ES2444515A1 - Compounds associated with silicon diimide, method for obtaining same, and application thereof in the production of an amorphous, porous material - Google Patents

Abstract

Compounds related to silicon diimide, method of obtaining it, and its application in the preparation of an amorphous porous material. The present invention refers to a compound of the general formula: SixM1-xNyHz where M refers to at least one element from the group formed by germanium, aluminum and gallium; x is between 0 and 0.5; y is between 2 and 4; and z is between 2 and 8; said compound containing bonds between the silicon atoms and nitrogen atoms and between the element M and the nitrogen atoms. Likewise, the present invention refers to a method for obtaining the compound by means of an ammonolysis reaction with the precursor compounds in ionic liquid and gaseous ammonia at a temperature between -15ºC and 200ºC. Another object of the invention is the method of preparing an amorphous porous material from the described compound, as well as the material itself and its multiple uses.

Description

COMPOUNDS RELATED TO SILICON DIMIDE, METHOD OF OBTAINING, AND SUAPPLICATION IN THE PREPARATION OF AN AMORFO POROUS MATERIAL Field of the Invention

The present invention falls within various application sectors, among which are the chemical sector in general, the ceramic and the luminescent materials. In the first case, these materials can be used in two different ways. First, as catalysts for the synthesis of a very large set of chemical compounds of high added value, because they contain basic centers that are capable of catalyzing chemical reactions. Secondly, they can be used as catalyst supports, for example as a support for noble metal nanoparticles, which are capable of giving rise to bifunctional reactions, in which both the support with its basic catalytic centers and the supported metal

15 would intervene in the catalytic reaction. They could also be used in the preparation of membranes for the filtration of gases and liquids or as a stationary phase for chromatography.

With regard to the ceramic sector, they could be used as precursors of the corresponding nitrides, such as silicon nitride or aluminum nitride, with a high specific surface area and small crystal size.

The materials described in the present invention could also be used as a basis for the preparation of luminescent materials, by their suitable combination with metals belonging to the alkali metal, alkaline earth metal or rare earth groups.

25 State of the art

Porous inorganic materials based on networks that contain bonds between silicon atoms and oxygen atoms, and which may also contain aluminum atoms, of which crystalline microporous silicates such as zeolites would be the best known examples, have great application as catalysts , selective adsorbents or ion exchangers in numerous industrial sectors. The properties of this type of materials are determined by the nature of the bond between silicon atoms, and eventually also aluminum, and the oxygen atoms that make up the structure. The networks of this type of materials are constituted by MO4 tetrahedra, where M represents a silicon or aluminum atom, joined together through the oxygen atoms of the vertices, so that their physicochemical properties are determined by the nature of the atoms that make up the network, both those in tetrahedral coordination, such as silicon and aluminum, and those of oxygen, which binds to two tetrahedra. Thus, the substitution of oxygen atoms for nitrogen atoms, whose intrinsic atomic properties are very different from those of the oxygen atom, gives rise to compounds with particular properties that differ from those of oxygen-based compounds. For this reason, the physicochemical properties of the various crystalline forms of silica, SiO2, for example, are very different from that of an analogous compound such as silicon nitride, Si3N4. Indeed, although in both cases the silicon atom is in tetrahedral coordination linked to four oxygen atoms of the vertices of a tetrahedron in the first case, [SiO4], or four of nitrogen in the second, forming units [SiN4] , in the first case each oxygen atom is shared between two tetrahedra, due to the valence (II) of the oxygen, while in the case of nitrogen each atom of this

45 element is shared by three tetrahedra, because it is trivalent. Because of these chemical and structural differences, the properties of silicon nitride are very different from those of silicon oxide, which makes the former have a specific field of application within ceramic materials that silicon oxide does not have.

From the point of view of the electronic structure, the group formed by a nitrogen atom linked to a hydrogen atom, expressed in a simplified way as [NH], is isoelectronic with the oxygen atom, and has two free valences of the three which possesses the nitrogen to bond with other atoms, for example silicon atoms. That is, the group Si- [NH] -Si would be equivalent to the group of Si-O-Si atoms, the latter characteristic of the silica and the various silicates. In this way, materials that from the point of

55 The organization of chemical bonds would be analogous to amorphous silica, but they would have very different chemical properties due to the presence of the group [NH]. This type of compounds would have a general empirical formula Si [NH] 2, analogous to the formula SiO2 in the case of silica, in which two oxygen atoms would have been replaced by two groups [NH]. In addition, this type of materials would be precursors of silicon nitride, since its treatment at a very high temperature would cause the release of ammonia and its subsequent transformation into silicon nitride Si3N4, in which there would no longer be any hydrogen atom attached to atoms of nitrogen.

