PL208938B1 - The manner of obtaining of modified (poly)siloxans - Google Patents

Description

Description of the invention

The subject of the invention is a process for the preparation of modified polysiloxanes of the general formula I, in which R ¹ is an alkoxy, glycidoxy, phenoxy or phenylic group, n takes values from 1 to 25 and from 0 to 50, as a result of a catalytic hydrosilylation reaction of olefins of the general formula 2 in which R ¹ is as defined above, with poly (methylhydrogen) siloxanes of the general formula in which m and n are as defined above.

The hydrosilylation process is the most frequently used method of synthesizing organofunctional siloxanes and polysiloxanes. By selecting the appropriate olefins, polysiloxanes having the desired properties can be obtained. It is known to obtain poly (methylalkyl) siloxanes by modification of poly (methylhydrogen) siloxanes by hydrosilylation of olefins catalyzed by transition metal complexes [Marciniec B. (Ed.) Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford, 1992].

Hydrosilylation reactions of olefins with polyhydrogen siloxanes are carried out mainly in the presence of platinum complexes at various degrees of oxidation, e.g. bis (triphenylphosphine) (ethylene) platinum (0) [Pt (PPh3) 2 (CH2 = CH2)], dichlorobis (triphenylphosphine) platinum (II) [PtCl2 (PPh3) 2], hexachloroplatinic acid (IV) H2PtCl6 in cyclohexanone [Marciniec B., et al., Appl. Organometal. Chem., 11, 843,1997].

The modification of the siloxanes with allyl glycidyl ether usually takes place in the presence of catalysts based on hexachloroplatinic (IV) acid or carbon-supported platinum (Pt / C) [Matisons J.G., Provatas A., Macromolecules, 27, 3397, 1994; Leblanche-Colbier A., Loucheux C., Europ. Polym. J., 24, 1137, 1988].

Patent application PL 351451 discloses a method for the preparation of polysiloxanes by reacting a suitable siloxane with a suitable allyl ether in the presence of bis- (1,5-cyclooctadiene) -di-pi- (trimethylsiloxy) -dirodium (I) as a catalyst for the hydrosilylation reaction. The molecular rhodium (I) siloxy complex used is completely soluble in the reaction medium, therefore distillation is necessary to purify the reaction product from catalyst residues, which is almost impossible with long polysiloxane chains. An alternative is column chromatographic purification, which is also difficult with polymers and therefore most applications use a crude polymer containing a catalyst. The presence of even trace amounts of the catalyst very often disqualifies polysiloxanes, even when used in biological systems.

Polysiloxanes containing long-chain alkyl groups constitute a large group of compounds commonly referred to as silicone waxes. Due to their excellent lubricating, moisturizing and hydrophobizing properties, these compounds are used in a number of applications in the cosmetics, textile, automotive industries and as polishing agents [USA. 5,397,566 (1995), USA 5,939,056 (1999)]. The simplest method of obtaining this group of compounds is hydrosilylation carried out mainly in the presence of homogeneous platinum catalysts [Marciniec B. (Ed.) Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford, 1992] or rhodium [Wyszpolska A., Maciejewski H., Chadyniak D., Pawluć P., Marciniec B., Pol. J. Chem. Technol, 5 (4), 14, 2003].

Summary of the Invention, wherein the poly (methylhydrogen) siloxane of the general formula 3, wherein n and m are as defined above, is reacted hydrosilylation of olefins of general formula 2, wherein R ¹ is as defined above, lies in the fact that the catalyst is a heterogenised siloxyl complexes of rhodium (I) of general formula 4, wherein the diene is cyclooctadiene, norbornadiene or tetrafluorobenzobarrelen and L is a phosphine ligand of the general formula 5, wherein R ² represents an alkyl group or a phenyl or another unit HSiOX from the surface of silica Formula 6, wherein X is hydrogen or silicon. The reaction according to the invention is carried out under an inert gas atmosphere at a temperature of 60 to 100 ° C.

