following steps:

1. a) providing at least one starting material;
2. b) providing a shaped body, wherein the shaped body comprises at least one catalytically active material (ie active component); and
3. c) direct grinding (mechanochemical conversion) of the at least one starting material to form a product by bringing these starting materials into contact with the shaped body by energy-transferring contact, in particular repeated energy-transferring contacting;

wherein the shaped body has an inert core material and at least one outer layer which is formed from the catalytically active material (ie active component) and wherein the outer layer is arranged on the surface of the core material.

Here, an inert core material is a material that does not take part directly in the chemical reaction, namely because on the one hand it has no (or no measurable) catalytic property for the chemical reaction itself and/or because it is protected by the layer arranged on its surface (the catalytically active material and / or the intermediate layer) can not participate in the reaction. Preferably, the inert core material itself has no (or no measurable) catalytic property for the chemical reaction in which the shaped body defined herein or the ground shaped catalyst body is used.

It is particularly advantageous here if the mass of the core material is in excess of the mass of the catalytically active material, with the general advantages resulting from this being listed below. Thus, it is desirable that the ratio between the mass of the core material and the mass of the catalytically active material is in the range from 5,000,000:1 to 2:1, preferably in the range from 100,000:1 to 100:1, most preferably in the range from 100,000:1 to 1,000:1. Consequently, the core material essentially determines the density of the shaped body and thus the energy input during the mechanochemical conversion.

General Benefits

Because only the outer layer (herein also referred to as “outer layer”) of the shaped body is formed from the catalytically active material, the shaped body not only serves as a catalyst, but the catalytic properties of the catalytically active material and the bulk Properties of the molded body (e.g. hardness, density, deformability, modulus of elasticity, thermal conductivity, electrical conductivity and formability during production) are decoupled from one another. The outer layer, which is formed from the catalytically active material, therefore makes up preferably <10% by weight, particularly preferably <1% by weight, very particularly preferably <0.1% by weight of the total weight of the shaped body.

On the one hand, this allows the shaped body to be designed according to the invention, with only the outer layer (here also referred to as the “outer layer”) of the shaped body being formed from the catalytically active material, such that soft metals (which have high deformability and/or high abrasion such as gold) can be immobilized/deposited on hard and/or heavy core materials (which allow a high input of kinetic energy into a chemical reaction, such as steel, zirconium oxide, tungsten carbide).

On the other hand, an alternative design of the shaped body nevertheless allows hard and/or heavy metals or alloys (which have low deformability and/or low abrasion, but are usually very expensive, such as platinum or palladium) to soft core materials ( which, compared to shaped bodies that are formed as a solid material from a catalytic material, allow a reduction in the input of kinetic energy into a chemical reaction) of the shaped body can be immobilized/deposited.

All in all, the catalytic activity (e.g. by selecting the most suitable catalytically active material) and the impact energy to be introduced can be adjusted in a targeted manner independently of one another via the shaped bodies.

Since only the outer layer is formed from the catalytically active material in the direct mechanocatalysis (i.e. mechanochemical process for direct heterogeneous catalysis of a chemical reaction) according to the invention, the core material can consequently be formed from a significantly cheaper material. As a result, the present invention allows a thin layer of a catalytically active but very expensive material such as platinum to be deposited onto an inert but very cheap material such as steel while maintaining the same catalytic activity as a bulk material.

In addition, this structure of the shaped body allows the decoupling of the density of the shaped body and the material of the shaped body or the catalytically active material. This means that the core material of the shaped body can be made of a light material, for example a plastic, and only the outermost layer can be made of a catalytically active material, for example a catalytically active metal. By "fine tuning" the structure of the shaped body, this allows control over the energy input and thus the avoidance of degradation of the shaped body and the reaction products due to excessive energy input. This advantageously avoids the formation of unwanted by-products and increases the yield of the desired product. In addition, the longevity of the shaped body can be increased, abrasion of the grinding material can be reduced and contamination of the product by material abrasion can be reduced at the same time.

Nevertheless, the structure according to the invention of the shaped body with the outer layer of a catalytically active material allows a greater variety in the selection of the catalytically active material. For example, the inventors have recognized that not all materials can be used to form a shaped body from a solid material of the catalytically active material (e.g. a solid (milling) ball) that can withstand the mechanical stress during the milling process, because this, for example would be soft (e.g. gold). In contrast, it allows the inventive method that as the core material for the Molding a hard material (e.g. steel, zirconium oxide, tungsten carbide) can be used and preferably any solid catalytically active material can be used as the coating material. In the context of the invention, the aforementioned hard core materials (in particular steel, zirconium oxide, tungsten carbide, bronze, copper, brass, Hastelloy) are heavy materials which are characterized by a high density of more than 6 g/cm ³ and thus a ""high" energy input into the mechanochemical reaction.

As a result, the concept of coating a core material with the catalytically active material according to the invention allows the catalytically active material to be provided via the outer layer for the mechanochemical conversion and at the same time the activation energy required for the chemical reaction to be released via the density and/or hardness of the provide core material. In particular, all catalytically active metals can be deposited on “soft” core materials (as described below) in order to enable chemical reactions with low or moderate activation energies, while at the same time the abrasion of the catalytically active material during the mechanochemical conversion is significantly reduced.

It goes without saying that it is therefore not necessary to add a catalytically active material in the form of granules and/or in powder form, and it is particularly preferred to dispense with it entirely.

In a preferred embodiment of the present invention, at least one of the starting materials in the heterogeneously catalyzed chemical reaction is used as a solid.

The solids content of all components—educts (ie reactants or a second active component) and inert materials—in (or during) the heterogeneously catalyzed chemical reaction is preferably more than 30% by weight.

If the direct mechanocatalysis according to the invention is a solid reaction, the addition of a solvent can also be dispensed with and the solubility of the starting materials and/or products in a solvent suitable for this purpose is advantageously no longer important. Consequently, chemical reactions and compounds are also accessible that previously could not be implemented or produced in solvent-based reactions.

In addition, the accumulation of unnecessary waste is reduced by the (solvent-free) mechanochemical process. This represents a serious ecological and economic advantage over conventional methods, since waste does not have to be disposed of separately, which saves time, money and energy (especially for large-scale or industrial application).

In addition, the catalysts used (homogeneous and/or heterogeneous) advantageously do not have to be removed from the reaction mixture first after the chemical conversion (reaction) has taken place, but can be easily removed from the reaction mixture due to the size of the shaped bodies.

In addition, the method according to the invention particularly advantageously allows purely mechanical energy to be used for direct heterogeneous catalysis of a chemical reaction, such as the formation of organic bonds such as polymerization processes, and thus the reaction can be carried out under mild reaction conditions.

The inventors of the present invention have also found that the mechanochemically catalyzed reactions usually take place faster than in comparable classic chemical processes, which reduces the time and energy expenditure.

In a particularly preferred embodiment of the present invention, the method for directly heterogeneously catalyzing a chemical reaction is carried out as a solid phase reaction. The term “solid phase reaction” means here that all starting materials are added to the reaction as solids. Advantageously, this means that the addition of a solvent can be completely dispensed with, which on the one hand makes it possible to dispense with separating the product from one or the solvent and, on the other hand, purifying the solvent after the chemical conversion of the starting materials (i.e. reaction) can be dispensed with.

According to a preferred embodiment, the solids content of all components—educts (reactants or second active components) and inert material—in (or during) the heterogeneously catalyzed che mix reaction at least more than 30% by weight, preferably at least 50% by weight, very particularly preferably at least 65% by weight, even more preferably at least 80% by weight, such as 81% by weight, 82% by weight %, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, such as 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 % by weight based on all components of the reaction mixture. This means that a large part or even the majority of the components provided for the chemical reaction, ie the starting materials directly involved in the reaction and any added inert material, with the exception of the shaped body, is a solid under the given reaction conditions. The starting materials are added in the form of (possibly porous) powder or granules

For example, in reactions that are catalyzed by bases or acids, the reaction mixture can have a high proportion of preferably at least 30% by weight, preferably at least 50% by weight (ie in excess), very particularly preferably at least 65% by weight, even more preferably at least 80% by weight of all components of the reaction mixture, at least one second active component added as a further reactant involved in the reaction (e.g. bases, acids), which is a solid under the given reaction conditions and thus also serves as bulk material . For example, (earth) alkali metal carbonates (eg Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ ), (earth) alkali metal hydroxides (eg NaOH) or organic bases are added in the form of solids in coupling reactions. The addition of the high proportion of a solid second active component is particularly advantageous when the majority of the starting materials are liquids under the given reaction conditions. In contrast to the shaped body or the catalytically active material, the second active component also serves as a bulk material and is therefore preferably added to the reaction mixture in the form of (possibly porous) powder or granules. Provision can be made for the second active component to be added at least in excess in relation to the other starting materials in the present reaction, for example in a 2-fold, 3-fold, 4-fold, 5-fold or 6-fold overprotection .

