PL219119B1 - New catalytic converters immobilized on new ionic liquids - Google Patents

Description

transition metal complexes; and novel 4,4-disubstituted morpholine salts, which are ionic liquids, useful for obtaining immobilized catalysts. The invention also relates to the use of new catalysts.

There are known immobilized catalysts in which a homogeneous metal complex catalyst is bound to a solid organic or inorganic support by modification of the coordination sphere.

On the one hand, immobilized catalysts retain the catalytic properties of a homogeneous catalyst, and on the other hand, their removal from the reaction medium, after its completion, does not require the use of complex processes because, after lowering the temperature, they usually fall out as a solid or easily form a separate liquid phase, and then they can separate them either by decanting or by separating the layers. In general, immobilized catalysts allow the multiple use of the same portion of the catalyst in many successive repetitions of the same synthesis process, which significantly reduces the cost of the process.

One way to immobilize catalysts is to combine them with ionic liquids.

Van den Broeke (J. Van den Broeke, F. Winter, B. J. Deelman, G. Van Koten, Org. Lett. 4, (2002), 3851) used ionic liquids based on fluorinated imidazolium derivatives for the immobilization of rhodium complexes. The fluorinated derivative of the Wilkinson complex was used as a catalyst for the hydrosilylation of 1-octene. The catalyst immobilized in this way made it possible to use the same portion of the catalyst 15 times while reducing its catalytic activity to about 30%.

Polish patent applications No. P-380 735 and No. P-380 736 disclose platinum and rhodium catalysts immobilized with phosphonium ionic liquids. These catalysts, as disclosed in the patent application No. P-380 737, are used in the hydrosilylation reaction of allyl-glycidyl ether, polyether and 1-hexadecene with tri- and polysiloxanes, while these catalysts retain high catalytic activity in subsequent cycles of the reaction carried out with using the same batch of catalyst.

Ionic liquids are organic compounds with a melting point lower than 100 ° C. These compounds are a potential source of environmentally friendly chemical reaction media. Ionic liquids may be called "design solvents" because their physical properties (ie, melting point, viscosity, density, hydrophobicity, or hydrophilicity) can be modified, for a particular application, by the appropriate selection of an anion or cation.

Ionic liquids are widely used in many fields and the scope of their application is constantly and rapidly expanding. The scope of the potential and actual use of ionic liquids requires a comprehensive assessment of their impact on the safety of the environment and health. The ecotoxicity of ionic liquids with imidazolium, pyridinium, amnium or phosphono cations is quite well researched. Studies of the ecotoxicity of ionic liquids containing morpholine anion have shown that these liquids are much less toxic than ionic liquids with an aromatic ring (imidazolium or pyridine).

Due to the low toxicity of ionic liquids containing a nitrogen atom in the alicyclic system, it can be expected that they will be the heart of the future “ecological” ionic liquids.

As shown by the research of C. Pretti (Pretti C, Chiappe C, Baldetti I., Brunini S., Monni G., Intorre L., Ecotoxicol. Environ. Safe., 2009, 72, 1170-1176.) 4-methylmorpholine ([emmorph] [Br]) and 4-butyl-4-ethylmorpholine ([ebmorph] [Br]) have much lower toxicity than the commonly used imidazolium or ammonium bromides, e.g. EC50 toxicity value against D. magna (Daphnia magna) for [emmorph] [Br] is> 476 mg / l and for [ebmorph] [Br] it is> 397 mg / l, which means low toxicity, while for 3-butyl-1-methylimidazolium bromide the toxicity is high (8, 03 mg / l) and similarly for tetrabutylammonium bromide - 9.51 mg / l, which means high toxicity. Pretti based the toxicity level on EC50 values according to the following criteria:

EC50 [mg / l] Toxicity

100-1000 low

10-100 average

1-10 high

0.1-1 very high

PL 219 119 B1

The aim of the invention was to obtain catalysts immobilized on low-toxic ionic liquids and to obtain appropriate low-toxic ionic liquids and their use.

The present invention relates to novel 4,4-disubstituted morpholino salts of general formula 1:

₁ in which R ¹ is a linear alkyl containing from 1 to 14 carbon atoms, ₂

R ² is benzyl or butyl sulfonate and A is anions: bisulfate, methyl sulfonate or toluenesulfonate.