Different methods have been described for the preparation of compound Si [NH] 2, which is called silicon diimide. These methods are generally based on the reaction between a reactive silicon compound and ammonia, under different reaction conditions. The oldest example (M. Persoz, Ann. Chim. Phys. 44 (1830) 315) is the reaction between silicon halides, in particular silicon tetrachloride, with ammonia, according to

reaction:

SiCl4 + 6NH3 → Si (NH) 2 + 4 NH4Cl (1)

5 Although this is a seemingly simple reaction, it should be borne in mind that the synthesis of silicon diimide entails a polymerization process of silicon atoms, since as stated above, silicon diimide contains Si-N- bonds. If they do not exist in silicon tetrachloride, initial, which is a molecular compound in which there are only links between the silicon atom and each of the four chlorine atoms in the molecule. This polymerization process is extremely important, since it affects the properties of the resulting material, such as the surface area, the pore volume, the pore volume distribution and its chemical properties. Indeed, the process of forming silicon diimide by the reaction between a molecular compound containing silicon, such as silicon tetrachloride, and ammonia, is analogous to the process of forming silica gels that occurs when hydrolyze, that is, when silicon molecular compounds, such as silicon halides or alkoxysilanes, such as are reacted with water,

15 such as tetraethoxysilane, well-known processes that result in obtaining very diverse materials characterized by having textural properties, such as surface area and porosity, which depend on the particular method with which they were obtained.

The reaction described in equation (1) has been carried out under different conditions, for example by using organic solvents, as described in US 4,196,178 (1980) and in Mazdiyasni and Cooke, J. Am. Ceram. Soc. 56 (1973) 628, using the latter n-hexane as solvent. These procedures also present an additional problem such as the separation of the ammonium chloride formed in the reaction, which requires the treatment of the solid with liquid ammonia to dissolve the ammonium chloride, leaving a silicon diimide residue (Cornell, Lin and Philipp, NASA Technical Memorandum 102570, 1990).

25 Other methods for the formation of silicon diimide involve the use of precursors other than silicon halides, that is, silicon compounds that can also react with ammonia. For this purpose, the use of tetraaminoalkyl silanes has been described, compounds with the general formula Si (NRR ’) 4, where R is an organic group (US 5,258,169 (1993)).

The use of silicon diimide as a precursor for the synthesis of silicon nitride has been described in various publications (Kaskel et al., Phys. Chem. Chem. Phys., 4 (2002) 1675-1681); Lange, Wötting and Winter, Angew. Chem. Int. Ed. Engl. 30 (1991) 1579-1597). In addition to its interest as a precursor for the synthesis of silicon nitride, silicon diimide has an interest in itself as a basic catalyst (Kaskel and Schlichte, J. Catal., 201

35 (2001) 270-274); as a support for metal catalysts (Cheng et al., Chem. Mater., 18 (2006) 5996-6005); as a precursor in the preparation of filtration membranes (Cheng et al., J. Membr. Sci., 280 (2006) 530-535); and in the preparation of luminescent materials (Schlieper et al., Z. Anorg. Allg. Chem. 621 (1995) 1380; Zeuner et al., Chem. Mater. 21 (2009) 2467).

A very important aspect with a view to the application of silicon diimide in these various fields is its textural properties, that is, its specific surface area, distribution and average pore size, as well as the nature of the functional groups it presents. Regarding this last aspect, it should be borne in mind that silicon diimide not only contains Si-NH-Si groups, where the NH group would constitute a basic active center capable of catalyzing reactions typically catalyzed by bases, but also 45 has a variable proportion of Si-NH2 terminal groups that are also basic centers. In order to control the pore size of the materials resulting from the heat treatment of the silicon diimide, a necessary step when it is desired to use this material at elevated temperatures, such as in catalysis, aminosilane type compounds have been used as a precursor , in particular tris (dimethylamino) silylamine [(CH3) 2N] 3SiNH2, which is reacted with ammonia in acetonitrile and in the presence of various long chain amines, which act as pore size modifiers (Farrusseng et al., Angew. Chem. Int. Ed. 40 (2001) 4204-4206). The materials thus obtained heated in an ammonia stream at a temperature of 550 ° C are microporous, with a pore diameter between 11 and 16 Å. Along the same lines, Rovai et al. (Angew. Chem. Int. Ed. 38 (1999) 2036-2038) report that when the same aminosilane described in the previous reference is heated in the presence of ammonia at 110 ° C, silicon diimide with a very small surface area 55 is obtained , of only 50 m2 / g. When this solid is treated with trifluoromethanesulfonic acid, cycilazanes (cyclic compounds containing Si-N-Si bonds) are formed, which treated with ammonia give rise to a gel similar to silicon diimide but containing residual methyl groups, which must be treated in a stream of ammonia at 50 ° C and 15 hours for the complete elimination of these methyl groups and obtaining a porous silicon diimide gel. The same method has been used by Roser et al., Microp. Mesop Mater., 156 (2012) 196-201. Methylchlorosilane starting silicon compounds have also been used (Bradley et al., Adv. Mater., 10 (1998) 938-942; Vollmer et al., J. Mol. Cat. A: Chemical, 146 (1999) 87 -96), which are reacted in a first stage with ammonia in a solvent such as tetrahydrofuran to give cyclosilazanes, which are then polymerized by the addition of catalytic amounts of potassium hydride and methyl idouro. The solid product thus obtained is treated in an ammonia stream at 650 ° C, and the resulting material is

65 microporous, with an average pore diameter of 7 Å and an area of about 400 m2 / g.