In order to ensure the high proportion of solid components during the mechanochemically catalyzed reaction (e.g. if the majority of the starting materials are liquids under the given reaction conditions), the reaction mixture can alternatively also preferably contain a solid inert material or an inert solid (i.e. an additive which is not participates directly in the reaction) with a high proportion of preferably at least 30% by weight, preferably at least 50% by weight (ie in excess), very particularly preferably at least 65% by weight, even more preferably at least 80% by weight. % measured on all components of the reaction mixture. Examples of suitable solid inert materials are (earth) alkali metal halides (e.g. NaCl, KCl, CaCl ₂ , BaCl ₂ ), inert metal oxides (e.g. BeO, MgO, TiO ₂ , ZrO ₂ , ZnO, Al ₂ O ₃ , SiO ₂ ), mixed oxide ceramics such as ATZ / ZTA, aluminum nitride (AIN), silicon carbide (SiC), silicon nitride (Si ₃ N ₄ ), tungsten carbide (WC), boron carbide (B ₄ C), cubic boron nitride (c-BN) or graphite. The inert material thus serves exclusively as bulk material and is therefore preferably added to the reaction mixture in the form of (possibly porous) powder or granules. It can be provided that the solid inert material is added at least in excess, such as for example 2-fold, 3-fold, 4-fold, 5-fold or 6-fold overprotection in relation to the present reaction.

The added proportion of the solid second active component or the inert solid is preferably chosen so that the total proportion of solids, i.e. all components involved in the reaction (educts (reactants or second active components) and the inert material before the start of the chemical reaction is more than 30 % by weight, preferably at least 50% by weight, very particularly preferably 65% by weight, even more preferably at least 80% by weight, such as 81% by weight, 82% by weight, 83% by weight , 84% by weight, 85% by weight, 86% by weight, 87% by weight, 88% by weight, 89% by weight, 90% by weight, such as 91% by weight, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt% calculated on all The person skilled in the art knows that he can determine the amount of second active component to be added or inert solid to be added by simply determining the difference, first determining the amount of starting material to be used (e.g. by weighing) and then determining the amount of two Iter active component or inert solid is preferably added as a difference to the aforementioned threshold values before the mechanochemically catalyzed reaction.

The high total proportion of solids, as defined above, of all components involved in the reaction in the form of starting materials (i.e. reactants or second active components) but also as inert material during the mechanochemically catalyzed conversion advantageously enables better energy transfer, which leads to higher conversions of the starting materials .

Conversely, it has been shown that in the case of mechanochemically catalyzed reactions in which the vast majority of the starting materials are solids under the given reaction conditions, the addition of small amounts of a liquid as a grinding aid to the mechanochemically catalyzed reaction with an amount in the range between 0 and 1 μl of liquid per mg of material (so-called η value) favors the mechanochemically catalyzed conversion (so-called “liquid assisted grinding”). The added liquid does not serve as a solvent as in a classic solution, but as a grinding aid improves the mass transfer of the reactants during the mechanochemically catalyzed conversion.

Detailed definition of the invention

catalyst

A "catalyst" or a "catalytically active material" as used herein means a substance that affects the reaction rate of a chemical reaction and lowers the activation energy without itself being consumed or altered during or by the chemical reaction. Consequently, the catalyst emerges from the reaction unchanged and does not become part of the reaction product. Advantageously, regeneration of the catalyst or of the catalytic material is not necessary during the reaction or afterwards.

According to the invention, the mechanochemical process is “direct heterogeneous catalysis” (also referred to herein as “direct heterogeneous catalysis of a chemical reaction” or “catalytic reaction”). For the purposes of the present invention, this means that the catalytically active material not only serves as a co-catalyst, intermediate or regeneration agent for the actual catalyst, but rather induces the catalytic reaction itself.

"Energy-transferring bringing into contact" of the shaped body during step (c) of the direct mechanochemical conversion of the at least one starting material into a product means in the context of the present invention that the collision between the shaped body and the starting material (in the reaction space) results in an energy input into the system takes place, e.g. temperatures above 1000°C and pressures in the gigapascal range occur locally for a short time. At least in a grinding vessel (e.g. a planetary ball mill) up to 100 g acceleration acts on the shaped body (e.g. in the form of a grinding ball), so that corresponding to E _kin = ½ mv ² a high amount of kinetic energy (and the short-term hotspots between the shaped bodies) is transferred to the reactant molecule or the contact pressure of the shaped body on a wall of the reaction vessel is very high.

Advantageously, the mechanochemical reactions take place at temperatures in the reaction space (e.g. the grinding vessel) that are much lower than in classic thermally activated reactions in a flask. Advantageously, the reaction space (with the starting materials or products contained therein) itself and the atmosphere in the reaction space remain below the temperature that is normally required for classic heterogeneous catalysis.

The energy-transferring contacting of the starting materials with the shaped body in step (c) is preferably carried out repeatedly over a period of at least 5 minutes, very particularly preferably over a period of between 10 minutes and 48 hours. Repeated contacting over a longer period of time is hardly desirable for industrial processes.

In order to minimize unwanted deformation of the shaped body during the mechanochemical process, the catalytically active material has a bulk modulus of at least 160 GPa, preferably at least 175 GPa.

It is also desirable for the catalytically active material to have a Mohs hardness of at least 3.0, preferably at least 3.5, very particularly preferably at least 4.0, which advantageously makes it possible to avoid undesired (metal) abrasion of the shaped body (cf. Table 3).

Due to the high compression modulus and the high moss hardness, the shaped body, which comprises or consists of the catalytically active material, can be used repeatedly in a mechanochemical process. Not least because of this, the mechanochemical method disclosed herein is advantageously suitable for large-scale technical fields of application.

In addition, it has been shown that the use of catalytically active materials that have a high bulk modulus and / or a high Mohs hardness is advantageous in the mechanochemical process disclosed herein, since they are significantly more active, which is reflected in (significantly) higher sales in the chemical reactions (see Table 3). One reason for this seems to be an increased energy transfer to the educts associated with the higher bulk modulus or the higher Mohs hardness, which leads to a higher efficiency in the ball-wall collisions.

The table below lists the bulk modulus and the Mohs hardness of catalytically active materials which are particularly preferably used in the mechanochemical process according to the invention. bulk modulus [GPa] Mohs hardness Ru 220 6.5 Rh 380 6.0 no 180 3.8 Pd 180 4.8 pt 230 4.3 feet 170 4.0 co 180 5.0 Ouch 220 3.0 Cu (reference) 138 3.0

The catalytically active material preferably comprises a metal from the group consisting of an (elemental) metal from groups 3 to 13 of the periodic table (PSE), preferably gold (Au), silver (Ag), copper (Cu), palladium (Pd), Platinum (Pt), Ruthenium (Ru), Rhodium (Rh), Rhenium (Re), Nickel (Ni), Iron (Fe), Cobalt (Co), Chromium (Cr), Yttrium (Y), Titanium (Ti), Vanadium (V), ruthenium (Ru), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), iron (Fe), cobalt (Co), gold (Au) or a mixture are particularly preferred thereof, in particular an alloy with these metals. It can also be provided that the catalytically active material is one of the aforementioned (elemental) metals, i.e. that the catalytically active material does not contain any other components, such as catalytically active (metal) salts, regenerating agents for regenerating the catalytically active material or the like are added.

According to a preferred embodiment of the present mechanochemical method, a metal alloy such as a Pt/Au, Pd/Au, Fe/Co, Fe/Ni, Fe/Cr, Fe/Mn, Ni/Pt, Ni/Pd, Pt/Cu, Pd/Cu, Cu/Sn or Cu/Zn alloys are used. The use of alloys advantageously allows the degree of hardness of the catalytically active material and thus also of the shaped body to be adjusted in a targeted manner, as a result of which the energy transfer and input during the direct mechanochemical conversion of the at least one starting material into a product can be improved by bringing it into contact with the shaped body in an energy-transferring manner . In addition, by using alloys whose bulk modulus and/or Mohs hardness meets the values defined herein as the catalytically active material, undesired material abrasion and/or undesired deformation of the catalytically active material and, as a result, of the shaped body during the mechanochemical process can be advantageously minimized or even be prevented.

In principle, there are endless possibilities to increase the hardness of catalytically active materials very simply by adding another metal. In addition, metal alloys such as Cu/Ni, Cu/Al, Cu/Mn, Cu/Ag, Co/Mn, Ni/Ag alloys and mixtures, in particular a multicomponent alloy thereof, have proven to be particularly suitable catalytically active materials proven.

The person skilled in the art knows that he can also add other metals in smaller or larger amounts to all of the aforementioned alloys, if required, in order to thereby, for example, specifically adjust the properties, in particular the bulk modulus and/or the Mohs hardness of the catalytically active material, in accordance with the required reaction conditions, but also its reactivity to modify and therefore the aforementioned alloys only represent the basis or the main component. The catalytically active material can thus also be a multicomponent alloy of the aforementioned alloys.