In a second aspect, the invention relates to a process for the preparation of 4,4-disubstituted morpholine salts of general formula 1a:

₁ in which R ¹ is a linear alkyl containing from 1 to 14 carbon atoms, ₂

R ² is benzyl and A is methylsulfonate or toluenesulfonate, which consists in a two-step reaction of 4-alkyl-4-benzylmorpholine halides of general formula 2:

₁ in which R ¹ is as defined above, X is chlorine, bromine or iodine with potassium hydroxide or sodium hydroxide, and then in a second step, the product of the first step is reacted with methylsulfonic or toluenesulfonic acid. In the first step, the 4-alkyl-4-benzylmorpholine halide of formula 2 is reacted with at least a stoichiometric amount of hydroxide at a temperature of 20 to 60 ° C, preferably 30 ° C, in methanol, and then the resulting inorganic salt precipitate is separated. After removal of the inorganic salt, an at least stoichiometric amount of methylsulfonic acid or toluenesulfonic acid in relation to the hydroxides is added to the reaction mixture containing 4-alkyl4-benzylmorpholine hydroxide and optionally residual sodium or potassium hydroxide at a temperature of 20 to 60 ° C, preferably 25 ° C. C, then the methanol was evaporated under reduced pressure.

The crude product is purified by dissolving it in a solvent in which the substrates and by-products do not dissolve, preferably acetone or acetonitrile. The resulting precipitate is separated, and the solvent of the separated solution containing pure product is evaporated, and the product is then dried, preferably under reduced pressure.

The process of the invention for the preparation of 4,4-disubstituted morpholine salts of general formula 1b:

PL 219 119 B1 in which:

• R ¹ represents a straight-chain alkyl group containing from 1 to 14 carbon atoms, R ² represents a benzyl group;

• A represents bisulfate (VI);

₁ consists in the reaction of 4-alkyl-4-benzylmorpholine halides of the general formula 2, where R ¹ is as defined above, X is chlorine or bromine or iodine with at least a stoichiometric amount of sulfuric acid (VI) at a temperature of -10 to 5 ° C, preferably -5 ° C, in methylene chloride, then the resulting hydrogen halide from the reaction mixture is degassed by passing dry air through it, and the degassed product is separated and dried under reduced pressure.

Variation of the process according to the invention for the preparation of 4,4-disubstituted morpholine salts of general formula 3:

₁ in which R ¹ is a linear alkyl containing from 1 to 14 atoms, and A is hydrogen (VI) involves reaction of 4-alkyl-4- (4-butylosulfonianu) morpholine of the general formula 4:

₁ where R ¹ is as defined above with at least a stoichiometric amount of sulfuric acid (VI) at a temperature of -10 to 5 ° C, preferably -5 ° C, in methylene chloride, and then the product obtained is separated and dried under reduced pressure .

In a third aspect, the invention relates to an immobilized catalyst in which a transition metal complex, in particular platinum or rhodium, is immobilized in an ionic liquid which is a 4,4-disubstituted morpholine salt of general formula 1:

₁ wherein wherein R ¹ is a linear alkyl containing from 1 to 14 carbon ₂ atoms, R ² is benzyl or butylowodorosulfonową and A is mesylate, tosylate, or hydrogen (VI).

Immobilized catalysts bound in ionic liquids of the general formula 1, któ12 wherein R ^1, R ² and A are as defined above, according to the invention are, in particular, complexes of platinum and rhodium, selected from the group of Pt _{(PPh3) 4,} Pt ( PPh ₃ ) ₂ Cl ₂ , PtCl ₄ , K ₂ PtCl ₄ , K ₂ PtCl ₄ , Rh (PPh ₃ ) ₃ Cl, [{Rh ^ -Cl) - (cod)} ₂ ], and most preferably: Pt (PPh ₃ ) ₂ Cl ₂ , Rh (PPh ₃ ) ₃ Cl and [{Rh ^ -Cl) (cod)} ₂ ].

A process for the preparation of the catalyst of the invention is to dissolve a transition metal complex, especially a platinum or rhodium morpholinium ionic liquid of the general wzo12 sculpture 1, wherein R ^1, R ² and A are as defined above.

This process is carried out at elevated temperature, which enables faster and even dispersion of platinum and rhodium complexes in the entire volume of the ionic liquid. After complete mixing and dissolution of the catalyst in the ionic liquid, the whole is cooled to room temperature, at which the immobilized catalyst can be stored for a long time without losing its catalytic properties. The cooled catalyst is either a liquid or a solid.

PL 219 119 B1

The catalyst according to the invention immobilized in the ionic liquid does not dissolve in the reaction medium, while in the course of the hydrosilylation process, two liquid phases are formed and the reaction takes place at the interface of the immobilized catalyst / reaction medium at which the active platinum or rhodium catalyst is available.