Kaskel et al. (Phys. Chem. Chem. Phys., 4 (2002) 1675-1681) report that the treatment at a temperature of at least 800 ° C of the mixture resulting from the reaction (1), which is carried out in order to eliminate the Ammonium chloride and obtaining solids containing less than 2% chlorine, results in non-stoichiometric solid silicon and nitrogen mesoporous products. However, these materials have a severe inconvenience to

5 their use in catalysis, and is that they contain a very small number of NH groups, because the NH groups that are coordinated to two silicon atoms, forming the Si-NH-Si cluster, are active in catalysis, while the dehydrogenation of silicon diimide that occurs at high temperature according to the procedure described by Kaskel et al. It results in the formation of compounds that have the nitrogen atom coordinated to 3 silicon atoms, which is strongly prevented from activating molecules through basic catalysis mechanisms. This drawback not only affects the use of these materials as catalysts, but would also exist for all those applications that require the presence of a high proportion of NH groups in the material.

In short, the procedures that have been described so far for obtaining porous materials

15 derivatives of silicon diimide require the use of expensive silicon precursors, with various stages of reaction and separation of the intermediate products formed, and also generally lead to the formation of solids that in most cases are microporous, it is that is, they have pore diameters smaller than 2.0 nm, or they are mesoporous but have the disadvantage of containing a small proportion of active NH groups. These facts represent a serious inconvenience for their use as catalysts, especially in the liquid phase and when it is desired to process large molecules, due to the problems that these bulky molecules have to access the active centers of the catalyst.

Therefore, based on the background, it is an objective of the present invention to provide a new method for obtaining compounds related to porous silicon diimide that does not have the

25 drawbacks of the methods described above, in which, in addition, a part of the silicon atoms is replaced by atoms of other elements that also form bonds of the MN4 type, such as for example germanium, aluminum and gallium. It is also an objective of the present invention the high surface area nanoporous materials obtained by heat treating these compounds in high temperature ammonia stream.

General Description of the Invention

The present invention relates, in a first object, to a compound of the general formula:

35 SixM1-xNyHz

where M refers to at least one element of the group consisting of germanium, aluminum and gallium; x is between 0 and 0.5; and is between 2 and 4; and z is between 2 and 8; said compound containing bonds between silicon atoms and nitrogen atoms and between element M and nitrogen atoms.

The compound described is a compound related to silicon diimide, which is prepared by the reaction between precursor chemical compounds of the elements that compose it and ammonia gas in an ionic liquid.

Thus, a second object of the present invention is constituted by a method of obtaining the compound described above, characterized in that it comprises the step of subjecting to ammonolysis reaction a mixture of precursors of said compound containing the elements M and Si in a ionic liquid, through a stream of gaseous ammonia at a temperature between -15ºC and 200ºC, including both limits. The method has the peculiarity that it is carried out without the presence of organic compounds that tend to act as structure directing agents, unlike the procedures known so far in the field.

The process described in this invention is based on the use of an ionic liquid as a means of

55 reaction. Ammonia is very soluble in ionic liquids (Yokozeki et al., Ind. Eng. Chem. Res., 46 (2007) 1258; Applied Energy, 84 (2007) 1258), reaching a solubility close to what it has in water, which is much higher than what it has in the organic solvents commonly used in the ammonolysis reaction. This high solubility of ammonia in ionic liquids allows it to act as a mineralizing element in the polymerization reactions that lead to the formation of the compound network from the ammonolysis reaction of silicon tetrachloride with ammonia, that is, in In the present case the solvent plays an active role in the process of preparing the compound related to silicon diimide. This is a differential fact of the present invention that is absent from the rest of the procedures reported so far, in which the organic solvent used is simply a means of controlling the temperature produced by the ammonolysis reaction, which is strongly exothermic, while at the moment

Invention the ammonia dissolved in the ionic liquid plays the role of mineralizing agent, as do hydroxyl ions, for example, in the preparation of silica gels by hydrolysis in medium.

Basic silicon compounds such as silicon alkoxides.

Ionic liquids have the characteristics suitable for use in the present invention, since, in addition to being excellent solvents for ammonia, they are liquid at room temperature and in the range of 5 temperatures used in the present invention and have high chemical stability. , so that they do not react with the reagents present in the synthesis medium.

The solid thus obtained, after being washed with methanol and filtered, can be heat treated in an ammonia stream at an elevated temperature to obtain an amorphous solid material having a high surface area.

10 specific and a high pore volume, and may have a narrow pore size distribution in the range between 1 nm and 50 nm. This procedure has the additional advantage that the ionic liquid can be recovered from the methanol used in the washing, and reused.

The possibility of obtaining a porous amorphous material from the compound here can also be contemplated.