The catalytically active material very particularly preferably consists of a material from the table below or a mixture thereof, where appropriate the bulk modulus and the Mohs hardness of the catalytically active material are to be taken into account. PSE Group 10 metal nickel palladium platinum alloy with it Monel (NiCu33) PdCu30 PtAu10 Hastelloy (NiMo30) PdAg40 PtCu4 Nichrome (NiCr20) PdSn15 Group 11 metal of the PSE Silver gold alloy with it AgPt5 AuCu18AI6 Brass (e.g. CuZn35) AgCu25 white gold Bronze (e.g. CuSn12) (AuNi10) Aluminum bronze (e.g. CuAl10Fe5Ni5) other metals iron rhodium chrome alloy with it 1.4301 (e.g. X5CrNi18-10) Pt30Rh ODS Pt20Rh FeCr50 1.4104 (e.g. X14CrMoS17) FCS Pt10Rh

In particular, strengths of up to approx. 700 MPa, in special cases even up to 1,500 MPa, compared to pure copper can be advantageously achieved through the use of Cu alloys.

The catalytically active material is particularly preferably a metal from the group consisting of a metal from groups 3 to 13 of the periodic table, particularly preferably a metal from groups 3 to 10, preferably Ru, Rh, Ni, Pd or Pt, very particularly preferably Pd or includes or consists of Pt.

In order to reduce costs and to counteract any abrasion of material, in particular of the catalytically active material, those shaped bodies which have no catalytically active material or which do not consist exclusively of it are preferably also added to the process. Based on the present invention, it is clear that in this case the shaped body preferably also comprises or consists of a core material which has a low modulus of elasticity (E modulus) or high compressive strength, such as steel, ZrO ₂ , TiO ₂ , Al ₂ O ₃ , WC, SiC, Si ₃ N ₄ , B ₄ C, BN, glass or mixed oxide ceramics such as ATZ / ZTA, but also BeO and MgO. Advantageously, the use of harder core materials for the shaped body, which have a low modulus of elasticity, offers better energy transfer and thus greater efficiency in the ball-wall impacts. However, the duration of the grinding process can also be increased.

Since possible abrasion - if it occurs - occurs primarily when the wall/surface of a grinding vessel is brought into contact with shaped bodies that are designed as grinding balls and less by bringing the shaped bodies into contact with the powder (mixture mixture), possible abrasion can be caused by a high quantity used Starting material (in the form of a solid and/or liquid) and/or in combination with a shortened milling time can be greatly reduced.

It has been shown that the layer comprising the catalytically active material remains in firm contact with the core material under mechanical stress (i.e. grinding), so that per (completely continuous) chemical reaction process or stress process (i.e. per synthesis) at least 80 %, particularly preferably at least 85%, very particularly preferably at least 90%, in particular at least 95% of the layer with the catalytically active material and the core material still form a connected unit after exposure.

Possible reactions

Processes for carrying out catalytic reactions are described in the literature and are sufficiently known to those skilled in the art.

The mechanochemical method according to the invention is preferably used for the reaction of organic compounds, preferably for the linking of organic compounds, as described below by way of example.

Examples of organic catalysis reactions in which the mechanochemical process according to the invention can be used for direct heterogeneous catalysis are hydroformylation, hydrogenation, isomerization, reduction, the dehydrogenation reaction, olefin metathesis, hydroformylation, arylamination, hydrosilylation, the cross-coupling reaction ( i.e. C-C, C-O or C-N couplings such as Suzuki coupling, Heck reaction, Negishi coupling, Yamamoto coupling, Reductive couplings, Ullmann coupling, Glaser coupling, Scholl reaction, Cadiot-Chodkiewicz coupling , Sonogashira coupling, Buchwald-Hartwig coupling, Tsuji-Trost reaction, coupling with Grignard compounds), olefin dimerization, olefin oligomerization, cyclopropanation, reduction of haloarenes, and polymerization (homo- and copolymerization) and telomerization reactions. The polymerization can also take place as a cross-coupling reaction (so-called metathesis polymerization).

Hydroformylation, hydrogenation, arylamination, hydrosilylation, Heck reaction, Suzuki coupling, Kumada coupling, Stille coupling, Sonogashira coupling, olefin metathesis, cyclopropanation, reduction of haloarenes, polymerization or telomerization reactions can be mentioned as preferred examples of heterogeneously catalyzed chemical reactions will.

Preferred organic catalysis reactions in which the mechanochemical method of the invention for direct heterogeneous catalysis can be used are the cross-coupling reaction (as defined above) and polymerisation (homo- and copolymerisation).

The table below lists preferred metals that can be used directly as catalytically active material in some of the mechanochemical processes listed herein for direct heterogeneous catalysis: reaction type catalytically active material (i.e. acting directly as a catalyst) Cross couplings (CC, CN, CO) e.g.: Palladium, platinum, nickel, iron Suzuki clutch palladium, nickel Heck reaction palladium, nickel Negishi clutch palladium, nickel Yamamoto clutch nickel Reductive clutches nickel Sonogashira clutch palladium Buchwald-Hartwig coupling palladium, iron Tsuji-Trost reaction palladium Coupling with Grignard connections Iron, Magnesium, Zinc, Palladium, Nickel Glaser coupling Copper (or its alloys) Ullmann coupling Copper (or its alloys) hydrogenation Palladium, platinum, nickel, cobalt, iron isomerization cobalt, iron, palladium reduction Iron, Palladium, Platinum, Ruthenium dehydration reactions Silver Gold olefin metathesis ruthenium hydroformylation rhodium

Acids or bases can be added to the catalytic reaction as required.

The term "leaving group" means an atom or group (charged or uncharged) which, by participating in a specific reaction, is separated from an atom in what is considered the residual or main part of the molecule (see also PAC , 1994, 66, 1134).

According to a preferred embodiment of the present invention, the reaction product that can be obtained by the mechanochemical method according to the invention is a polymer—which is obtained as a result of a chain reaction of a plurality of monomer units. The polymers that can be synthesized by the mechanochemical process of the present invention include homopolymers, random copolymers, random copolymers, alternating copolymers, and block copolymers, and combinations thereof. Such polymers can be synthesized analogously to methods known to those skilled in the art and already extensively described in the literature. Other polymers can be found in the working examples. For example, they can be suitably prepared by aryl-aryl coupling reactions such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling.

Preferred processes for the polymerisation are those which lead to CC, CO or CN coupling, particularly preferably to CC couplings, such as the Suzuki polymerisation, e.g. B. in the WO 00/53656 described, the Yamamoto polymerization, such as. B. in T. Yamamoto et al., Progress in Polymer Science 1993, 17, 1153-1205, or in the WO 2004/022626 A1 described, and the Stille coupling.

The term "monomer unit" or "monomer" denotes the underlying repeat unit, which is the smallest underlying unit whose repeat constitutes a regular macromolecule, oligomer molecule, block, or chain (PAC , 1996, 68, 2291).

The monomers which are polymerized to form the polymers are known to those skilled in the art and can be prepared by methods known to them.

If only one starting material is used as a monomer for the polymerization (self-polymerization), this is of course designed as a bifunctional chemical compound of the structure. In the case of self-condensation, the monomer has a so-called AB structure, where A is a first functional group which is suitable for reacting with B as a second functional group to form a new chemical compound.

Examples of polymerisations, among the other types of reactions disclosed herein, are also ring-opening metathesis polymerisation (ROMP) carried out in the presence of metals such as Pd, Rh, Ru, molybdenum and alloys thereof as the catalytically active material.

In addition, the method disclosed herein can also be used for depolymerizations, Fe, Ni and alloys thereof preferably being used as catalytically active material.

The best energy transfer occurs when at least one reactant is present in the reaction mixture as a solid (i.e. as a solid, undissolved component).

The person skilled in the art knows that when at least two starting materials are provided in step (a) of the process according to the invention, he can add the starting materials to one another in stoichiometric or substoichiometric ratios to the reaction vessel.

Likewise, the starting material(s) can also be added continuously or discontinuously (e.g. in several stages) to the mechanochemical process according to the invention.

Likewise, one or more starting materials of the mechanochemical process according to the invention can be gaseous and added continuously or discontinuously. Examples where at least one reactant is gaseous are the methanol-to-olefin (MTO) synthesis, the Fischer-Tropsch synthesis (e.g. on Fe, Ni, Co), cracking reactions (e.g. on Cr, Ni), isomerization Reactions (e.g. on Ni, Al), water gas shift reaction (e.g. on Fe), CO oxidation (e.g. Pt, Pd, Rh, Ru), CO ₂ reduction (e.g. on Pd, Pt, Cu, Fe, Re ), the Haber-Bosch process (e.g. on Fe, Pt), the Ostwald process (e.g. on Pt, Rh), ethylene oxide synthesis (e.g. on Ag), hydrogenation reactions such as fat hardening (e.g. on Ni, Rh, and elements the 8th subgroup of the PSE) or the Andrussow process (e.g. Pt, Rh) or cascade reactions thereof.

molding

In the context of the invention, the term "moulding" refers to an object with a constructive shape to which this was actively given and which was produced, for example, by non-cutting shaping (e.g. by pressing, transfer molding or injection molding) in tools that are closed on all sides. Alternatively, the shaped body is an intentionally shaped body/object in the form of pellets (e.g. obtained by dropping into a liquid), rings, sticks or pellets.