The catalyst according to the invention, unlike homogeneous catalysts, does not lose catalytic activity even after repeated use, and at the same time maintains high activity and selectivity.

In a fourth aspect, the invention relates to an olefin hydrosilylation process which comprises the reaction of olefins of general formula 5:

RCH = CH2 (5) where R is an alkyl group with a C2-C16 content, with (poly) siloxanes of general formula 6:

wherein n has values from 1 to 25 and m from 0 to 50, in the presence of an immobilized catalyst according to the invention.

The immobilized platinum or rhodium catalyst is used in an amount of 10 ^-2 to 10 ^-6 moles of meta-3 -5 -1 -5 l transition per 1 mole of Si-H bonds, preferably from 10 ^-3 to 10 ^-5 , and most preferably from 10 ^-1 to 10 ^-5 moles. It is preferred that the ionic liquid together with the catalyst immobilized therein constitutes from 10 to 20% by weight of the total mass of the reactants involved in the process, since the greater amount of the ionic liquid in the reaction medium hinders the process and mass exchange in the reaction mixture during the reaction. The hydrosilylation process according to the invention is carried out at a temperature not lower than the melting point of the liquid in which the platinum or rhodium complex is immobilized, preferably at a temperature of 100-110 ° C.

After completion of the reaction, it is cooled to solidify the ionic liquid with the immobilized catalyst, and then the solidified catalyst is separated, for example by decantation. The separated catalyst can be reused several times in subsequent processes.

New immobilized catalysts are reusable in subsequent synthesis cycles. Ionic liquids from the group of morpholine ionic liquids are less ecotoxic than previously used and used imidazolium ionic liquids.

In addition to being used for immobilization, the ionic liquids according to the invention can be used as a chemical reaction medium. As demonstrated by the Pretti study of the toxicity of ionic liquids containing morpholine derivatives against D. rerio. (Danio rerio) that morpholine bromides [emmorph] [Br] EC50 => 476 mg / li [ebmorph] [Br] - EC50 => 397 mg / l are less toxic even than the commonly used triethylamine (used as a reagent or solvent) - EC50 = 44 mg / l, and therefore they can act as solvents as its substitutes.

The method of obtaining morpholine ionic liquids and immobilized catalysts based on platinum and rhodium complexes and the use of the obtained new heterogeneous complexes in the hydrosilylation process are illustrated but do not limit the scope of the invention, the following examples. NMR determinations were made on a Mercury Gemini 300 spectrometer.

P r z k ł a d I

4-Benzyl-4-methylmorpholine bisulfate

In a flask equipped with a magnetic stirrer placed 0.017 mole of 4-benzyl ₃

-4-methylmorpholinium in 15 cm ³ of methylene chloride and placed in an ice bath, and then 0.017 mol of sulfuric acid (VI) was added dropwise. The reaction was carried out for two hours at -5 ° C. The product separated from the reaction mixture as the top liquid layer. A by-product, HCl, was removed from the reaction mixture by bubbling dried air through it. The air was dried by passing it through a sodium hydroxide scrubber. A scrubber with KOH solution (equimolar with respect to the amount of HCl evolved in the reaction) and phenolphthalein was placed behind the flask with the reaction mixture. Air was blown through the mixture until the pink za6 disappeared

Phenolphthalein was dyed in a washer after the reaction flask and then the product was separated in a separating funnel. The product was dried in a vacuum oven.

The product was obtained in the form of a colorless liquid with a yield of 89%.

The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

¹ H NMR (DMSO) δ ppm = 3.10 (s, 3H); 3.17 (s. 1H); 3.37 (t, J = 4.29 Hz, 2H); 3.56 (qw, J = 5.14 Hz, 2H); 3.98 (t, J = 1.71 Hz, 4H); 4.77 (s. 2H); 7.54 (m, 3H); 7.60 (m, 2H);

¹³ C NMR (DMSO) δ ppm = 45.0; 58.5; 59.9; 67.6; 127.3; 129.0; 130.4; 133.4.

Additionally, the purity of the compound was confirmed by elemental CHN analysis.

For C12H19NO5S (M = 289.35) the following values were established:

calculated: C = 49.81; H = 6.62; N = 4.84;

found: C = 49.21; H = 7.24; N = 5.39 percent.

