ES2351494B1 - ORGANIC-INORGANIC MICROPOROUS CRYSTAL MATERIAL BASED ON ALKALINERERAL CATIONS, PREPARATION PROCEDURE AND USES - Google Patents

Abstract

Crystalline microporous organ-inorganic material based on alkaline earth cations, preparation process and uses. # The present invention relates to a family of crystalline microporous organ-inorganic materials containing alkaline earth cations and dicarboxylic acids, their preparation process and their use as heterogeneous catalysts. reusable for reactions in organic chemistry, as molecular sieves and as gas and liquid absorbers.

Description

Crystalline microporous organ-inorganic material based on alkaline earth cations, preparation procedure and uses.

The present invention refers to a family of crystalline microporous organo-inorganic materials containing alkaline earth cations and dicarboxylic acids, their preparation process and their use as reusable heterogeneous catalysts for reactions in organic chemistry, such as molecular sieves and as liquid gas absorbers.

State of the art

The nanostructured organ-inorganic hybrid materials, also called MOFs (Metal-Organic Frameworks), have demonstrated during the last years their potential use as multifunctional crystalline materials with interesting properties and innovative applications.Amode example, it is worth mentioning the use of these types of materials such as heterogeneous catalysts, molecular sieves, gas absorbers, LED emitters and more recently applied in controlled drug release (B. Wangycol., Nature. 2008. 453, 207; F. Gándara ycol., Cryst. Growth Des. 2008,8,2, 378; P. Horcajadaycol., J. Am. Chem. Soc. 2008. 130, 6774). Currently, many research groups are trying to prepare MOFs with new structures and composition that can lead to a substantial improvement in the properties of these systems.

In recent years, the use of divalent and trivalent cations derived from transition metals and, more recently, from rare earths, has resulted in the preparation of a large variety of this family of microporous crystalline materials. However, if we extend our search to MOFs based on alkaline earth cations we find few reported examples (RKB Nielsenycol., Solid State Science. 2006,8, 1237; C. Vo Ikringery col., Solid State Science. 2007,9, 455; C .Volkringerycol., Cryst. Growth Des. 2008,8,658; S. Chenycol., Anorg. Allg. Chem. 2008. 634, 1591; CAWilliamsycol., Cryst. Growth Des. 2008,8 (3), 911), a despite interesting properties of sorption (O2, H2, CO2) (M. Dinca et al., J. Am. Chem. Soc. 2005, 127, 9376) and catalytic behavior (J. Spielmannycol., Angew. Chem. Int. Ed 2008, 47, 9434) offering these elements.

More specifically, it should be noted that MOFs have been proposed as a new class of heterogeneous catalysts, due, above all, to:

-

First, MOFs have a good dispersion of catalytically active centers, because they are part of an organic matrix.

-

Next, a large number of these compounds have micro mesoporism, which only favors catalytic activity but also has a very significant influence on selectivity.

-

In addition, due to the hybrid nature of these organ-inorganic materials, they are proposed as potential bifunctional catalysts, taking advantage of the acid-base characteristics of organic ligands and reactive properties of metals.

-

On the other hand, these types of compounds are mainly indicated for reactions in chemistry and obtaining high value-added products, since these are carried out under mild conditions.

Therefore, as shown in memory, the design of MOF-type systems based on alkaline earth cations and possessing catalytic and sorption properties is presented as an alternative of low cost and, above all, of a lower environmental impact, compared to the systems currently used at industrial level Table 1 shows the metals on which commonly used catalysts are based, for some of the most demanded reactions at the industrial level.

TABLE 1

Among the most important, the petrochemical industry annually uses large amounts of precious metals supported in various porous materials, such as silica or inorganic salts (CaCO3), as a catalyst for hydrogenation reactions, especially olefins.