The shaped body comprises a core material on the surface of which at least one catalytically active material is arranged, the catalytically active material preferably being arranged at least partially as a layer, particularly preferably as a continuous layer, on the surface of the core material.

It is preferred that the outer layer of the shaped body is constructed from a solid material, i.e. no macropores or mesopores, very particularly preferably also no mesopores, which advantageously minimizes or even undesired material abrasion and/or unwanted deformation of the shaped body during the mechanochemical process is prevented.

The catalytically active material - like the core material - is particularly preferably made up of a solid material (e.g. as an immobilized coating or in the form of a film), i.e. the catalytically active material has no macropores or mesopores, very particularly preferably no mesopores.

That is, so that the shaped body or the catalytically active material can be used as an energy-transferring component during the direct mechanochemical conversion or undesired (metal) abrasion and the associated entry of particulate shaped body material or catalytically active material into the reaction mixture is prevented and also undesired deformation of the shaped body or catalytically active material during the mechanochemical process is minimized or even prevented, the shaped body or the catalytically active material used according to the invention are not used in the form of a powder or bulk material. The same also applies to the catalytically active material if the shaped body consists of this.

Provision can be made, for example, for at least one layer of the outer surface of a segment of the shaped body (e.g. in the case of an extruder screw or a grinding vessel) to comprise or consist of the catalytically active material.

The catalytically active material is preferably at least partially formed on the surface of the shaped body as a layer, e.g. as an immobilized coating or in the form of a film which clings to the shaped body (positively).

The layer of the catalytically active material can be obtained here on the shaped body, depending on the materials used, by coating methods known to those skilled in the art. These include, for example, bath electroplating, pen electroplating, sputtering, chemical vapor deposition (CVD), atomic layer deposition, electrochemical coating simply in the bath, dip coating .: dip coating), spray coating. In particular, bath electroplating and pen electroplating have proven to be particularly suitable as simple coating processes.

According to a preferred embodiment of the invention, the layer on the surface of the shaped body is designed as a multiple coating. The multiple coating is particularly useful when the material (actually used as the catalytically active material in the reaction) does not sufficiently adhere to the surface of the core material. In this case, an “intermediate layer” (i.e. a layer that is arranged between the surface of the core material and the catalytically active material) arranged in the multilayer coating can serve as an adhesion promoter. The intermediate layer thus supports/mediates the (indirect) adhesion of the catalytically active material to the core material of the shaped body. An example of this is the application of a layer of gold (Au) to the surface of the core material, with a layer of ruthenium being applied to the layer of gold.

In this case, the intermediate layer can be thinner than the layer applied to it, which layer comprises or consists of the catalytically active material.

For better adhesion promotion between the core material and the catalytically active material or between the core material and the intermediate layer, it can be provided that the surface of the core material is bonded to functional groups (e.g. SH groups, NH ₂ groups) before the layer is applied. or is functionalized by ligands.

It can also be provided that to improve the adhesion between the core material and the catalytically active material or between the core material and the intermediate layer, the surface of the core material a) by etching (e.g. with CrO ₃ ⁺ and H ₂ SO ₄ or pickling with oxidative metal salt solutions), b) is roughened by the application of crystallization nuclei, e.g. Pd, c) by treatment with so-called nucleation accelerators, e.g. tetrafluoroboric acid, d) by treatment with plasma or e) by mechanical treatment. This pretreatment of the surface of the core material improves germ adhesion during coating with the catalytically active material or the intermediate layer.

Depending on the layer of catalytically active materials to be applied, copper, gold, palladium and nickel in particular have proven to be materials for forming the intermediate layer (also referred to herein as the base layer). The catalytically active material (i.e. the metal) can then be applied to this.

According to a preferred embodiment, the shaped body comprises at least one, two, three, four or more intermediate layers, which are arranged between the surface of the core material and the layer of the catalytically active material. This is desirable because the intermediate layer, in addition to its function as an adhesion promoter, can also serve as a diffusion barrier, as a conductive layer or to adapt the ball properties. The arrangement of the intermediate layer on the shaped body thus allows targeted adjustment with regard to the aforementioned properties.

The layer thickness of the outer layer (i.e. which comprises or consists of the catalytically active material) and/or the intermediate layer is typically, independently of one another, in the range between 1 nm and 1 mm, preferably in the range from 2 nm to 100 μm, very particularly preferably in the range from 2 nm to 10 μm, more preferably in the range between 10 nm and 1.5 μm, very preferably in the range between 100 nm and 800 nm, such as between 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm , 450nm, 500nm, 550nm, 600nm, 650nm and 700nm and 750nm.

The core material can be chosen depending on the desired reaction parameters.

If, according to a preferred embodiment, high energy inputs are desired, then on the one hand materials that have a high density are suitable as core materials for the shaped body (e.g. grinding ball or grinding vessel). This can be steel, for example.

If, according to an alternative preferred embodiment, low energy inputs into the chemical reaction are desired, materials that have a low density are suitable as core materials for the shaped body (e.g. grinding ball or grinding vessel). This can, for example, be a polymer (as defined herein) or a light metal (e.g. aluminium) or a composite material.

The need for high or low energy inputs is determined by the activation energy of the chemical reaction to be carried out. The person skilled in the art is familiar with the activation energies of the reactions or can look them up in the relevant technical literature. It was also found that excessive energy inputs are to be avoided in order to prevent abrasion of the grinding materials during the mechanochemical reaction and/or destruction/decomposition of the reaction products and possibly also the educts.

If high energy inputs are desired, then materials that have a low modulus of elasticity (E modulus) or high compressive strength, such as steel (E modulus = 210 GPa), zirconium dioxide ZrO ₂ (E modulus = 205 GPa), titanium dioxide TiO ₂ (E modulus = 293 GPa), aluminum oxide Al ₂ O ₃ (E modulus = 300-380 GPa), tungsten carbide WC (E modulus = 550-630 GPa), sintered or hot-pressed silicon carbide SiC (modulus of elasticity = 450 GPa), silicon nitride Si ₃ N ₄ (modulus of elasticity = 310 GPa), boron carbide B ₄ C (modulus of elasticity = 440-470 GPa), cubic Boron nitride c-BN or mixed oxide ceramics such as ATZ / ZTA (modulus of elasticity = 240-350 GPa), but also beryllium oxide BeO (modulus of elasticity = 390 GPa) and magnesium oxide MgO (modulus of elasticity = 310 GPa). Advantageously, the use of harder core materials for the molded body, which have a low modulus of elasticity, offers a bes Greater energy transfer and thus greater efficiency in ball-wall collisions. The aforementioned core materials (steel, ZrO ₂ , WC only to a limited extent) are, in the context of the invention, light to medium-heavy materials which are characterized by an average density in the range from 3 to 6 g/cm ³ and thus a "medium" Energy input into the mechanochemical reaction result.

Nevertheless, the inventors have found that a high energy input, for example through the use of grinding materials that have a high modulus of elasticity, is not desirable in all cases, since this results in undesirable by-products or coking of the starting materials and/or products. Very good results have therefore been achieved in particular through the use (in relation to the aforementioned core materials) of soft polymer balls, e.g. made of polymethyl methacrylate (PMMA), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polythiophene (PT), polyamides, Acrylonitrile butadiene rubber (NBR), acrylonitrile butadiene styrene copolymer (ABS), polysterols (PS), fluorinated hydrocarbons such as Teflon, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluoroalkoxy polymers (PFA) or combinations thereof achieved as the material for the molding. In the context of the invention, the aforementioned core materials are light materials which are characterized by a low density of less than 3 g/cm ³ and as a result result in a “low” energy input into the mechanochemical reaction.

The person skilled in the art knows that in the case of electrochemical coatings of the aforementioned materials, a conductive lacquer should be added in order to improve contact/durability.

The aforementioned materials, which are used as the core material for the shaped body, are also suitable for use as solid intermaterial because of their chemical stability and inactivity and because of their high modulus of elasticity.

Alternatively, the shaped body, particularly preferably the outer layer of the catalytically active material, is designed as a composite material, with the catalytically active material being embedded in the structure of the shaped body or the outer layer or forming a network structure within the outer layer.

Irrespective of this, the shaped body can be used as an energy-transmitting component of a ball mill (i.e. as the grinding vessel and/or at least one grinding ball), an eccentric vibratory mill (i.e. as at least one grinding ball), a rotor impact mill (i.e. as the grinding vessel and/or a rotor), a pin mill ( i.e. as the milling vessel and/or at least one pin) or an extruder (i.e. wholly or partly as the extruder screw or wholly or partly as the inner wall of the extruder barrel) for the continuous and mostly industrial implementation of the invention.