P r z x l a d II

4-Benzyl-4-methylmorpholine toluenesulfonate

In a reactor equipped with a magnetic stirrer, 0.014 mol of iodide _{3 was placed}

4-benzyl-4-methylmorpholinium dissolved in 20 cm ³ of methanol and 0.014 mol of sodium hydroxide dissolved in 20 ml of methanol. The reaction was carried out for 30 minutes at 25 ° C. An inorganic salt precipitated, which was filtered off, and 0.015 mol of toluenesulfonic acid was added to the filtrate. The reaction was carried out for 3 hours at 30 ° C. Then, methanol was evaporated on a vacuum evaporator.

The obtained crude product was further dissolved in acetone, in which the remainder of the sodium iodide precipitated. The salt was filtered off and the solvent of the filtrate containing the product was evaporated. The product was dried for 24 hours in a vacuum oven at 25 ° C. The product was obtained in the form of a solid, m.p. 127-130 ° C in a yield of 89%.

The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

¹ H NMR (DMSO) δ ppm = 2.29 (s, 3H); 3.07 (s, 3H); 3.34 (t, J = 4.29 Hz, 2H); 3.54 (qw, J = 7.50 Hz, 2H); 3.96 (t, J = 1.73 Hz, 4H); 4.73 (s. 2H); 7.14 (d, J = 4.55 Hz, 2H); 7.52 (m, 7H);

¹³ C NMR (DMSO) δ ppm = 20.8; 44.8; 58.4; 59.8; 67.5; 125.5; 127.2; 128.1; 128.8; 130.3; 133.2; 137.8; 145.5.

The performed elemental analysis of CHN for C19H25NO4S (M = 363.47) confirmed the correctly identified structure.

Values calculated in%: C = 62.78; H = 6.93; N = 3.85; correlate with the obtained values: C = 62.32; H = 6.48; N = 4.34.

P r x l a d III

4-Benzyl-4-methylmorpholine methylsulfonate

_{0.022 mol of bromide 3 was} placed in a reactor equipped with a magnetic stirrer

4-benzyl-4-methylmorpholinium dissolved in 15 cm ³ of methanol and 0.024 mole of potassium hydroxide dissolved in 20 ml of methanol.

The reaction was carried out for 45 minutes at 35 ° C. Potassium bromide precipitated as a white solid which was filtered off.

0.024 mol of methylsulfonic acid was added to the filtrate.

The reaction was carried out at 25 ° C for 2 hours and then the solvent was evaporated.

The obtained crude product was further dissolved in acetonitrile, in which the unreacted potassium hydroxide precipitated and the remaining by-product (potassium bromide) was filtered off, and the filtrate's solvent was evaporated.

The product was dried in a vacuum oven.

The product is a viscous, slightly yellow liquid at room temperature. Yield 94.5%. Compound purity was confirmed by elemental CHN analysis.

For C13H21NO4S (M = 287.37) the following values were established:

calculated: C = 54.33; H = 7.37; N = 4.87;

found: C = 54.78; H = 6.83; N = 4.38 percent.

¹ H NMR (DMSO) δ ppm = 2.44 (s, 3H); 3.09 (s, 3H); 3.36 (t, J = 4.25 Hz, 2H); 3.56 (qw, J = 5.23

Hz, 2H); 3.98 (t, J = 2.69 Hz, 4H); 4.75 (s. 2H); 7.54 (m, 3H); 7.59 (m, 2H);

¹³ C NMR (DMSO) δ ppm = 39.8; 44.9; 58.5; 59.9; 67.5; 127.2; 128.9; 130.4; 133.3.

PL 219 119 B1

P r x l a d IV

4- (4-Hydrosulfonylbutyl) -4-methylmorpholine hydrogen sulfate

0.0067 mol of 4- (4-butylsulfonate) -4-methylmorpholinate dissolved in 20 cm of chloroform was placed in a reactor equipped with a magnetic stirrer and placed in an ice bath, and then 0.0067 mol of sulfuric acid (VI) was added dropwise.

The reaction was carried out for 2 hours at the temperature of -5 ° C.

The product separated from the reaction mixture as the top layer of liquid which separated in the separating funnel.

The product was dried in a vacuum oven.

The product was obtained with a yield of 98%.

The performed elemental analysis of CHN for C9H21NO8S2 (M = 335.39) confirms the correctly identified structure. Values calculated in%: C = 32.23; H = 6.31; N = 4.18 correlate with the obtained values: C = 32.76; H = 5.83; N = 4.69.