The invention uses a new rhodium (I) complex as a catalyst, which is obtained as a result of the exchange reaction of siloxyl ligands in the metal coordination sphere between molecular siloxyl binuclear complexes of the general formula 7, in which the diene is as defined above, and R ³ is an alkyl group. or phenyl or siloxy mononuclear complexes of general formula 8 in which diene, R ² , R ³ are as defined above, and with silanol groups located on the silica surface. The reaction according to the invention is carried out in an anhydrous, deoxygenated and non-rhodium-coordinating solvent and in a gas atmosphere.

The modified polysiloxanes of the general formula I obtained by the process according to the invention, in which R ¹ , before having the meaning given above, constitute a group of compounds of particular interest.

These properties are widely used in the cosmetics, textile and polymer processing industries, as well as in the production of polyurethane foams, mainly as surfactants, emulsifiers and foam regulating agents. These compounds may also undergo further reactions due to the reactive end group (epoxy, hydroxy) [Hill R.M., (ed), Silicone Surfactants, Marcel Dekker, Inc, New York, 1999; Kircheldorf H.R. (ed), Silikon In Polimer Synthesis, Sprinter, 1996].

The use of a heterogenized rhodium catalyst in the invention, which is a new catalyst, allowed in the known hydrosilylation reaction to be carried out with high efficiency and selectivity (typical for homogeneous catalysts), and at the same time allowed for easy isolation of the product from the catalyst. In the previous solutions, especially when using homogeneous catalysts, it was impossible to remove the catalyst from the product due to its high viscosity as well as its high boiling point. The catalyst system used in the invention allows easy isolation of the product after the reaction is completed (by decanting), and the catalyst after separation from the product does not lose its activity and can be reused, which significantly reduces the production cost.

The following examples illustrate the invention.

Example I - catalyst preparation

In a glass, two-necked, round-bottomed flask with a capacity of 50 ml, equipped with a magnetic stirrer, di-n-trimethylsiloxyl dicyclooctadiendirod (I) 1.2 g (2x10 ^-3 mol) and previously dried at 350 ° C were placed under an inert gas (argon). C Aerosil 200 silica (6 g 7,6x10 ^-3 mol). 20 mL of benzene was added to the mixture, the mixture was stirred at room temperature for 24 hours. Then the benzene was evaporated under reduced pressure and 20 mL of pentane was added. The supernatant solution was decanted and the precipitate was washed three times with pentane and dried under reduced pressure. The catalyst [(HSiO) (eSiOX) Rh (cod)] (Aerosil 200) was obtained with the following rhodium content: 4.104x10 ^-4 mol Rh / g (data obtained by ICP-OES technique).

¹³ C MAS-NMR (ppm) = 75.19 (= CH-, cod); 31.02 (CH2, COD) ²⁹ Si MAS-NMR (ppm) = 99.68 (Q ^2), 106.88 (Q ^3), 110.38 (Q ^4).

P r z x l a d II

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.01 g (4, 33 x 10 ^-6 mol) obtained as in Example 1, followed by 2 mL decane (internal standard), 11.6 mL heptamethyltrisiloxane (4.34 x 10 ^-2 mol) and 7.7 mL allyl glycidyl ether (6.5 x 10 ^-2 mol). The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-glycidoxypropyl) methyl bis (trimethylsiloxy) silane were determined by gas chromatography. A yield of 92% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In a 99% conversion, a 92% yield was obtained (3-glycidoxypropyl) methylbis (trimethylsiloxy) silane. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction six times without any visible decrease in activity. The structure of the obtained (3-glycidoxypropyl) methylbis (trimethylsiloxy) silane was confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

P r z x l a d III

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.01 g (4, 33 x 10 ^-6 mol) obtained as in Example 1, followed by 2 mL decane (internal standard), 11.6 mL heptamethyltrisiloxane (4.34 x 10 ^-2 mol) and 7.7 mL allyl glycidyl ether (6.5 x 10 ^-2 mol). The reaction mixture was heated for two hours at 60 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-glycidoxypropyl) methyl bis (trimethylsiloxy) silane were determined by gas chromatography. A yield of 95% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, the yield was (3-glycidoxypropyl) methylbis (trimethylsiloxy) silane in 95% yield.