It has proven to be advantageous that not all grinding balls are coated with the catalytically active material, i.e. grinding balls that do not have any catalytically active material are also used in the reaction. It has been shown that the conversion can be increased as a result, since only one grinding ball is catalytically active (especially in the case of catalytically highly active materials or sensitive reactions) and the inactive grinding balls are only there to provide impact energy.

Nevertheless, it can be advantageous that two different types of shaped bodies, in particular grinding balls, are used, the outer layers of which differ with regard to the catalytically active material used. This is particularly advantageous when the chemical reaction is merely one step of a "complex chemical reaction" (as defined herein). Since this can catalyze a subsequent step and/or a preceding step. This is particularly advantageous when the subsequent reaction--induced by the coating of shaped bodies with another catalytically active material--leads to a shift in the equilibrium toward the products. Consequently, in the mechanochemical process, a first type of shaped body can be provided which has a first core material and a first catalytically active material arranged on its surface, and a second type of shaped body can be provided which has a second core material and a second catalytically active material arranged on its surface has catalytically active material. The first and the second core material as well as the first and the second catalytically active material can each be selected independently of one another.

For the same reason, it can alternatively be provided that a first part of the surface of the core material is covered with a first catalytically active material and a second part of the surface of the core material terials is formed with a second catalytically active material, wherein the first and the second catalytically active material are each independently selected. In this case, the first catalytically active material preferably catalyzes a different chemical reaction (preferably within a complex chemical reaction, such as a cascade reaction) than the second catalytically active material. Preferably, the ratio between the degree of coating of the first catalytically active material to the degree of coating of the second catalytically active material is in the range from 10:1 to 1:10, more preferably in the range from 5:1 to 1:5, most especially preferably in the range of 3:1 to 1:3.

It goes without saying that with this arrangement of the partial coating, too, an intermediate layer (for example for improved adhesion promotion) can be arranged between the core material and the outer layer of the catalytically active materials.

As a result, depending on the type of reaction, the costs for the individual materials and/or to ensure a homogeneous input of energy, it can be provided that in the mechanochemical process (a) only shaped bodies are used which comprise a core material with a layer of a catalytically active material, (b) at least two types of shaped bodies are used, with only one type of shaped bodies comprising a core material with a layer of a catalytically active material (the other shaped bodies are uncoated and therefore catalytically inactive and are only used to provide the impact energy or to introduce energy be) or (c) that at least two types of shaped bodies are used, the first type having a first core material and a first catalytically active material arranged on its surface, and a second type of shaped body being provided which has a second core material and a their surface arranged second active material.

If at least two different types of shaped bodies are used for the mechanochemical reaction to be catalyzed, it can be provided that the different types of shaped bodies have different sizes. It can thus be ensured that the input of impact energy or the input of energy that is introduced into the chemical reaction by each shaped body is of the same magnitude.

If the shaped body is designed as a grinding ball, the grinding balls preferably have a diameter of at least 2 mm, particularly preferably at least 5 mm, very particularly preferably at least 10 mm, for ideal energy transfer. According to a preferred embodiment of the present invention, the core material of the sphere to be coated has a diameter of 1 mm to 30 mm.

It has been shown that the energy transfer to the starting materials is particularly good if a grinding vessel (mill), such as a ball mill or a planetary ball mill, is used as the reaction vessel for direct heterogeneous catalysis. Such grinding vessels have a grinding reactor and (freely movable) grinding balls arranged therein. The basic structure of such grinding vessels is known to those skilled in the art. According to a preferred embodiment of the invention, the shaped body is therefore a grinding reactor and/or one or more grinding balls, the catalytically active material being applied at least partially to their surface. Alternatively, entire components, such as the grinding reactor or the (freely movable) grinding balls arranged therein, can also consist entirely or partially of the catalytically active material.

According to a preferred embodiment, a mixer mill, a planetary ball mill, an extruder or an agitator ball mill is used for the chemical conversion of the starting materials. The best sales were achieved with these mill types.

The grinding frequency, e.g. in the case of conversion in a mixer mill, is preferably in the range from at least 15 Hz to 75 Hz, particularly above 20 Hz, very particularly preferably in the range from at least 20 Hz to 50 Hz.

Optimum results, for example when implemented in a planetary mill, could also be achieved at rotary speeds in the range from 200 to 1600 rpm, preferably in the range from 400 to 1600 rpm, very particularly preferably in the range from 600 to 1600 rpm.

The degree of filling of the grinding vessel used is very particularly preferably in the range from 20 to 40% by volume of grinding balls and 20 to 40% by volume of ground material (ie filling comprising educts (reactants or second active components) and inert material).

It has been shown that the milling time, i.e. the final reaction time, in which case the energy-transferring contacting of the starting materials with the shaped body in accordance with step (c) takes place repeatedly, for the mechanochemical reaction is in the range from 1 minute to 48 hours, preferably less than 8 hours, especially less than 4 hours. The energy-transferring bringing into contact of the starting materials with the shaped body in step (c) also preferably takes place repeatedly over a period of at least 5 minutes, particularly preferably at least 10 minutes.

For example, it has been shown that to carry out the method according to the invention for direct heterogeneous catalysis of a chemical reaction, e.g. a polymerisation in a ball mill with at least 2 solid grinding balls (e.g. consisting of pore-free palladium or platinum as the catalytically active material) within a few hours, preferably the polymer polyparaphenylene (PPP) can be prepared from the monomer (e.g. 4-bromophenylboronic acid) for at least 8 hours at room temperature. The reaction of iodobenzene with phenylboronic acid (see embodiment 3 herein) can be mentioned here as a further explicit example reaction. With the aid of the process according to the invention and the use of a grinding ball coated with catalytically active palladium, it is possible to convert these completely into biphenyl within a few hours at room temperature.

A particular advantage of synthesizing polymers using the process of the invention is that the mostly limiting factor - i.e. the precipitation of the polymer during the polymerization - does not occur since the reaction is carried out as a solid phase reaction from the outset.

As a result, completely new possibilities can be advantageously realized in the chemical conversion of starting materials.

In a preferred embodiment of the present invention, the shaped body is suitable for transferring the energy required for direct mechanochemical conversion to the starting materials and/or for (homogeneously) mixing the starting materials. The shaped body can be configured in any conceivable shape (preferably as defined herein).

When using a grinding device (e.g. a mill), the shaped body is therefore designed, for example, as the grinding reactor and/or at least one grinding ball. On a laboratory scale, it has been shown that grinding balls with a diameter of between 5 and 15 mm are usually particularly suitable. Depending on the material used, in particular the catalytically active material, the grinding balls have a mass in the range between 1.95 g and 26.21 g.

Particularly advantageously, the grinding vessel and the grinding balls can be reused with the coating of the catalyst.

Alternatively, it is expedient for some reactions, in particular for the continuous and mostly industrial implementation of the invention (e.g. polymerization for the production of films), that the shaped body is an extruder screw.

It can certainly be provided that the direct heterogeneously catalyzed chemical reaction, which is realized by the method according to the invention, is only a partial step (i.e. a pre-reaction or an intermediate reaction; e.g. a first reaction stage, a second reaction stage, etc.) within a complex chemical represents reaction.

A "complex chemical reaction" is understood here as the conversion of at least two reactants into an end product, with the chemical reaction being composed of several reaction stages, with e.g. within a cascade reaction after each individual reaction stage the corresponding reactant(s). ) are converted into an intermediate or end product.

It may be necessary here for at least one further starting material to be added externally to the product from the preceding reaction stage or the reaction vessel during the complex chemical reaction before each further reaction stage. The further starting material can be the same or a different starting material from one of the preceding reaction stages. This kind of chemical Reaction is appropriate, for example, when, in a multi-stage reaction, an intermediate stage with an intermediate is followed or is to be followed by a further reaction stage.

The present invention also relates to a shaped catalyst body (as defined in more detail above as shaped body), in particular a shaped reaction catalyst body for direct heterogeneous catalysis of a chemical reaction, which comprises a catalytically active material, the catalytically active material being a metal from the group consisting of gold ( Au), Silver (Ag), Copper (Cu), Palladium (Pd), Platinum (Pt), Ruthenium (Ru), Rhodium (Rh), Rhenium (Re), Nickel (Ni), Iron (Fe), Cobalt ( Co), chromium (Cr), vanadium (V) or a mixture thereof.

According to a preferred embodiment, the catalytically active material is characterized by a bulk modulus of at least 160 GPa and a Mohs hardness of at least 3.0.