Description of the invention

Therefore, in a first aspect, the present invention refers to a crystalline microporous organ-inorganic material AEPF, AlkalineEarth PolymericFramework (share time material of the invention), characterized in that it presents as a repeat unit the following generic formula:

where:

-

Month an alkaline earth cation, in oxidation state +2,

-

A is a host molecule, comprising a solvent selected from the list comprising ethanol, propanol, butanol, toluene, cyclohexane, hexane, heptane, octane, pyridine and any combination thereof, from the reaction medium,

-

For an organic group, it is preferably an aromatic group selected from phenyl, naphthyl or diphenyl, which is branched or not with other groups, that is, an isolated or several aromatic group linked together by means of a branched (C1-C6) alkyl branched, which may be substituted, preferably substituted by a halogen,

-

x represents a value less than or equal to 4 (x ≤ 4), preferably less than 2 (x ≤ 2),

-

and represents a value between 0.5y2, (0.5≤ y≤ 2),

-

z represents a value between 0 and 4, (0 ≤ z ≤ 4) and

-

n is the number of host molecules and represents a value between 0 and 4 (0 <n ≤ 4), preferably between 0 and 2 (0 <n ≤ 2).

The term "alkyl" refers, in the present invention, to aliphatic, linear or branched chains, having carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, nhexyl, etc. Preferably, the alkyl group has between 1 and 4 carbon atoms. The alkyl groups may be optionally substituted by one or more substituents such as halogen, hydroxyl, azidao or carboxylic acid.

By "halogen" is meant, in the present invention, an atom of bromine (Br), chlorine (Cl), iodine (I) or fl uor (F), preferably fl uor (F).

In a preferred embodiment, M is selected from Mg, Ca, SroBa.

In another preferred embodiment, A is a solvent selected from the list comprising ethanol, propanol, butanol, toluene, cyclohexane, hexane, heptane, octane, pyridine or any combination thereof.

In another preferred embodiment, R is represented by the general formula R1-C (R2) 2-R1, where R1 is an aromatic group selected from enthephenyl, naphthyl diphenyl and R 2 is a group selected from intermethyl, ethyl, isopropyl, terbutyl

oCF3. Preferably, R1 is a phenyl group and R2 is a CF3 group and, therefore, R is represented by:

In another preferred embodiment, the ratio x: y: z is 0.5: 1: 1 and n represents a value between 0 and 2 (0 <n ≤ 2).

"AEPF crystalline microporous organ-inorganic materials" in the present invention means those nanostructured hybrid organ-inorganic materials, also called MOFs (from English, Metal-Organic Frameworks), which have demonstrated their potential use over the last few years. As multifunctional crystalline materials with interesting properties and exciting applications. These MOFs are crystalline compounds that consist of metal ions or clusters often coordinated to rigid organic molecules to form structures of one, two or three dimensions that can be porous. In some cases, the pores are stable to the removal of host molecules (often solvents) and can be used for storage of gases such as hydrogen and carbon dioxide. MOFs are also known as hybrid and polymer coordination matrices, although these terms are not strictly identical.

In Scheme 1, the AEPF family of carboxylic acids is represented in a generic way.

Scheme1

The Scheme 2 represents a preferred analysis of the family of carboxylic acid components of EPA, where R is a diphenyl as described above:

Scheme2

In a preferred embodiment, in the chemical composition of the organ-inorganic material of the invention, M is Ca, the ratio x: y: zes 0.5: 1: 1 and nes menorque1 (n ≤ 1). More preferably, the organ-inorganic material of the invention is AEPF-1, and is represented by the following repeating unit of empirical formula:

where:

-

x represents a value of 0.5,

-

and represents a value of 1,

-

z represents a value of 1,

-

n represents a value 0.7y

-

Ase selected from ethanol, propanol, butanol, toluene, cyclohexane, hexane, heptane, octane or any

of their combinations. Preferably propanol, and even more preferably isopropanol.

In another more preferred embodiment, the chemical composition of the inorganic-inorganic material of the invention, AEPF2, is represented by the following repeating unit of empirical formula:

where: -x represents a value of 0.5, -y represents a value of 1, -z represents a value1,

-

n represents a value0.

In another preferred embodiment, in the chemical composition of the organ-inorganic material of the invention, M is Sr, the ratio x: y: z is 0.5: 1: 1, n is less than 1 (n ≤ 1) and A is pyridine. More preferably, the organoorganic material of the invention is AEPF-3, and is represented by the following unit of repetition of empirical formula:

where: -x represents a value of 0.5, -y represents a value of 1, -z represents a value of 1, -n represents a value between 0 and 1 (0 <n ≤ 1).