P r x l a d IV

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.017 g (7, 38 x 10 ^-6 mol) obtained as in Example 1, then poly (methylhydrogen) siloxane 16 mL (7.4 x 10 ^-2 mol) and allyl glycidyl ether 13 mL (0.11 mol). Mie4

The reaction mixture was heated for one hour at 100 ° C. After this time the reaction mixture was decanted, ¹ H NMR analysis showed 99% conversion of the polysiloxane and selective formation of the hydrosilylation product - poly [(3-glicydoksypropylometylo) (dimethyl) siloxane]. After decanting the reaction mixture, a new portion of the substrate was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction six times without any visible decrease in activity.

Example V - catalyst preparation

Glass flask, two-necked, round-bottomed with a capacity of 50 mL, equipped with a magnetic stirrer, in an atmosphere of inert gas (argon) cyklooktadientricykloheksylofosfinatrimetylosiloksylorod (I) 1.9 g (3,3x10 ^-3 mol) and dried in advance at 350 ° C silica Aerosil 200 5 g (6,4x10 ^-3 mol). Then, 20 mL of pentane was added to the mixture, the mixture was stirred at room temperature for 24 hours. The supernatant solution was decanted and the precipitate was washed three times with pentane and dried under reduced pressure. Catalyst obtained

[(HSiO) Rh (cod) (PCy ₃ )] (Aerosil 200) with the following rhodium content: 1.24x10 ^-4 mol Rh / g (data obtained by ICP-OES technique).

¹³ C MAS-NMR (ppm) = 26.63 (-CH2-, -Cy) ²⁹ Si MAS-NMR (ppm) = 103.79 (Q ³ ), 108.12 (Q ⁴ ) ³¹ P MAS-NMR (ppm) = 23.42.

P r x l a d VI

[(HSiO) Rh (cod) (PCy ₃ )] (Aerosil 200) 0.028 g (3 , 48x10 ^-6 mol) obtained as in example V and poly (methylhydrogen) siloxane 7.5 mL (3,47x10 ^-2 mol) and allyl glycidyl ether with 6 ml (5,2x10 ^-2 mol). The reaction mixture was heated for one hour at 100 ° C. After this time, analysis of the ¹ H NMR showed 99% conversion of the polysiloxane and selectively gives the product a hydrosilylation-poly [(3-glicydoksypropylometylo) (dimethyl) siloxane].

P r o x l a d VII

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.019 g (7, 8x10 ^-6 mol), prepared as in example I, then successively with 4 ml decane (internal standard), heptametylotrisiloksan 20 mL (7,8x10 ^-2 mol) and allyl phenyl ether 16 mL (0.12 mol). The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-phenyloxypropyl) methylbis (trimethylsiloxy) silane were determined by gas chromatography. Yield of 99% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In 99% conversion, (3-phenyloxypropyl) methylbis (trimethylsiloxy) silane was obtained in 99% yield. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction five times without any visible decrease in activity. The structure of the obtained 3-fenyloksypropylometylobis (trimethylsiloxy) silane was confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

P r x l a d VIII

In a glass, two-neck, round-bottom flask with a capacity of 50 mL, equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.095 g (3, 9x10 ^-5 mol) obtained as in Example 1, followed by 2 mL decane (internal standard), 10 mL heptamethyltrisiloxane (3.9x10 ^-2 mol) and 8 mL allyl phenyl ether (5.9x10 ^-2 mol). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-phenyloxypropyl) methylbis (trimethylsiloxy) silane were determined by gas chromatography. The yield was 84% (GC). In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. With a conversion of 88%, a yield of 84% gave (3-phenyloxypropyl) methylbis (trimethylsiloxy) silane.