15 described related to the silicon diimide without obtaining the latter previously, that is, starting from said derivative in its pure state, once already prepared. Thus, a third object of the present invention is a method of preparing an amorphous porous material from the compound of interest herein, characterized in that it comprises the step of thermally treating said compound, by means of an atmosphere of gaseous ammonia at a temperature between 500 ° C and

20 1200 ° C, including both limits, for a time between 30 minutes and 10 hours, including both limits.

The present invention is characterized in that the heat treatment of the compound described in an atmosphere of ammonia at a temperature between 500 ° C and 1200 ° C for a time between 30 minutes and 10 hours gives

This results in a solid material that has a high surface area and can have an average pore size between 1 nm and 50 nm, and which has a very small sulfur and residual carbon content. In addition, this process leads to the formation of a product resulting from the heat treatment that has a high concentration of NH groups, which are active centers capable of promoting reactions catalyzed by bases.

The efficiency of this process of heat treatment in ammonia to remove the remains of ionic liquid and other organic compounds that may be occluded in the uncalcined product can be determined by analyzing the nitrogen and sulfur content. The infrared spectrum of calcined products shows the presence of bands that are assigned to different vibration modes of Si-N links, and links

35 N-H. The presence of these N-H bonds is particularly relevant from the point of view of catalytic applications, since N-H groups are active centers in basic catalysis reactions.

A fourth object of the present invention is an amorphous porous material obtainable by the above procedure, characterized in that it comprises a pore volume distribution comprised

40 between 1 nm and 50 nm, including both limits.

Since the amorphous porous material has novel properties that differentiate it from other similar materials already known, the present invention also covers the amorphous porous material itself regardless of whether it is obtained by the process described above.

The fifth and final object of the invention is the use of porous amorphous material as a catalyst, as a catalyst support, in membranes for filtration of gases and liquids, as a precursor of nitrides in the manufacture of ceramic products, or in the manufacture of materials. luminescent.

50 First, amorphous porous materials can be used as catalysts for the synthesis of a very large set of chemical compounds with high added value, because they contain basic centers that are capable of catalyzing chemical reactions. Secondly, they can be used as catalyst supports, for example as a support for noble metal nanoparticles, which are capable of giving rise to bifunctional reactions, in which both the support with its basic catalytic centers and metal

55 supported would intervene in the catalytic reaction.

Likewise, as stated, they could be used in the preparation of membranes for the filtration of gases and liquids, or as a stationary phase for chromatography.

60 They could also be used as precursors of the corresponding nitrides, such as silicon nitride or aluminum nitride, of high specific surface area and small crystal size.

The materials described in the present invention could also be used as a basis for the preparation of luminescent materials, by their suitable combination with metals belonging to the groups of the

65 alkali metals, alkaline earth metals or rare earths.

Detailed description of the invention

Preferably, in the general formula of the compound x is between 0.05 and 0.5; that is, it always has a certain amount of Si attached to the atoms of N, accompanying the element M.

As regards the process for obtaining the compound, the silicon precursors used are preferably selected from the group consisting of:

-

silicon halides of formula SiX4 where X designates chlorine, bromine or iodine (for example, and more preferably, silicon tetrachloride);

-

aminosilanes of the general formula SiX4 (NRR ') x, where R and R' are identical or different and represent alkyl groups with a number of carbon atoms between 1 and 6, or vinyl, phenyl or hydrogen groups, where X represents chlorine, bromine, iodine or hydrogen, the value of x being between 0 and 4 (for example, and more preferably, chloroaminosilanes); Y

15 -Any mix of them.

On the other hand, the precursors of M are preferably compounds of general formula MX, where M represents germanium, aluminum or gallium; e y is 4 for germanium and 3 for aluminum and gallium, while X represents a halogen atom (for example, and more preferably, anhydrous chlorides of the indicated elements). In this way, the precursor can be anhydrous aluminum trichloride, anhydrous gallium trichloride, or germanium tetrachloride.

Since the type of compounds such as that described herein, such as silicon diimide, is sensitive to air and moisture, it is preferable to use ionic liquids in the present invention that have a preferably hydrophobic character, but in no way can this be considered a limitation of the invention He

1-ethyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] amide ionic liquid has a melting point of -18 ° C, has a high thermal stability and the ammonia solubility therein is very high, resulting in a Ionic liquid suitable for the present invention. Other ionic liquids also suitable for use according to the process described in the present invention are derivatives of the imidazolium ring having the general formula

R

N +

X

N

R '

In which R and R 'designate alkyl organic groups that may be the same or different and represent organic groups with a number of carbon atoms between 1 and 10, and where X designates an anion, as for example it may preferably be selected from the group consisting of: bis [(trifluoromethyl) sulfonyl] amide anion, chloride, tetrafluoroborate and tetrafluorophosphate anion. Preferably, the number of carbon atoms is between 1 and 6, and more preferably between 1 and 4.