In a second aspect, the present invention relates to a process for the preparation of the organinorganic material of the invention (from now on the procedure of the invention), which comprises:

a) preparation of a reaction mixture comprising:

-

an alkaline earth cation,

-

a HOOC-R1C (R2) 2-R1-OOOH dicarboxylic acid, where R1 is an aromatic group selected from phenyl, naphthyl or diphenyl and R2 is a group selected from methyl, ethyl, isopropyl, terbutyl or CF3, preferably in the form of salt,

-

a host molecule A, which comprises a solvent selected from the list comprising ethanol, propanol, butanol, toluene, cyclohexane, hexane, heptane, octane, pyridine and any combination thereof, which is derived from the reaction medium and

-

Water;

b) heat treatment of the reaction mixture of step (a) at a temperature between 80 ° C and 220 ° C, until its crystallization is achieved.

In a preferred embodiment of the process of the invention, the reaction mixture has a composition, in terms of molar ratios, between the ranges: -M / dicarboxylic acid = 0.25-1 -H2O / S = 4.5-10.3 -H2O / M = 300-800

In another preferred embodiment of the process of the invention, the heat treatment to which the reaction mixture is subjected in step (b) is performed at a temperature between 100 ° C and 200 ° C. Preferably, the heat treatment is carried out at a temperature between 130 ° C and 180 ° C. Said heat treatment can be carried out in static or with stirring of the mixture.

Once the crystallization is complete, the crystalline product is separated by filtration, washed with water and common organic solvents and air dried.

Therefore, another preferred embodiment of the process of the invention further comprises:

c) separation, washing and heat treatment of the crystalline product obtained in step (b) at a temperature between 40 ° C and 150 ° C.

More preferably, the separation, washing and heat treatment stage of the crystalline product obtained in step (b) takes place at a drying temperature of between 100 ° C and 120 ° C and increases during a time between 10 and 20 h.

Thermogravimetry analysis determines the content (n) of When the material is heated to temperatures of up to 150 ° C in an atmosphere of N2.

The IR spectroscopy technique allows the characterization of these materials. Thus, the IR spectra of these materials can be recorded in the transmission mode by preparing wafers of these solids that are transparent to infrared radiation by compression at pressures between 1 and 10Tmx cm2 for a time between 1 and 5min.

X-ray diffraction demonstrates the purity and crystallinity of the material.

The surface area of these materials can be determined using gas adsorption isotherms (N2 and Ar) using Langmuir algorithms.

In a final aspect, the present invention refers to the use of the organ-inorganic material of the invention as a catalyst in a process of compound conversion, which comprises contacting a feed of compounds, as substrates, with an amount of the invention material and other compounds. reagents

In a more preferred embodiment, the compound conversion process is a hydrogenation of alkenes using H2 as a reducing agent.

Scheme3

Where R, R ’, R”, R ”’ represent alkyl or aryl groups.

In another more preferred embodiment, the compound conversion process is a hydroformylation of alkenes. Scheme4

Where R represents an alkyl or aryl group.

In another more preferred embodiment, the compound conversion process is a hydrosilylation of aldehydes using as a reagent an organic compound derived from silane.

Scheme5

Where R, R ’, R”, R1 represent alkyl or aryl groups.

In another more preferred embodiment, the compound conversion process is a hydrosilylation of ketones using as a reagent an organic compound derived from the silane.

Scheme6

Where R, R ’, R”, R1, R2 represent alkyl or aryl groups.

In another more preferred embodiment, the compound conversion process is a hydrosilylation of alkenes using as a reagent an organic compound derived from the silane.

Scheme7

Where R, R ', R ", R1; R2 represent alkyl or aryl groups.

In another aspect, the present invention relates to the use of the organ-inorganic material of the invention as a selective absorbent component of compounds, which comprises contacting a feed of a mixture of compounds, including isomers, with an amount of the material of the invention. .