P r x l a d IX

In a glass, two-neck, round-bottomed flask with a capacity of 100 mL, equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.028 g (1, 15x10 ^-5 mol) obtained as in Example 1, followed by 25 mL poly (methylhydrogen) siloxane (0.115 mol) and 23.6 mL allyl phenyl ether (0.17 mol). The reaction mixture was heated for one hour at 60 ° C. After this time the reaction mixture was decanted, ¹ H NMR analysis showed 99% conversion of the polysiloxane and selective formation of the hydrosilylation product - {poly (3-fenyloksypropylometylo) (dimethyl) siloxane}. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction five times without any visible decrease in activity.

P r z k ł a d X

In a glass, two-necked, round bottom flask with a capacity of 50 ml, equipped with a reflux condenser and a magnetic stirrer, the catalyst was placed under an inert gas (argon) atmosphere.

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.015 g (6.15x10 ^-6 mol) prepared as in Example 1, followed by 3 mL decane (internal standard), heptamethyltrisiloxane 16.6 mL (6 , 2x10 ^-2 mol) and allyl butyl ether, 13 ml (8,9x10 ^-2 mol). The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-butyloxypropyl) methylbis (trimethylsiloxy) silane were determined by gas chromatography. A yield of 96% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, a 96% yield was obtained (3-butyloxypropyl) methylbis (trimethylsiloxy) silane. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction twice without a visible decrease in activity. The structure of the obtained (3-butyloksypropylo) methylbis (trimethylsiloxy) silane was confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

P r z x l a d XI

In a glass, two-neck, round-bottom flask with a capacity of 50 mL, equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.008 g (3, 3x10 ^-6 mol) obtained as in example I, followed by 2 mL decane (internal standard), 8.5 mL heptamethyltrisiloxane (3.3x10 ^-2 mol) and 7 mL allyl-butyl ether (4.8x10 ^-2 mol) . The reaction mixture was heated for six hours at 60 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-butyloxypropyl) methylbis (trimethylsiloxy) silane were determined by gas chromatography. The yield was 97% (GC). In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, a 97% yield was obtained (3-butyloxypropyl) methylbis (trimethylsiloxy) silane.

P r x l a d XIII

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.036 g (1, 48 x 10 ^-5 mol) obtained as in Example 1, and then 32 mL poly (methylhydrogen) siloxane (0.15 mol) and 32 mL allyl-butyl ether (0.22 mol). The reaction mixture was heated for one hour at 100 ° C. After this time the reaction mixture was decanted, ¹ H NMR analysis showed 99% conversion of the polysiloxane and selective formation of the hydrosilylation product - poly [(3-butyloksypropylometylo) (dimethyl) siloxane]. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction twice without a decrease in activity.

P r x l a d XIV

[(HSiO) Rh (cod) (PCy ₃ )] (Aerosil 200) 0.025 g (3 , 1x10 ^-6 mol), prepared as in example V and poly (methylhydrogen) siloxane 6.8 ml (3,1x10 ^-2 mol) and allyl butyl ether, 6.8 ml (4,7x10 ^-2 mol). The reaction mixture was heated for one hour at 100 ° C. After this time, analysis of the ¹ H NMR showed 99% conversion of the polysiloxane and selective formation of the hydrosilylation product of poly [(3-butyloksypropylometylo) (dimethyl) siloxane].

P r x l a d XV

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.021 g (8, 6x10 ^-6 mol) obtained as in example 1, and na6

Thereafter, 3 mL decane (internal standard), 23 mL heptamethyltrisiloxane (8.6 x 10 ^-2 mol) and allylbenzene 12.5 mL (9.4 x 10 ^-2 mol) were successively. The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3-phenylpropyl) methylbis (trimethylsiloxy) silane were determined by gas chromatography. A yield of 90% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted and then the product was distilled off. With a 92% conversion, a 90% yield was obtained (3-phenylpropyl) methylbis (trimethylsiloxy) silane. The structure of the obtained (3-phenylpropyl) methylbis (trimethylsiloxy) silane was confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

P r x l a d XVI

In a glass, two-necked, round bottom flask with a capacity of 50 ml, equipped with a reflux condenser and a magnetic stirrer, the catalyst was placed under an inert gas (argon) atmosphere.