Examples V-IX

Preparation of the immobilized catalyst

Table 1 presents the list of individual catalysts. In a ₃ cm ³ flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of the ionic liquid were placed, followed by the addition of 10 ^-5 moles of an appropriate metal complex. It was heated for 0.5 hours at 100 ° C. After cooling the mixture, a complex bound to the ionic liquid was obtained, which can be used as the mobilized catalyst for them, e.g. in hydrosilylation reactions.

T a b e l a 1

Example Ionic liquid Complex V 4-Benzyl-4-methylmorpholine bisulfate [Rh (Cl) (PPh3) 3] VI 4-Benzyl-4-methylmorpholine bisulfate [Rh ^ -OSiMe3) (cod) h] VII 4-Benzyl-4-methylmorpholine bisulfate [Pt (PPh3) 2Cl2] VIII 4-Benzyl-4-methylmorpholine toluenesulfonate [Rh (Cl) (PPh3) 3] IX 4- (4-Hydrosulfonylbutyl) -4-methylmorpholine hydrogen sulfate [Rh (Cl) (PPh3) 3]

Example X ₃

In a 250 cm ³ flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of the catalyst obtained according to Example 5 were placed, and then a mixture of 33 cm ³ (0.185 mol) was added to the flask. -heptamethyltrisiloxane and 30 cm ³ (0.185 mol) octene-1. The reaction was carried out for 1 hour at 110 ° C. After this time, IR and GC analysis showed 98% conversion of the siloxane. After cooling, the product was decanted from the catalyst phase and used for the next reaction. Reactions were repeated ten times with the following siloxane conversion: 98, 98, 98, 99, 99, 99, 99, 99, 98%.

Example XI ₃

In a 250 cm ³ flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of the catalyst obtained according to example 6 were placed, and then a mixture of 50 cm ³ (0.185 mol) 1,1,1,3,5,5 was added to the flask. 5-heptamethyltrisiloxane and 30 cm ³ (0.185 mol) octene-1. The reaction was carried out for 1 hour at 110 ° C. After this time, IR and GC analysis showed 99% conversion of the siloxane. After cooling, the product was decanted from the catalyst phase and used for the next reaction. Reactions were repeated ten times with the following siloxane conversion: 99, 99, 99, 99, 99, 99, 99, 99, 99.

Example XII ₃

In a 250 cm ³ flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of the catalyst obtained according to example 7 were placed, and then a mixture of 50 cm ³ (0.185 mol) 1.1,1,3,5.5 was added to the flask. 5-heptamethyltrisiloxane and 30 cm ³ (0.185 mol) octene-1. The reaction was carried out for 1 hour at 110 ° C. After this time, IR and GC analysis showed 90% conversion of the siloxane. After cooling, the product was decanted from the catalyst phase and used for the next reaction. Reactions were repeated ten times with the following siloxane conversion: 90, 89, 86, 84, 84, 80, 68, 61, 55.

PL 219 119 B1

Example XIII ₃

In a 250 cm ³ flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of the catalyst obtained according to example 8 were placed, and then a mixture of 50 cm ³ (0.185 mol) 1.1,1,3,5.5 was added to the flask. 5-heptamethyltrisiloxane and 30 cm ³ (0.185 mol) octene-1. The reaction was carried out for 1 hour at 110 ° C. After this time, IR and GC analysis showed 99% conversion of the siloxane. After cooling, the product was decanted from the catalyst phase and used for the next reaction. Reactions were repeated ten times with the following siloxane conversion: 99, 99, 99, 99, 99, 99, 98, 99, 90.

Example XIV ₃

In a 250 cm ³ flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of the catalyst obtained according to example 9 were placed, and then a mixture of 50 cm ³ (0.185 mol) 1.1,1,3,5,5 was added to the flask. 5-heptamethyltrisiloxane and 30 cm ³ (0.185 mol) octene-1. The reaction was carried out for 1 hour at 110 ° C. After this time, IR and GC analysis showed 99% conversion of the siloxane. After cooling, the product was decanted from the catalyst phase and used for the next reaction. Reactions were repeated ten times with the following siloxane conversion: 98, 99, 96, 93, 93, 91, 88, 96, 92.