According to a preferred embodiment, the catalyst milled shaped body (as defined in more detail above as shaped body) comprises a core material on the surface of which a catalytically active material is applied as a layer, the catalytically active material comprising or consisting of a metal from groups 3 to 13 of the periodic table , preferably consisting of Au, Ag, Cu, Pd, Pt, Ru, Rh, Re, Ni, Fe, Co, Cr, V, particularly preferably a metal from groups 6 to 10, in particular from Ru, Rh, Ni, Pd, Pt, Co, Au, a mixture thereof or an alloy based on a metal selected from the group consisting of a metal from groups 6 to 10 of the periodic table, preferably Ru, Rh, Ni, Pd, Pt, Co, Au or Cu - such as for example Pt/Au, Pd/Au, Fe/Co, Fe/Ni, Fe/Cr, Fe/Mn, Ni/Pt, Ni/Pd, Pt/Cu, Pd/Cu -, Cu/Sn, Cu/Zn, Cu/Ni, Cu/Al, Cu/Mn, Co/Mn or Ni/Ag alloy, wherein the catalytically active material has no macro- or mesopores .

The present invention also relates to the use of a shaped catalyst mill body as defined herein as a heterogeneous catalyst in a process for directly heterogeneously catalyzing a chemical reaction.

extruder

The invention also includes the preferably solvent-free mechanochemical reaction with direct heterogeneous catalysis of a chemical reaction in an extruder as a shaped body, in which at least one educt is directly ground to form a product by means of energy-transferring bringing this educt into contact with the extruder (or the inner wall of the extruder ) is implemented. In this case, the inner wall of the extruder is coated or lined with the catalytically active material (as the outer layer of the wall of the extruder).

The extruder configuration can be designed in any conceivable form (as defined herein), the basic structure of such grinding vessels is known to the person skilled in the art and, in its preferred embodiment of the shaped body, is suitable for transferring the energy required for direct mechanochemical conversion to the starting materials and/or to mix the starting materials (homogeneously) with one another. The extruder configuration is preferably a combination of kneading and conveying elements (each examples of shaped catalyst mill bodies) of any size and number.

The process is preferably carried out in an extruder, the performance of which includes at least one of the following parameters.

Mechanochemical reactions in the reaction chamber of the extruder advantageously take place at temperatures between -30.degree. C. and 400.degree. C., in particular -30.degree. C. and 300.degree. C., preferably between 0.degree. C. and 200.degree. C., particularly preferably between 30 and 150.degree.

Optimum results, for example when implemented in an extruder, could be achieved at rotational speeds of up to 500 rpm, preferably in the range from 5 to 200 rpm, very particularly preferably in the range from 10 to 100 rpm.

It has been shown that the residence time for the mechanochemical reaction in the extruder, i.e. the final reaction time, wherein the energy-transferring bringing into contact of the starting materials with the shaped body according to step 1.c) takes place repeatedly, is in the range of less than 4 hours, preferably less than 2 hours particularly in the range of 1 minute up to 30 minutes.

The dosing speed of the starting materials at the extruder screw also has an influence on the catalytic activity, since extruder screws with diameters of 0.5 to 30 cm are used in industry, it makes sense to specify a coefficient of dosing speed and screw diameter (SD). A dosing coefficient of less than 42 g/(cm _SD s), preferably less than 17 g/(cm _SD s), particularly preferably between 8.5 and 0.085 g/(cm _SD s) is desirable.

exemplary embodiments

The present invention is to be explained in more detail on the basis of the following figures and exemplary embodiments, without restricting the invention to these.

• 1: GC/MS-Spektrum des erhaltenen Produkts aus der Suzuki-Kupplung mit einer palladinierten Kugel in einem PFA-Becher.
• 2: ¹H-NMR-Spektrum des erhaltenen Produkts aus der Suzuki-Kupplung mit einer palladinierten Stahlkugel in einem PFA-Becher.
• 3: ¹³C-NMR-Spektrum des erhaltenen Produkts aus der Suzuki-Kupplung mit einer palladinierten Stahlkugel in einem PFA-Becher.
• 4: GC/MS-Spektrum des erhaltenen Produkts aus der Glaser-Kupplung mit einer verkupferten Kugel in einem PFA-Becher.
• 5: Beschichtungsschritte eines Bronzebechers (18 ml) mit palladinierter Reaktionsoberfläche.
• 6: Beschichtungsschritte des ruthenieren einer Bronzekugel (
  
  10 mm).
• 7: Palladinierungsschritte einer Monelkugel (
  
  9,2 mm).
• 8: Direktes vergolden einer Stahlkugel (
  
  10 mm).
• 9: Palladinierungsschritte einer Stahlkugel (
  
  10 mm).
• 10: Palladinierungsschritte des Knetsegments eines Extruders.

while showing

• 1 : GC/MS spectrum of the product obtained from the Suzuki coupling with a palladium-plated sphere in a PFA beaker.
• 2 : ¹ H-NMR spectrum of the product obtained from the Suzuki coupling with a palladium-coated steel ball in a PFA cup.
• 3 : ¹³ C-NMR spectrum of the product obtained from the Suzuki coupling with a palladium-coated steel ball in a PFA cup.
• 4 : GC/MS spectrum of the product obtained from Glaser coupling with a copper-plated sphere in a PFA beaker.
• 5 : Coating steps of a bronze beaker (18 ml) with palladium-coated reaction surface.
• 6 : Coating steps of ruthenating a bronze ball (
  
  10mm).
• 7 : Palladium plating steps of a monel sphere (
  
  9.2mm).
• 8th : Direct gilding of a steel ball (
  
  10mm).
• 9 : Palladium plating steps of a steel ball (
  
  10mm).
• 10 : Palladium plating steps of the kneading segment of an extruder.

Example 1 - Palladium plated spheres as catalyst

Here the coated grinding balls were used directly as catalysts. A mixer ball mill (MM) was used for this.

For a standard synthesis in the MM, 496 mg of 4-iodophenylboronic acid (2.00 mmol) with 2.504 g (18.12 mmol) of K ₂ CO ₃ and two grinding balls (10 mm diameter) were placed in a 25 mL ZrO ₂ grinding jar. The reaction mixture was ground at 30 s ^-1 and converted to poly(para-phenylene) (PPP; see Table 1). The reaction product was then washed with water, 10% by weight HCl, ethanol and acetone and dried at 80° C. overnight.

Example 2 - Palladium as a catalyst in Suzuki polymerisation

The Suzuki coupling reaction according to exemplary embodiment 1, in which a polyparaphenylene is formed from 4-iodophenylboronic acid, can also be used successfully for sterically more demanding starting materials. The procedure is also suitable for polymerizing 1-bromo-2-phenylboronic acid.

Example 3 - Palladium as a catalyst in the Suzuki coupling

In the Suzuki coupling reaction, phenylboronic acid is reacted with various halogenated reactants to form biphenyls.

In a classical synthesis, 0.122 g (0.1 mmol) phenylboronic acid, 0.204 g iodobenzene (0.1 mmol), 1.0 g (0.1 mmol) K ₂ CO ₃ as base and a palladium-coated steel ball (10 mm 4, 04 g) provided as catalyst in a mixer mill (MM) in a PFA beaker (18 ml). The reaction ran at 30 s ^-1 for x hours. Then the reaction product was washed with water and isopropanol. The reaction was also successful with iodoanisole and brombenzene.

The resulting material was colorless crystalline and showed the characteristic GC/MS spectrum ( 2 ). Furthermore, it shows the NMR signals typical for biphenyl ( 3 ).

Example 4 - Nickel Coated Balls as Catalyst in Yamamoto Coupling

The Yamamoto coupling, which is similar to the Ullmann coupling and in which two haloaromatics are linked by means of nickel, was successful in the MM-500 vibratory mill (RETSCH GmbH, Haan, Germany). For a successful reaction, iodobenzene (liquid) as starting material was ground with a large excess of KOtBu (8-fold excess as solid second active component) with four 10-12 mm nickel-plated balls in a 25 ml PMMA grinding jar for 2.5 h in a vibratory mill . In addition, conversions could also be achieved in the IST-500 or the MM-400 with a grinding frequency of 30 Hz each.

Example 5 - Nickel Coated Spheres as Catalyst in Sonogashira-Hagihara Coupling

The Sonogashira–Hagihara coupling, which is commonly catalyzed by palladium, was accomplished under direct mechanocatalytic conditions with coated spheres. For a successful reaction, an alkyne species (usually phenylacetylene (liquid), more rarely biphenylacetylene (solid) or 1,1-diphenylprop-2-yn-1-ol (solid)), with a haloaromatic compound (usually iodbezole (liquid), but also chloronaphthalene (liquid), bromobenzene (liquid), 4-bromo-N,N-dimethylaniline (solid) or 6-methoxybromoonaphthalene (solid)) using nickel-plated balls, copper powder and 5 mol% copper iodide (solid). Various mineral bases were used as base and at the same time as bulk material.

Example 6 - Copper Coated Balls in Glaser Coupling

The Glaser coupling is useful for coupling two terminal alkynes where X is hydrogen (H), bromine (Br), or a phenyl group. The reactions with phenylacetylene (liquid), 4-bromophenylacetylene (solid) or biphenylacetylene (solid) could be successfully performed in a MM-400 at 30 Hz. In the mechanochemical conversion of the starting materials, coupling takes place within 90 minutes. The use of a copper-plated ball and an inert PFA grinding bowl lead to a successful reaction. K ₂ CO ₃ was used as bulk material. Nevertheless, the use of other mineral bases also leads to the desired target product, with the Glaser coupling also being able to be observed successfully in other reactions where, for example, hydroxides were used.