The method in question can be carried out in ammonia stream either at atmospheric pressure or under ammonia pressure, at a pressure between atmospheric pressure and 200 atm, including both limits. If he

The method is performed under ammonia pressure, said pressure is preferably between 1 and 50 atm.

Preferably, the method of obtaining the compound is carried out at a temperature between 20 ° C and 200 ° C, more preferably still between 15 ° C and 180 ° C.

The reaction time of ammonolysis is between 5 minutes and 50 days, more preferably between 1 hour and 10 days. In a preferred embodiment, this reaction time is between 30 minutes and 7 days, and in another preferred case between 30 minutes and one day.

This ammonolysis reaction is usually carried out in a flask through which the ammonia current is passed, although this practice should not be considered as limiting the invention.

In a preferred embodiment, after the ammonolysis reaction the product obtained from said reaction is heated at a temperature between 20 ° C and 200 ° C for a reaction time between 1 hour and 10 days, with or without ammonia gas pressure, and if it is under pressure it is between 1 and 200 atmospheres. This stage of maturation of the compound has a decisive influence on the properties of the material that can subsequently be obtained from it, and is usually carried out in an autoclave, although this aspect is not limiting of the invention. After this stage, it is convenient to keep the product in an inert atmosphere to avoid contact with the atmosphere and, as a consequence, its oxidation.

65 Preferably, after the ammonolysis reaction or after the heating of the product with or without ammonia gas flow when it is carried out, the product obtained from said reaction is washed with a solvent, to remove both the remnants of leftover elements (excess of ionic liquid) such as those formed during the reaction (ammonium chloride), and then the product is filtered, to have the compound in its purest form that can be used as a raw material in the preparation of an amorphous porous material as described in the section General description. In the most preferred case, the solvent is methanol.

An advantage of the present invention is that the excess ionic liquid of the reaction is dissolved in the solvent used in the wash, which is preferably methanol, and can be recovered and reused by well known methods that also allow the recycling of the methanol used in the washed.

In a preferred embodiment of the method of obtaining the compound related to silicon diimide, a precursor compound or mixture of several precursor compounds is arranged in a flask, to which at least one ionic liquid derived from the imidazolium cation is added according to the formula described above, where R and R 'may be the same or different and represent organic groups with a number of carbon atoms between 1 and 10, preferably between 1 and 4; X represents an anion, such as the anion

15 bis [(trifluoromethyl) sulfonyl] amide or the chloride anion.

The reaction mixture is introduced into a flask that is maintained at a temperature between -15 ° C and 200 ° C, and is contacted with gaseous ammonia, for a time between 5 minutes and a week, preferably between 30 minutes and a day. After that time, the reaction mixture is preferably introduced into an autoclave provided with a Teflon sheath, and heated to temperatures between 20 ° C and 200 ° C. After a reaction time between 30 minutes and 10 days, the autoclave is cooled to room temperature and introduced into a closed system containing an inert atmosphere, such as nitrogen, or helium, such as a glove bag or a “box dry ”, to avoid its contact with the air and therefore its oxidation. The contents of the autoclave are washed with dry methanol to remove the

Excess reagents, and filtered to recover a solid product.

In a preferred application of this invention, the reaction mixture obtained after the reaction of ammonolysis with gas ammonia and introduced into the stainless steel autoclaves is treated with high purity ammonia at temperatures between 20 and 200 ° C, and pressures between 1 and 200 atmospheres. After a reaction time between 1 hour and 10 days, the autoclave is cooled and its content is treated with methanol as explained above.

The washed and filtered compound can be further subjected to heat treatment to obtain an amorphous porous material, under the conditions specified in the previous section. In this case the temperature of the

The heat treatment, which is between 500 ° C and 1200 ° C, is preferably between 600 ° C and 800 ° C.

Regarding the use of the porous amorphous material as a catalyst, said use is preferred in reactions catalyzed by bases, such as those selected from alkylaromatic compound alkylation reactions with methanol or condensation reactions of organic compounds containing active CH2 methylene groups, such as reactions of condensation of Michael.

In case the material is used as a catalyst support, said catalyst is preferably constituted by nanoparticles of noble metals.

45 Description of the figures

Figure 1. Nitrogen adsorption / desorption isotherm of the sample treated in ammonia at a temperature of 600 ° C prepared as described in Example 1.

Figure 2. Pore size distribution of the sample whose isotherm is shown in Figure 1.

Figure 3. FTIR spectra of the samples treated in ammonia at 600 ° C prepared in Examples 1 (spectrum b) and 2 (spectrum a). In the region of the spectrum between 1400-600 cm -1, the samples

55 have two bands at 925 and 1030 cm-1 that can be assigned to the asymmetric tension vibrations of the Si-N bond (υas (Si-N)) and a band around 1200 cm-1 that can be attributed to the deformation of NH groups attached to silicon atoms (δ (NH)). Both spectra also have a band around 786 cm -1 corresponding to the deformation of the Si-NH2 (δ (Si-NH2)) groups.