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.019 g (7.8x10 ^-6 mol) prepared as in example 1, then 17 mL poly (methylhydrogen) siloxane (7.8x10 ^-2 mol) and allyl benzene (11 ml 8,3x10 ^-2 mol). The reaction mixture was heated for one hour at 100 ° C. After this time, analysis of the ¹ H NMR showed 99% conversion of the polysiloxane and selective formation of the hydrosilylation product of poly [(3-fenylopropylometylo) (dimethyl) siloxane].

E xample XVII

[(HSiO) Rh (cod) (PCy3)] (Aerosil 200) 0.04 g (5x10 ^-6 mol) obtained from as in Example 5, followed by poly (methylhydrogen) siloxane 10.8 mL (4.9 x 10 ^-2 mol) and allylbenzene 7 mL (5.3 x 10 ^-2 mol). The reaction mixture was heated for one hour at 100 ° C. After this time, analysis of the ¹ H NMR showed 95% conversion of the polysiloxane and selective formation of the hydrosilylation product - {poly (3-fenylopropylometylo) (dimethyl) siloxane}.

E xample XVIII

^{[(HSiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.006 g (2.4x10 -6} moles) was placed in a 50 mL glass, two-necked, round-bottom flask equipped with a reflux condenser and a magnetic stirrer. ) obtained as in example I, followed by 1 mL decane (internal standard), 6.5 mL heptamethyltrisiloxane (2.4 × 10 ^-2 mol) and 4.5 mL 4-allyl-1,2-dimethoxybenzene (2.6 × 10 ^{- 2} moles). The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the heptamethyltrisiloxane conversion and the yield of (3- (3,4-dimethoxyphenyl) propyl) methylbis (trimethylsiloxy) silane were determined by gas chromatography. A yield of 90% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted and then the product was distilled off. At a 99% conversion, a 90% yield was obtained (3- (3,4-dimethoxyphenyl) propyl) methylbis (trimethylsiloxy) silane. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction eight times without a decrease in activity. The structure of [3- (3,4-dimethoxyphenyl) propyl] methylbis (trimethylsiloxy) silane was confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

E xample XIX

^{[(HSiO) (HSiOX) Rh (cod)] (Aerosil 200) 0.036 g (1.48x10 -5} mol) was placed in a 100 mL glass, two-necked, round-bottom flask equipped with a reflux condenser and a magnetic stirrer. ) obtained as in Example 1, and then poly (methylhydrogen) siloxane 32 mL (0.15 mol) and 4-allyl-1,2-dimethoxybenzene 28 mL (0.16 mol). The reaction mixture was heated for one hour at 100 ° C. At this time, the reaction mixture was decanted, ¹ H NMR analysis showed 85% conversion of the polysiloxane and selective formation of the hydrosilylation product poly {((3- (3,4-dimethoxyphenyl) propyl) methyl) (dimethyl) siloxane}. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction nine times without a decrease in activity.

Claims (1)

The method of obtaining modified polysiloxanes of the general formula I, in which R ¹ is an alkoxy, glycidoxy, phenoxy or phenyl group, n takes values from 1 to 25 am - from 0 to 50, as a result of a catalytic hydrosilylation reaction of olefins of the general formula 2, in wherein R ¹ is as defined above, with poly (methylhydrogen) siloxanes of general formula III in which m and n are as defined above, characterized in that a heterogenized rhodium (I) siloxy complex of general formula 4 is used as the catalyst, in which the diene is cyclooctadiene, norbornadiene or tetrafluorobenzobarrelene, and L is a phosphine ligand of general formula 5, wherein R ² is an alkyl or phenyl group or a further SiOX unit from the silica surface of the general formula 6, where X is hydrogen or silicon, the reaction being carried out under an inert gas atmosphere at a temperature of 60 to 100 ° C.