In another aspect, the present invention refers to the use of the organ-inorganic material of the invention as a selective molecular sieve, which comprises contacting a feed of a mixture of compounds, including isomers, with an amount of the material of the invention passing through said material only those molecules that by their shape and / or size can do it, retaining the others.

In another aspect, the present invention relates to the use of the organ-inorganic material of the invention as a controlled drug delivery system.

The experts on the subject will assess that the present invention can be carried out within a wide range of parameters, concentrations and equivalent conditions without departing from the spirit and scope of the invention without undue experimentation. While this invention has been described in relation to such embodiments, it is understood that any subject of additional modifications is intended. This document is intended to cover any variant, use

or adaptation of the invention following the general principles of the same and including the variants derived from the present disclosure, as provided by known or customary practices of the technical sector to which the invention belongs.

Description of the fi gures

Fig. 1. Show the powder X-ray diffraction pattern for the AEPF-1 compound.

Fig. 2. Shows the powder X-ray diffraction pattern for the AEPF-2 compound.

Fig. 3. Shows the powder X-ray diffraction pattern for the AEPF-3 compound.

Fig. 4. Shows the structural view of the AEPF-1 compound. The molecules of the host organic compound have been removed from the figure for a better understanding of the structure.

Examples

The following examples are presented as an additional guide for medium-sized expertise in the field and in no case should be considered as a limitation of the invention. These tests carried out by the inventors show the specificity and effectiveness of the microporous crystalline inorganic AEPF inorganic material object of the present invention.

Example 1

Synthesis of AEFP-1

A solution of H2L (400 mg, 1 mmol) in 9 ml of isopropanol (Propan-2-ol, CH3CH (OH) CH3) is mixed with another solution of Ca (CH3CO2) 2 · 4H2O (178 mg, 1mmol) in 10 ml of distilled water, under continuous stirring agitation.

The resulting dispersion is heated at 170 ° C, under autogenous pressure of the system, for 72 h. Then, the mixture is cooled rapidly to room temperature. The product is filtered successively times with distilled water and ketone.

Scheme 2 represents the carboxylic acid component of AEPF-1, called H2L from now on.

In AEPF-1, the X-ray diffraction pattern of [Ca (C25.5F9O6H15) · 0.7C3H7O] as synthesized, obtained by the powder method using a fixed divergence slit, with a Bruker Advance equipment equipped with copper anti-cathode, It is characterized by the angular values, the corresponding inter-planar spacings (d) and the relative intensities (I / I0) shown in Table 2 in Figure 1. A discrepancy of 0.3 ° is estimated, depending on the alignment of the equipment, the crystallinity of the sample and degree of purity.

By diffraction of the single crystal X, the structure of the AEPF-1 material has been determined. It belongs to the monoclinic crystalline system, spatial group P 2 / n and the cell parameters are: a = 18.791 (1) A˚, b = 7.5961 (5) A˚, c = 20.9987 (5) A˚, β = 104.6 (1) º .

Following the same procedure, replacing the propanolporbutanol (C4H10O), toluene (methylbenzene, C6H5 CH3), hexane (C6H14) heptane (C7H16), octane (C8H18), the respective compound AEPF-1 isostructural is obtained, [Ca (C25.5F9O6H15) nA] <n ≤ 1), with a slight variation in the relative intensity of the diffraction peaks due to the variation in composition as used.

Example 2

Synthesis of AEFP-2

Through a drying process, between 100 ° C and 120 ° C and vacuum for a time between 10 and 20h, of the AEPF-1 compound, the AEPF-2 compound is obtained.

Scheme 2 represents the carboxylic acid component of AEPF-2.

In AEPF-2, the X-ray diffraction pattern of [Ca (C25.5F9O6H15)] as synthesized, obtained by the powder method using a fixed divergence slit, with a Bruker Advance equipment equipped with copper anti-cathode, It is characterized by the angular values, the corresponding inter-planar spacings (d) and the relative intensities (I / I0) shown in Table 3 and Figure 2. A discrepancy of 0.3 ° is estimated, depending on the alignment of the equipment, the crystallinity of the sample and degree of purity.