Figure 4. Pore size distribution of the sample treated in ammonia stream at a temperature of 600 ° C prepared according to example 3.

Examples

65 Three examples of the present invention are described below, which in no case can be considered as limiting examples of the invention.

Example 1:

In a reaction vessel, 47.5 g of the 1-ethyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] amide ionic liquid are weighed and then 14.2 g of SiCl4 are added. The reaction vessel is immersed in an ice-water bath and is

5 connects a bubbler with silicone and a safety glass. The gaseous ammonia is then added while maintaining the mixture under constant magnetic stirring. After the reaction a highly viscous white gel is obtained.

Then, in a glove bag the contents of the reaction vessel are extracted, homogenized,

10 introduces 17 ml volume stainless steel autoclaves with glass sleeves fitted with a valve.

The autoclaves are then contacted with gaseous ammonia at a partial pressure of ammonia in the 7.5 atm system, 0.6 g of gaseous ammonia being dissolved in the mixture contained in the autoclaves. TO

The autoclaves are then heated in an oven at 180 ° C for 43 hours in a static regime.

After this process, the solids obtained are extracted inside the glove bag, washed with previously re-distilled dry methanol and filtered under a stream of nitrogen.

The product obtained is introduced into a quartz tubular reactor and treated in an ammonia stream at a temperature of 600 ° C for two hours. Figure 1 shows the nitrogen adsorption isotherm of the calcined material, whose surface area determined from the adsorption isotherm was found to be 629 m2 / g, and the pore volume of 1.43 cm3 / g. Figure 2 shows the pore volume distribution, showing that the distribution is centered at 12 nm, that is, in the range of the mesopores. In the

Figure 3 depicts the infrared spectrum of the material, in which the bands due to the presence of Si-N and N-H bonds are clearly identified.

Example 2:

The ammonolysis reaction is carried out following the procedure described in Example 1. The gel obtained is extracted inside a glove bag, homogenized and introduced into 60 ml volume stainless steel autoclaves provided with covers. Teflon and heated in an oven at 180 ° C for 43 hours in static mode.

The solids obtained after this process are subjected to the same washing and filtering treatment described in Example 1. The solid product is treated with ammonia at 600 ° C under the same conditions as those described in Example 1. The product thus treated has a surface area of 251 m2 / g and a pore volume of 0.07 cm3 / g.

In Figure 3 it represents the infrared spectrum of the material, in which the bands 40 due to the presence of Si-N and N-H bonds are clearly identified.

Example 3:

In a reaction vessel, 47.5 g of the ionic liquid 1-ethyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] amide is weighed

45 and then 14.2 g of SiCl4 and 1.11 g of AlCl3 are added. The reaction vessel is immersed in an ice-water bath and connected to a silicone bubbler and a safety glass. The gaseous ammonia is then added while maintaining the mixture under constant magnetic stirring. After the reaction a highly viscous white gel is obtained.

50 Then, in a glove bag, the contents of the reaction vessel are extracted, homogenized, placed in 17 ml volume stainless steel autoclaves with glass covers fitted with a valve. The autoclaves are then contacted with gaseous ammonia at a partial pressure of ammonia in the 7.5 atm system, 0.6 g of gaseous ammonia being dissolved in the mixture contained in the autoclaves. The autoclaves are then heated in an oven at 180 ° C for 43 hours

55 static.

After this process, the solids obtained are extracted inside the glove bag, washed with previously re-distilled dry methanol and filtered under a stream of nitrogen. The product thus obtained is subjected to the ammonia treatment at a temperature of 600 ° C as described in Example 1. The solid thus

60 obtained has a surface area of 336 m2 / g and a pore volume of 1.06 cm3 / g. The pore volume distribution is shown in Figure 4, showing that the distribution is centered at 13 nm.

Claims (22)

1. A compound of general formula: 5 SixM1-xNyHz where M refers to at least one element of the group consisting of germanium, aluminum and gallium; x is between 0 and 0.5; and is between 2 and 4; and z is between 2 and 8; said compound containing bonds between silicon atoms and nitrogen atoms and between element M and nitrogen atoms. 2. The compound described in the preceding claim, wherein x is between 0.05 and 5, including both limits. A method of obtaining the compound described in any one of claims 1 or 2, characterized in that it comprises subjecting to ammonolysis reaction a mixture of precursors of the compound containing the elements Si and M in an ionic liquid, by means of a stream of gaseous ammonia at a temperature between -15ºC and 200ºC, both limits included. 4. The method according to the preceding claim, wherein the silicon precursors used are selected from the group consisting of: - silicon halides of formula SiX4 where X designates chlorine, bromine or iodine; -aminosilanes of the general formula SiX4 (NRR´) x, where R and R´ are identical or different and represent 25 alkyl groups with a number of carbon atoms between 1 and 10, or vinyl, phenyl or hydrogen groups, where X represents chlorine, bromine, iodine or hydrogen, the value of x being between 0 and 4; Y

-

Any mix of them.

5.