Example 7 - Palladium Coated Spheres in the Heck Reaction

The Heck reaction is suitable for converting aryl halides into olefins. The reactions with styrene (liquid), bromobenzene (liquid) could be carried out successfully in a planetary ball mill at 800 rpm. The mechanocatalytic conversion of the reactants takes place within 60 minutes. A successful reaction is achieved by using palladium-coated balls and an inert zirconium oxide grinding bowl. K ₂ CO ₃ was used as bulk material.

Example 8 Coated Kneading Elements as a Catalyst in the Suzuki Coupling in the Extruder

The Suzuki coupling reaction according to exemplary embodiment 3, in which the reaction of the starting materials takes place in a ball mill, can also be carried out in an extruder. Accordingly, coated kneading elements are just as suitable as coated balls.

The reaction mixture was chosen so that at least 50 g of reaction mixture are present. There was thus provided 4.6 g (37.7 mmol) of phenylboronic acid, 7.7 g of iodobenzene (37.7 mmol), 37.7 g (272.8 mmol) of K ₂ CO ₃ as the base. Palladium-coated kneading segments served as the catalyst.

Coating process:

Coating methods for producing a shaped body (as defined herein) are specified below by way of example, in which a core material is coated with at least one layer of a catalytically active material. It is understood herein that the final layer is the catalytically active material. The core material to be coated is, for example, a grinding ball or a grinding vessel.

Coated core materials:

10 mm):

1. a) 1.4034 (ASIN bzw. Werkstoffnummer)
2. b) 1.4401
3. c) 1.0304
4. d) 1.4125
5. e) 1.3505
6. f) 1.4301

Mahlkugeln aus Nickel (

10 mm)
Mahlkugeln aus Bronze (

10 mm) / Mahlbecher aus Bronze (Volumen: 18 ml)
Mahlkugeln aus K-Monel/ Monel® K-500 (

9,2 mm)Steel grinding balls (

10mm):

1. a) 1.4034 (ASIN or material number)
2. b) 1.4401
3. c) 1.0304
4. d) 1.4125
5. e) 1.3505
6. f) 1.4301

Nickel grinding balls (

10mm)
Bronze grinding balls (

10 mm) / bronze grinding bowl (volume: 18 ml)
Grinding balls made of K-Monel/ Monel® K-500 (

9.2mm)

Electrolyte composition:

Copper coatings: copper sulphate 300 mg, sodium hydroxide, potassium carbonate, water 100 ml
Ruthenium coatings: ruthenium(III) chloride 50 mg, water 20 ml
Gold plating: Commercially available gold electrolyte consisting of gold(I) cyanide in alkaline solution.

Nickel Plating: Commercially available nickel electrolyte consisting of nickel sulfamate solution.

Palladium coating: Commercially available palladium electrolyte consisting of palladium nitrate or palladium sulphate solution with complexing agents and additives.

1.1 Copper plating of steel grinding balls:

First, the metal surface of the core material consists of steel and is degreased using various solvents or special cleaning agents. The metal surface is then activated/pickled in an activator solution (10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 minute using a stainless steel or graphite electrode. After rinsing with deionized water, the copper coating is applied in a copper electrolyte (alkaline / 3 g/l) with a copper electrode 4 V (0.4 A) for approx. 1.5 minutes. rinsed with water. The molding thus obtained has a layer thickness of copper of about 500 nm.

Here, the layers of copper represent the outer layer, which serves as the catalytically active material.

1.2 Nickel plating of steel grinding balls with an intermediate layer of copper as an adhesion promoter:

First, the metal surface is degreased using various solvents or special cleaning agents. The metal surface is then activated/pickled in an activator solution (10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 minute using a stainless steel or graphite electrode. After rinsing with deionized water, a copper coating is first applied as a later intermediate layer in a copper electrolyte (alkaline / 3 g/l) with a copper electrode 4 V (0.4 A) for approx. 1.5 minutes. After rinsing again with deionized water water, a nickel coating is applied in a nickel electrolyte (60 g/l) using a nickel electrode at 5 to 7 V (0.8 A) for a period of approx. 2 minutes. Finally, the grinding ball obtained in this way is rinsed with deionized water. The molding thus obtained has a layer thickness of nickel of about 119 nm. The copper layer serves as an adhesion-promoting intermediate layer. The layer of nickel herein represents the outer layer serving as the catalytically active material.

1.3 Gold plating of steel grinding balls with an intermediate layer of copper and a layer of nickel as an adhesion promoter:

In the case of the steel grinding ball coated with copper and nickel obtained under point 1.2, a gold coating is applied in a gold electrolyte (8 g/l) with a stainless steel, platinum or graphite electrode at 5 to 10 V (0.1 A) for approx. 1.5 min Finally, the grinding ball obtained in this way is rinsed with deionized water. The layers of copper and nickel serve as an adhesion-promoting first and second intermediate layer. The layer of gold herein represents the outer layer serving as the catalytically active material.

1.4 Direct gold plating of steel grinding balls:

First, the metal surface is degreased using various solvents or special cleaning agents. The metal surface is then activated/pickled in an activator solution (10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 minute using a stainless steel or graphite electrode. After rinsing with deionized water, the gold coating is applied in a gold electrolyte (8 g/l, a gold-cyanide complex) with a stainless steel, platinum or graphite electrode at 5 to 10 V (0.1 A) for approx. 1.5 min Finally, the grinding ball obtained in this way is rinsed with deionized water. The layer of gold herein represents the outer layer serving as the catalytically active material.

1.5 Palladium plating of a quadruple coated steel grinding ball:

The metal surface of the core material consists of steel and is degreased using various solvents or special cleaning agents. This is followed by activation/decapping the metal surface in an activator solution (10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 min with a stainless steel or graphite electrode. The grinding ball cleaned in this way is rinsed with deionized water. This is followed by successive coating with (1) copper in a copper electrolyte (alkaline / 3 g/l) with a copper electrode at 4 V (0.4 A) for approx. 1.5 min, then with (2) nickel in a nickel electrolyte (60 g/l) with a nickel electrode at 5 to 7 V (0.8 A) for approx. 2 min, with (3) gold in a gold electrolyte (8 g/l) with a stainless steel, platinum or graphite electrode 5 to 10 V (0.1 A) for approx. 1.5 min and finally the gold layer is coated as the third intermediate layer with palladium in a palladium electrolyte (2 g/l) with a platinum or graphite electrode 3-5 V (0 ,1 A) for approx. 1 min. Of course, the molding is rinsed with deionized water after each coating step. The layers of copper, nickel and gold serve as an adhesion-promoting first, second and third intermediate layer. The layer of palladium herein represents the outer layer serving as the catalytically active material.

1.6 Ruthenizing of a steel grinding ball:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Activation/decapping of the metal surface in an activator solution (usually 10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 min with a stainless steel or graphite electrode.
• - Rinse (deionized water)
• - Copper coating in copper electrolyte (alkaline / 3 g/l) with copper electrode 4 V (0.4 A) approx. 1.5 min.
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)
• - Pickling: Wash with 10% sulfuric acid and rub off
• - Rinse (deionized water)
• - Ruthenium coating in ruthenium electrolyte (2.5 g/l) at 45-60 °C with platinum or graphite electrode 3 V (0.1 A) approx. 4 min.

2.1 Copper plating of nickel:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Activation/decapping of the metal surface in an activator solution (usually 10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 min with a stainless steel or graphite electrode.
• - Rinse (deionized water)
• - Copper coating in copper electrolyte (alkaline / 3 g/l) with copper electrode 4 V (0.4 A) approx. 1.5 min.
• - Rinse (deionized water)

2.2 Gold plated nickel:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Activation/decapping of the metal surface in an activator solution (usually 10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 min with a stainless steel or graphite electrode.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)

2.3 Palladium plating of nickel:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Activation/decapping of the metal surface in an activator solution (usually 10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 min with a stainless steel or graphite electrode.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)
• - Palladium coating in palladium electrolyte (2 g/l) with platinum or graphite electrode 3-5 V (0.1 A) approx. 1 min.
• - Rinse (deionized water)

2.4 Ruthenate nickel:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Activation/decapping of the metal surface in an activator solution (usually 10% hydrochloric acid, 5-10% sulfuric acid) at 3 V (1.0 A) for approx. 1 min with a stainless steel or graphite electrode.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)
• - Pickling: Wash with 10% sulfuric acid and rub off
• - Rinse (deionized water)
• - Ruthenium coating in ruthenium electrolyte (2.5 g/l) at 45-60 °C with platinum or graphite electrode 3 V (0.1 A) approx. 4 min.