By means of X-ray diffraction of the polycrystalline sample, the space group and cell parameters of the AEPF-2 material have been determined. It belongs to the monoclinic crystalline system, spatial group P 2 / c and the cell parameters are: a = 24,614 (1) A˚, b = 7,367 (5) A˚, c = 31,519 (5) A˚, β = 89,858 (1 ) º.

Example 3

Synthesis of AEFP-3

Add 101mg of H2L (1mmol) and 51mg of SR (CH3CO2) to a mixture of 10ml of H2O and 0.5ml of pyridine (C5H5N).

The resulting mixture is heated at 180 ° C, under autogenous system pressure, for 48 h. The mixture is then cooled rapidly to room temperature. The product is filtered and washed several times with distilled water and ketone. The diffraction pattern of the solid obtained white is shown in Figure 3.

In AEPF-3, the X-ray diffraction pattern of [Sr (C25.5F9O6H15) · nC5H5N] (0 <n ≤ 1) as synthesized, obtained by the powder method using a fixed divergence slit, with a Bruker Advance equipment equipped With copper anticode, it is characterized by the angular values, the corresponding inter-planar spacings (d) and the relative intensities (I / I0) shown in Table 4 and Figure 3. It is estimated a discrepancy of 0.3 °, depending on the alignment of the equipment, the crystallinity of the sample and degree of purity.

The structure of the AEPF-3 material has been determined by monocrystalline X-ray diffraction. They belong to the monoclinic crystalline system, spatial group P 2 / n and the cell parameters are: a = 18,588 (1) A˚, b = 7.8223 (5) A˚, c = 21.399 (1) A˚, β = 105.9 (1) º.

TABLE 2

ES2351 494A1 ES2351 494A1

TABLE 3

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TABLE 4

Example 4

Application Hydrogenation of alkenes

The hydrogenation of styrene (vinylbenzene, C8H8) with H2 (Scheme7) is achieved with 100% selectivity and conversion of 100% alkene by treating a mixture of alkene dissolved in toluene with a pressure of H2a of 5atm, in the presence of the catalyst of Example1 in a catalyst / alkene ratio of 1% cool. The reaction temperature can vary between ambient and 100ºC, achieving an optimum speed at 70ºC.

Scheme7

Example 5

Aldehyde Hydrosilylation Application

Hydrosilylation of benzaldehyde (C6H5CHO) with diphenylsilane (Scheme8) is achieved with 100% selectivity and conversion of 100% aldehyde by treating a mixture of aldehyde and silane in a ratio of 1: 2 dissolved in dry toluene in the presence of the catalyst of Example 1 in a catalyst ratio / 10% molar aldehyde.

Scheme8

Example 6

Hydrosilylation application of ketones

Hydrosilylation of acetophenone with diphenylsilane (Scheme 9) achieves 100% selectivity and conversion of 70% mayo acetophenone by treating a mixture of ketone and silane in a ratio of 1: 2 dissolved in dry solvent at 90 ° C, in the presence of the catalyst of Example 1 in a catalyst / acetone ratio of 10% molar.

Scheme9

Example7

Alkenes Hydrosilylation Application

Hydrosilylation of styrene with diphenylsilane (Scheme 10) achieves 100% selectivity to the linear product and conversion of 100% alkene by treating a mixture of alkene and silane in a ratio of 3: 1 dissolved in dry toluene at 90 ° C, in the presence of the catalyst of Example 1 in a catalyst / alkene ratio of 10% molar .

ES2351 494A1

Scheme 10

Claims (24)

1. Organ-inorganic material of formula: where: -It is an alkaline earth cation, -A is a host molecule, comprising a solvent selected from the list comprising ethanol, propa nol, butanol, toluene, cyclohexane, hexane, heptane, octane, pyridine and any of its combinations, -It is an aromatic group selected from phenyl, naphthyl or diphenyl, which is branched not with other groups, -x represents a lower value equal to 4 (x ≤ 4), -and represents a value between 0.5y2 (0.5≤ y≤ 2), -z represents a value between 0 and 4 (0 ≤ z ≤ 4) and -n represents a value between 0 and 4 (0 ≤ n ≤ 4). 2. Material according to claim 1, wherein M is selected from Mg, Ca, SroBa.