The method according to the preceding claim, wherein the silicon halide is silicon tetrachloride, and the aminosilane is a chloroaminosilane.

6.

The method according to any one of claims 3 to 5, wherein the M precursors are compounds of

general formula MX, where M represents germanium, aluminum or gallium; e y is 4 for germanium and 3 for aluminum and 35 gallium, while X represents a halogen atom.

7.

The method according to the preceding claim, wherein the precursor of M is selected from the group consisting of anhydrous aluminum trichloride, anhydrous gallium trichloride and germanium tetrachloride.

8.

The method according to any one of claims 3 to 7, wherein the ionic liquid is a hydrophobic liquid.

9.

The method according to the preceding claim, wherein the ionic liquid is selected from 1-ethyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] amide and an imidazolium ring derivative having the general formula:

R N + X N R ' where R and R 'designate the same or different alkyl organic groups with a number of carbon atoms between 1 and 10, and where X designates an anion. The method according to the preceding claim, wherein the number of atoms is between 1 and 4.

eleven.

The method according to any one of claims 9 or 10, wherein the X anion is selected from the group consisting of: the bis [(trifluoromethyl) sulfonyl] amide anion, the chloride anion, tetrafluoroborate and tetrafluorophosphate.

12.

The method according to any one of claims 3 to 11, wherein the ammonia stream is at atmospheric pressure or at a pressure between atmospheric pressure and 200 atm, including both limits.

The method according to the preceding claim, wherein the ammonia pressure is preferably between 1 and 50 atm. 14. The method according to any one of claims 3 to 13, wherein the ammonolysis reaction temperature is between 20 ° C and 200 ° C, including both limits. The method according to any one of claims 3 to 14, wherein the ammonolysis reaction time is between 5 minutes and 50 days. 16. The method according to any one of claims 3 to 15, wherein after the ammonolysis reaction the product obtained from said reaction is subjected to a heating step at a temperature comprised 10 between 20 ° C and 200 ° C for a reaction time between 1 hour and 10 days, with or without gas ammonia pressure, at pressures between 1 and 200 atm when performed with gas ammonia pressure. 17. The method according to any one of claims 3 to 16, wherein after the ammonolysis reaction or after the heating step, the product of said reaction is washed with a solvent and filtered. fifteen

18.

The method according to the preceding claim, wherein the solvent is methanol.

19.

The method according to any one of claims 17 or 18, wherein the excess ionic liquid of the

The reaction is dissolved in the solvent used during washing, recovering both the solvent and the ionic liquid. 20. The method according to the preceding claim, wherein the ionic liquid is recovered and reused in the ammonolysis reaction. 21. The method according to any one of claims 17 to 20, wherein the compound is subjected to heat treatment by atmosphere of gaseous ammonia at a temperature between 500 ° C and 1200 ° C, including both limits, for a time between 30 minutes and 10 hours, including both limits, until obtaining a porous amorphous material. 22. A porous amorphous material obtainable by the method described in claim 21, which comprises a pore volume distribution between 1 nm and 50 nm, including both limits.  23. A porous amorphous material derived from a compound of general formula 35 SixM1-xNyHz where M refers to at least one element of the group consisting of germanium, aluminum and gallium; x is between 0 and 0.5; and is between 2 and 4; and z is between 2 and 8; said compound containing bonds between silicon atoms and nitrogen atoms and between the element M and the atoms of 40 nitrogen; comprising a distribution of pore volume between 1 nm and 50 nm, including both limits. 24. Use of the amorphous porous material described in any one of claims 22 or 23, as a catalyst.  24. Use of the amorphous porous material described in any one of claims 22 or 23, as a catalyst support. 25. Use of the amorphous porous material described in any one of claims 22 or 23, in membranes 50 for filtration of gases and liquids. 26. Use of the amorphous porous material described in any one of claims 22 or 23, as a precursor of nitrides in the manufacture of ceramic products. Use of the porous amorphous material described in any one of claims 22 or 23, in the manufacture of luminescent materials, combined with metals belonging to the alkali metal, alkaline earth metal or rare earth groups. Quantity Adsorbed cm3 / g   Adsorption  0.0 0.5 1.0 Relative pressure P / P0   FIG. one 2.0 1.5 dV / log (D) (cm3 / gA0) 1.0 0.5  0.0 0 Pore diameter (A) FIG. 2 dV / log (D) (cm3 / gA0) Absorbance

925

1030

1200

786

b)

to)

1400

1200 1000 800 Number of waves (cm-1) FIG. 3 600

1.5

1.0 0.5 0.0 30 60 90 120 150 180 210 240 270 300 330 0 Pore diameter (A) FIG. 4 SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 201231192 SPAIN Date of submission of the application: 25.07.2012 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: See Additional Sheet RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

TO

F. CHENG et al., "Preparation of a mesoporous silicon aluminum nitride via non-aqueous sol-gel route", J. Mater. Chem., 2005, vol. 15, pages 772-777. 1-28