3.1 Nickel plating bronze:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)

3.2 Direct gilding of bronze:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)

3.3 Gilding bronze:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)

3.4 Palladium Bronze:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)
• - Palladium coating in palladium electrolyte (2 g/l) with platinum or graphite electrode 3-5 V (0.1 A) approx. 1 min.
• - Rinse (deionized water)

3.5 Ruthenizing Bronze:

• - Degrease the metal surface using various solvents or special cleaning agents
• - Rinse (deionized water)
• - Nickel coating in nickel electrolyte (60 g/l) with nickel electrode 5-7V (0.8 A) approx. 2 min.
• - Rinse (deionized water)
• - Gold coating in gold electrolyte (8 g/l) with stainless steel, platinum or graphite electrode 5-10 V (0.1 A) approx. 1.5 min.
• - Rinse (deionized water)
• - Pickling: Wash with 10% sulfuric acid and rub off
• - Rinse (deionized water)
• - Ruthenium coating in ruthenium electrolyte (2.5 g/l) at 45-60 °C with platinum or graphite electrode 3 V (0.1 A) approx. 4 min.

4.1 K-Monel/ Monel® K-500 gold plating:

• - See: 2.2 gilding nickel:

4.2 Palladium plating of K-Monel/ Monel® K-500:

• - See: 2.3 Palladium plating of nickel:

4.3 K-Monel/ Monel® K-500 ruthenate:

• - See: 2.4 Ruthenizing nickel:

Reactions:

• - Glaserkupplung (Homokupplung):

Copper-plated surfaces as outer layers as catalytically active material:

• - Glaser coupling (homo-coupling):

• - Carbonylierung
• - Oxidation
• - Stillekupplung
• - Suzukikupplung:

Palladium plated surfaces as outer layers as catalytically active material:

• - carbonylation
• - oxidation
• - Silent clutch
• - Suzuki clutch:

Electroplating a grinding ball

The grinding ball to be coated (example of a core material) is thoroughly cleaned and completely degreased before electroplating. The grinding ball is then pickled for about 1 minute at 3 V (1 A) with an activator solution (usually 10% HCl, 10% H ₂ SO ₄ ) using pin or bath plating. This is done using a stainless steel electrode. The ball is thoroughly rinsed with deionized water. Now the sphere is gold-plated with a gold electrolyte (8 g/l) at 5 V (0.1 A) for about 1.5 minutes with a stainless steel, platinum or graphite electrode using bath or pen plating. Depending on the surface to be gilded, this can be quicker (nickel, >1 min) or slower (steel up to 2 min.). The gold-plated ball is thoroughly rinsed (DI water). In order to deposit the palladium onto the ball, it is placed in a palladium electrolyte (2 g/l) at 3-5 V (0.1 A) for about 1 min. Platinum or graphite can serve as electrode material here.

Depending on the material, gold cannot be deposited directly onto the surface, so it is copper-plated first. This works using a copper electrode in a copper electrolyte at 3 - 4 V (0.4 A) for about 1.5 minutes. A layer of nickel can also be applied as a diffusion barrier and adhesion promoter. The nickel deposition is carried out by a nickel electrolyte (60 g/l) with a nickel electrode at 5-7 V (0.8 A) for about 2 min. carried out. Nickel plating is mainly used on copper surfaces. Then it can be coated as described above.

Non-conductive materials such as plastics (PTFE, PP, PMA, PFA), ceramics (zirconium oxide ZrO ₂ ), or natural materials (wood) must first be coated with a conductive paint. Copper, silver and graphite conductive paints are suitable for this. In order to coat the balls with the paint, it must be completely cleaned and degreased. The paint can now be brushed on or preferably sprayed. After the ball has dried, it can be electroplated as described above.

Various steels, nickel, copper, bronze, brass, monel, gold, palladium, rhodium, platinum, ruthenium, and other alloys containing nickel or copper are suitable as materials that can be electroplated directly. Table 1: Examples of suitable steel grades material number 1.0304 1.3505 1.4034 1.4125 1.4301 1.4401

In addition to palladium, other catalytically active transition metals can be coated. Rhodium, ruthenium, platinum, rhenium, osmium and others are particularly suitable for this purpose.

QUOTES INCLUDED IN DESCRIPTION

This list of the documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 2007/023295 A2 [0005, 0006]
• US 9206098 B2 [0006]
• US 9701542 B2 [0008]
• DE 102019117437 [0011]
• WO 0053656 [0071]
• WO 2004/022626 A1 [0071]

Claims (22)

Mechanochemical process for the direct heterogeneous catalysis of a chemical reaction, comprising the following steps: a) providing at least one starting material; b) providing a shaped body, wherein the shaped body comprises at least one catalytically active material; and c) direct grinding of the at least one starting material to form a product by bringing it into contact with the shaped body in an energy-transferring manner; characterized in that the shaped body has an inert core material and at least one outer layer which is formed from the catalytically active material and wherein the outer layer is arranged on the surface of the core material. procedure after claim 1 , wherein the layer thickness of the outer layer is in the range between 1 nm and 1 mm. procedure after claim 1 or 2 , wherein the outer layer, which is formed from the catalytically active material, makes up less than 10% by weight of the total weight of the shaped body. Procedure according to one of Claims 1 until 3 , wherein an intermediate layer is arranged between the surface of the core material and the outer layer. Procedure according to one of Claims 1 until 4 , wherein a first type and a second type of shaped body is provided, wherein the first type of shaped body has a first core material and a first catalytically active material arranged on its surface, and wherein the second type of shaped body has a second core material and a on its surface arranged second catalytically active material. Procedure according to one of Claims 1 until 5 , wherein a first part of the surface of the core material is formed with a first catalytically active material and a second part of the surface of the core material is formed with a second catalytically active material. Procedure according to one of Claims 1 until 6 , wherein at least one of the starting materials in the heterogeneously catalyzed chemical reaction is used as a solid. Procedure according to one of Claims 1 until 7 , wherein the solids content in the heterogeneously catalyzed chemical reaction is more than 30% by weight. Procedure according to one of Claims 1 until 8th , wherein the catalytically active material is a metal from the group consisting of a metal of groups 3 to 13 of the periodic table, preferably Au, Ag, Cu, Pd, Pt, Ru, Rh, Re, Ni, Fe, Co, Cr, V or comprises a mixture thereof. Procedure according to one of Claims 1 until 9 , wherein the catalytically active material has a bulk modulus of at least 160 GPa. Procedure according to one of Claims 1 until 10 , wherein the catalytically active material has a Mohs hardness of at least 3.0. Procedure according to one of Claims 1 until 11 , wherein the shaped body is designed as a component of a ball mill, an eccentric vibratory mill, a rotor impact mill, a pin mill or an extruder. Procedure according to one of Claims 1 until 12 , wherein a solid second active component is added to the chemical reaction in such a way that the total proportion of solids of all components involved in the chemical reaction is more than 30% by weight. Procedure according to one of Claims 1 until 13 , wherein an inert solid is added to the chemical reaction in such a way that the total proportion of solids of all components involved in the chemical reaction is more than 30% by weight. Procedure according to one of Claims 1 until 14 , wherein the method for directly heterogeneously catalyzing a chemical reaction is carried out as a solid phase reaction. Procedure according to one of Claims 1 until 15 wherein a liquid is added to the chemical reaction in an amount in the range between 0 and 1 µl of liquid per mg measured on all components of the chemical reaction. Procedure according to one of Claims 1 until 16 , wherein the energy-transferring contacting of the starting materials with the shaped body in step (c) takes place repeatedly over a period of at least 5 minutes. Procedure according to one of Claims 1 until 17 , wherein the outer layer of the shaped body consists of the catalytically active material. Procedure according to one of Claims 1 until 18 , wherein the shaped body is a grinding reactor and/or a grinding ball. Procedure according to one of Claims 1 until 19 wherein the heterogeneously catalyzed chemical reaction is a hydroformylation, hydrogenation, isomerization, reduction, dehydrogenation reaction, olefin metathesis, hydroformylation, arylamination, hydrosilylation, cross-coupling reaction, olefin dimerization, olefin oligomerization, cyclopropanation, reduction of haloarenes, polymerization, polymerization, or telomerization reactions. Ground shaped catalyst bodies for direct heterogeneous catalyzing of a chemical reaction as defined in any one of the preceding claims, comprising a catalytically active material, wherein the catalytically active material is a metal from the group consisting of Au, Ag, Cu, Pd, Pt, Ru, Rh, Re, Ni, Fe, Co, Cr, V, a mixture thereof or an alloy based on a metal from the group consisting of a metal from groups 3 to 13 of the periodic table, preferably Au, Ag, Cu, Pd, Pt, Ru, Rh, Re, Ni, Fe, Co, Cr, V, characterized in that the shaped body has an inert core material and at least one outer layer which is formed from the catalytically active material and wherein the outer layer is arranged on the surface of the core material. Use of a shaped catalyst mill body Claim 21 as a heterogeneous catalyst in a process for directly heterogeneously catalyzing a chemical reaction according to any one of Claims 1 until 20 .

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