Claims (17)

1. Ionic liquids of the general formula 1: ₁ in which R ¹ is a linear alkyl containing from 1 to 14 carbon atoms, ₂ R ² is benzyl or butyl sulfonate and A is anions: bisulfate, methyl sulfonate or toluenesulfonate. 2. Method of obtaining ionic liquids of general formula 1a: ₁ in which R ¹ is a linear alkyl containing from 1 to 14 carbon atoms, ₂ R ² is benzyl and A is methylsulfonate or toluenesulfonate, which consists in a two-step reaction of 4-alkyl-4-benzylmorpholine halides of general formula 2: GB ₁ 219 119 B1 in which R ¹ is as defined above, X is chlorine, bromine or iodine with potassium hydroxide or sodium hydroxide, and then in a second step, the product of the first step is reacted with methylsulfonic or toluenesulfonic acid. 3. The method according to p. The process of claim 2, wherein the reaction is carried out in methanol at a temperature of 20-60 ° C. 4. The method of obtaining an ionic liquid of general formula 1b: Wherein R ¹ is a straight chain alkyl group containing from 1 to 14 carbon atoms, R ² is a benzyl group and A is a bisulfate (VI) characterized in that a 4-alkyl-4-benzylmorpholine halide of general formula 2: reacts with an at least stoichiometric amount of sulfuric acid at -10 to 5 ° C. 5. The method according to p. 4. The process of claim 4, wherein the reactions are carried out in methylene chloride. 6. The method according to p. The process of claim 4 or 5, characterized in that the reactions are carried out at a temperature of 5 ° C. 7. Preparation of 4,4-disubstituted morpholine salts of general formula 3: ₁ in which R ¹ is a linear alkyl containing from 1 to 14 atoms, and A is hydrogen (VI), characterized in that the 4-alkyl-4- (4-butylosulfonianu) morpholine of the general formula 4: ₁ wherein R ¹ is as defined above with at least a stoichiometric amount of sulfuric acid (VI) at a temperature of from -10 to 5 ° C. 8. The method according to p. The process of claim 7, wherein the reactions are carried out in methylene chloride. 9. The method according to p. The process of claim 7 or 8, characterized in that the reactions are carried out at a temperature of 5 ° C. PL 219 119 B1 10. Immobilized catalysts containing a transition metal complex, characterized in that they contain a rhodium or platinum complex as a complex and an ionic liquid of the general formula: where R ¹ is a straight chain alkyl group having from 1 to 14 carbon atoms, R ² is benzyl or butyl hydrosulfonate and A is anions: bisulfate, methylsulfonate or toluenesulfonate. 11. New immobilized catalysts according to claim 1, 10, characterized in that they contain a complex selected from the group: Pt (PPh3) 4, Pt (PPh3lCh, PtCI4, ^ PtCU ^ PtCU RhCPPhsbCl, [{Rh (p-CD (cod) hl 12. Immobilized catalysts according to claim 1, 11. The process of claim 11, wherein the complex is selected from the group: Pt (PPh ₃ ) ₂ Cl ₂ , Rh (PPh ₃ ) ₃ Cl and [{Rh ^ -Cl) (cod)} ₂ ]. 13. Method of hydrosilizing olefins of general formula 5: RCH = CH2 (5) where R is an alkyl group with a C2-C16 content, with (poly) siloxanes of general formula 6: in which n takes values from 1 to 25 and m from 0 to 50, characterized in that the reaction is carried out in the presence of an immobilized catalyst of a rhodium or platinum complex and an ionic liquid of the general formula: where R ¹ is a straight chain alkyl group containing from 1 to 14 carbon atoms, R ² is a benzyl or butyl hydrogensulfonate group and A is an anions: bisulfate (VI), methylsulfonate or toluenesulfonate, the catalyst being used in an amount from ^10-2 to 10 ^-6 moles of transition metal to 1 mole of Si-H bonds. -3 -5 14. The method according to p. 13. The process of claim 13, wherein the amount of the catalyst is ^10-3 to ^10-5 moles per 1 mole of Si-H bonds. 15. The method according to p. 14. The process of claim 14, wherein the amount of the catalyst is from ^10-4 to 10 ^-5 moles per 1 mole of Si-H bonds. 16. The method according to p. 13, 14 or 15, characterized in that the catalyst is a complex selected from the group: Pt (PPh3) 4, Pt (PPh3) 2Cl2, PtCl4, K2PtCl4, K2PtCl4, Rh (PPh3) 3Cl, [{Rh ^ -Cl ) (cod) h]. 17. The method according to p. 14. The process of claim 14, wherein the catalyst is a complex selected from the group: Pt (PPh ₃ ) ₂ Cl ₂ , Rh (PPh ₃ ) ₃ Cl and [{Rh ^ -Cl) (cod)} ₂ ].