TO

WO 2006046012 A1 (THE UNIVERSITY OF HULL) 04.05.2006, page 5, lines 16-27; page 6, lines 14-23; page 8, lines 4-9; claims 1,6-10. 1-28

TO

F. CHENG et al., "Catalytic ammonolytic sol-gel preparation of a mesoporous silicon aluminum nitride from a single-source precursor", J. Organomet. Chem., 2007, vol. 692, pages 3816-3822. 1-28

TO

F. CHENG et al., "General method of preparation of mesoporous M / Si3N4 nano-composites via a non-aqueous sol-gel route", Chem. Commun., 2005, vol. 45, pages 5662-5664. 1-28

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 14.10.2013

Examiner E. Dávila Muro Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201231192 CLASSIFICATION OBJECT OF THE APPLICATION  C04B35 / 584 (2006.01) C04B35 / 624 (2006.01) C04B38 / 00 (2006.01) B01J21 / 06 (2006.01) Minimum documentation sought (classification system followed by classification symbols) C04B, B01J Electronic databases consulted during the search (name of the database and, if possible, search terms used) INVENES, EPODOC, WPI, XPESP, NLP, REGISTRY, CAPLUS State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201231192 Date of Completion of Written Opinion: 14.10.2013 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 1-28 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-28 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201231192 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

F. CHENG et al., J. Mater. Chem., 2005, vol. 15, pp. 772-777.

D02

WO 2006046012 A1 (THE UNIVERSITY OF HULL) 04.05.2006

D03

F. CHENG et al., J. Organomet. Chem., 2007, vol. 692, pp. 3816-3822.

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The invention relates to compounds related to the silicon diimide of the general formula SixM1-xNyHz where M = Al, Ge, Ga (claims 1-2), as well as the method of obtaining them by ammonolysis of a mixture of precursors of compounds containing Si and M in an ionic liquid in ammonia stream and at a temperature between -15 ° C and 200 ° C (claims 3-21). The invention also relates to the porous material obtained from these compounds (claims 22-23) and their use as catalysts or catalyst support, in gas and liquid filtration membranes, precursors in the preparation of ceramic products or in obtaining of luminescent products (claims 24-28). Document D01 discloses the preparation of a mesoporous silicon and aluminum nitride of formula Si3Al (NH) x (NH2) and (NMe2) z by a catalytic ammonolysis process from a single silicon-aluminum imide precursor of formula (C4H8O ) Al [HNSi (NMe2) 3] 3 in THF non-aqueous medium. The pyrolysis of the gel at 1000 ° C in NH3 stream allows to obtain an amorphous ceramic composite material of Si-Al-N composition in which Si is tetrahedrally coordinated with N and Al is present in the mixed forms AlN4, AlN5 and AlN6. This amorphous porous material has a high surface area of 190m2g-1 and a pore volume distribution of 2-9 nm. The difference between what is disclosed in D01 and the object of the invention lies in the presence in the precursor imide of peripheral groups Si (NMe2) 3 instead of Si (NH) 2. In addition, the ammonolysis reaction of the gel is carried out in THF as a solvent and not in the presence of an ionic liquid. Document D02 discloses a nanoporous material derived from silicon nitride SiN4, silicon oxynitride Si2N2O or silicon imidonitride Si3N4-2x (NH) 3x containing a group III metal (Al, B) or a transition metal (Ni, Pd, Pt) The material is prepared by a sol-gel process followed by pyrolysis at 1000 ° C in NH3 stream. It is used to prepare filters and gas sensors or catalysts for chemical reactions. Examples of mesoporous composite materials of Si3N4-Pd and Si3N4-Ni are disclosed in D02 but not with Al, Ge or Ga. Document D03, similar to D01, refers to the preparation of a mesoporous Si and Al nitride by means of solgel ammonolysis in a non-aqueous medium of a single H6Al6 (NiPr) 4 [NSi (NMe2) 3] 2 precursor so that it is obtained a Si and Al imide of the formula Al3SiN2 (NH) w (NH2) x (NMe2) and (NiPr) z which is then calcined at 1000 ° C in a stream of NH3. Also in this case the difference with the object of the invention is in the presence of Si (NMe2) 3 and (NiPr) groups in the imide precursor and that the reaction is not carried out in an ionic liquid. No documents have been found in the state of the art that refer to compounds derived from silicon diimide with the metals Al, Ga or Ge of the general formula SixM1-xNyHz nor to procedures for obtaining these compounds by ammonolysis of precursors containing Yes and an Al, Ga or Ge metal in the presence of an ionic liquid. Nor are there indications that lead the person skilled in the art to conceive the use of porous amorphous materials derived from compounds of the formula SixM1-xNyHz as catalysts or catalyst support, as integrating filtration membranes, nitride precursors in the preparation of ceramic products or for the manufacture of luminescent materials combined with alkali metals, alkaline earth metals or rare earth metals. Consequently, the characteristics of claims 1-28 are considered new and with inventive activity and industrial application according to articles 6.1 and 8.1 LP 11/1986. State of the Art Report Page 4/4