3.

Material according to any of claims 1 or 2, where the ratio x: y: z is 0.5: 1: 1n and represents a value between 0 and 2 (0 <n ≤ 2).

Four.

Material according to any one of claims 1 to 3, where R is represented by the general formula R 1 -C (R 2) 2-R 1, wherein R 1 aromatic group selected from between phenyl, naphthyl diphenyl and R 2 is selected from methyl, ethyl, isopropyl, terbutyl or CF 3.

5.

Material according to claim 4, wherein R1 is a phenyl group and R2 is a CF3 group, and is represented by:

6.

Material according to any of claims 1 to 5, of formula:

where:

-

x represents a value 0.5,

-

and represents a value1,

-

z represents a value1,

-

n represents a value of 0.7y

-

Ase selected from ethanol, propanol, butanol, toluene, cyclohexane, hexane, heptane, octane or any

of their combinations. 7. Material according to any of claims 1 to 6, of formula: where: -x represents a value of 0.5, -y represents a value of 1, -z represents a value of 1, -n represents a value of 0. 8. Material according to any of claims 1 to 7, of formula: where: -x represents a value of 0.5, -y represents a value of 1, -z represents a value of 1, -n represents a value between 0 <n ≤ 1. 9. Method for preparing the material according to any of claims 1 to 8, comprising: a) preparing a reaction mixture comprising: -a alkaline earth cation M, -a dicarboxylic acid HOOC-R1C (R2) 2-R1-COOH, where R1 is a selected aromatic group from phenyl, naphthyl or diphenyl and R2 is a group selected from methyl, ethyl, isopropyl, terbutyl or CF3,

-

a host molecule A, which comprises a solvent selected from the list comprising ethanol, propanol, butanol, toluene, cyclohexane, hexane, heptane, octane, pyridine and any combination thereof.

-

Water; b) heat treatment of the reaction mixture of step (a) at a temperature between 80 ° C and 220 ° C until its crystallization is achieved.

10. Procedure according to claim 9, wherein the dicarboxylic acid HOC-R1-C (R2) 2-R1-COOH, R1 is a phenyl group and R2 is a group CF3.

eleven.

Process according to any of claims 9 or 10, wherein the dicarboxylic acid of the reaction mixture of step (a) is in the form of salt.

12.

Procedure according to any one of claims 9 to 11, wherein the reaction mixture has a composition, in terms of molar ratios, between the ranges: -M / dicarboxylic acid = 0.25-1

-H2O / S = 4.5-10.3 -H2O / M = 300-800 13. Procedure according to any of claims 9 to 12, wherein the heat treatment is subjected to the reaction mixture in step (b) at a temperature between 130 ° C and 200 ° C. 14. Procedure according to any of claims 9 to 13, further comprising: a) separation, washing and heat treatment of the crystalline product obtained in step (b) at a drying temperature of between 40 ° C and 150 ° C.

fifteen.

Process according to claim 14, wherein the separation, washing and heat treatment of the crystalline product obtained in step (b) is carried out at a drying temperature of between 100 ° C and 120 ° C and valued for a time of between 10 and 20h.

16.

Use of the material according to any of claims 1 to 8 as a catalyst in a compound conversion process.

17.

Use of the material according to claim 16, wherein the compound conversion process is a hydrogenation of alkenes using H2 as a reducing agent.

18. Use of the material according to claim 16, wherein the process of conversion of compounds is a hydroformylation of alkenes.

19.

Use of the material according to claim 16, wherein the compound conversion process is a hydrosilylation of aldehydes using as a reagent an organic compound derived from silane.

twenty.

Use of the material according to claim 16, wherein the compound conversion process is a hydrosilylation of ketones using an organic compound derived from silane as reagent.

twenty-one.

Use of the material according to claim 16, wherein the compound conversion process is a hydrosilylation of alkenes using an organic compound derived from silane as reagent.

22

Use of the material according to any of claims 1 to 8 as a compound absorbent.

2. 3.

Use of the material according to any of claims 1 to 8 as a molecular sieve.

24. Use of the material according to any of claims 1 to 8 as a controlled drug delivery system.