PL235669B1 - New disubstituted disiloxysilsesquioxanes with the structure of incompletely closed cage and the method for obtaining disubstituted disiloxysilsesquioxanes with the structure of incompletely closed cage - Google Patents

Abstract

The subject of the application are new disyloxysilsesquioxanes with an unclosed cage structure and the general formula 2, in which: R are equal and mean isobutyl, R1, R2, R3 are equal or different and mean: - when R1, R2, R3 are equal, they mean: CH =CH2 or iPr; and when two of them are equal and mean Me, then the third means; H or CH=CH2 or (CH2)3Cl or (CH2)3O(CH2)2OH, while when two of them are equal and denote iPr, then the third one denotes H. The subject of the application is also a method of obtaining disyloxysilsesquioxanes with an unclosed cage structure and the formula general 2.

Description

Description of the invention

The present invention relates to novel disubstituted disiloxysilsesquioxanes having an open-cage structure and a method of obtaining disiloxysilsesquioxanes having an open-cage structure.

Polyhedral oligomeric silsequioxanes (POSS) are a group of organosilicon compounds with a well-defined, regular structure. Also, incompletely condensed silsesquioxanes with an open-cage structure (e.g. disilanol POSS (formula 1) with an incompletely condensed structure having 2 Si-OH groups) are increasingly used in many industries and in materials chemistry.

(1)

The hybrid structure, nanometric dimensions of silsesquioxanes and compatibility with a wide range of organic polymers make these compounds suitable for the synthesis of POSS-polymer nanocomposites with better mechanical and thermal properties than unmodified polymers. We are looking for new compounds with a hybrid, not fully condensed structure, having various types of substituents, e.g. siloxy groups, which will enable the formation of further derivatives as a result of further modifications. Effective methods are also sought to obtain incompletely condensed silsesquioxanes of an open cage structure, containing two reactive substituents in place of OH groups (e.g. siloxyl groups) surrounded by eight inert, non-reactive groups (e.g. alkyl, isobutyl). Organosilicon compounds of this type can be further transformed and are valuable substrates for synthesis and material chemistry. Due to the presence of siloxyl functional groups, siloxy-functionalized silsesquioxanes can be used as building blocks for the preparation of nanocomposites, they can show good affinity for polymers and can be used to functionalize polymers and improve their properties (mechanical, optical, thermal). Modified polymers based on silsesquioxanes have a number of applications, including in many industries, in microelectronics, optoelectronics, biomedicine, cosmetics, in the synthesis of optical materials and insulators.

Moreover, such compounds may find application in the synthesis of new functional inorganic-organic hybrid materials with unique properties.

The most commonly used methods of obtaining non-fully condensed silsesquioxanes are based on the hydrolytic condensation of RSiCh organotrichlorosilanes or organotrialkoxysilanes (M. Przybylak, H. Maciejewski, B. Marciniec, Polimery 2013, 58, No. 10, 741-747). A by-product of the hydrolytic condensation of chlorosilanes is reactive HCl which can react with many functional groups, e.g. with unsaturated groups and vinyl groups. For example, it is almost impossible to introduce, with high efficiency and chemoselectivity, a hydroxyl-containing substituent into a silsesquioxane molecule using the RSiCh organotrichlorosilane as a substrate, where the R substituent contains an OH group, because chlorosilanes react with the OH group and form many by-products, including homocondensation products of substrates. In addition, the substrates chlorosilanes are moisture sensitive compounds. These methods are inefficient as they lead to the production of many by-products, including substrate homocondensation products. The structure of the product is strongly influenced by many factors such as the duration of the process, temperature. The type of the R substituent in the organotrichlorosilane or the organotrialkoxysilane RSiXs (X = CI, OEt) is also important as it is the decisive factor whether a given product will have an incompletely or fully condensed cage structure, and the fully condensed product is undesirable or difficult in this case. for by-product separation. In these methods, only a silane with a large substituent can form an incompletely condensed cage. Another essential

The factor is the type of solvent used in the synthesis. Polar solvents stabilize the incompletely condensed silsesquioxanes because they hydrogen bond with the OH groups in the open cage POSS molecule. Long reaction times, even up to several months, low yields (max. 30-50%) and lack of selectivity, many by-products make these methods of little use in industrial production.

In order to obtain POSS derivatives with an incompletely condensed cage structure, the known catalytic hydrosilylation reaction of silsesquioxanes containing substituents with Si-H groups or unsaturated groups (directly at the POSS corners or in further substituent fragments) in the presence of a platinum catalyst (e.g. H2PtCl6 or Karstedt's catalyst) can be used. (DB Cordes, PD Lickiss, F. Rataboul, Chemical Reviews, 2010, 110, pp. 2090-2092). The reaction, however, makes it possible to obtain POSS derivatives containing substituents with introduced moieties distant from the incompletely condensed silsesquioxane cage since, for example, between the introduced group and the POSS cage is an unsaturated -CH2CH2 group. Thus, silsexioxanes with functional groups directly attached to the Si atoms of the incompletely condensed cage cannot be obtained by this method.

Marciniec disclosed a catalytic method of functionalisation of silisesquioxanes, which can be used to introduce functional groups into POSS with an incompletely condensed cage structure and consists in the silylating coupling of vinyl POSS derivatives with substituted styrenes and other olefins in the presence of Ru, Rh, Ir or Co hydride catalysts (e.g. [RuHCl (CO) (PPh3) 3] or [RuHCl (CO) (PCy3) 2]) and also carried out cross-metathesis of vinyl POSS derivatives with olefins in the presence of carbene complexes of the Grubbs type. (P. Żak, B. Marciniec, M. Majchrzak, C. Pietraszuk, Journal of Organometallic Chemistry, 2011, 696, 887-891). The starting substrates of this catalytic reaction must contain unsaturated groups e.g. vinyl groups in an incompletely condensed POSS cage, therefore the reaction yields POSS derivatives containing substituents with introduced moieties distant from the incompletely condensed cage and not directly at the silicon atoms of the cage. Between the introduced group and the POSS cage there is, for example, a -CH2CH2 group (from a vinyl moiety). The method does not make it possible to obtain silsexioxanes with functional groups directly attached to the Si atom in an incompletely condensed cage.

Satoh and colleagues (Y. Satoh, M. Igarashi, K. Sato, S. Shimada, ACS Catalysis 2017, 7, 1836-1840) presented a catalytic method for the synthesis of open-cage POSS derivatives in the reaction of silsesquioxane molecules containing Si- silanol groups OH with aryltrihydrogen silanes in the presence of a silver catalyst AuCl (PPh3) or AuCl and phosphine PPh3 or P (n-Bu) 3. The reaction is selective, however, only POSS with aryl dihydrogen silyl groups can be obtained by this method. The method does not provide siloxy-substituted incompletely fused silsesquioxanes with siloxyl groups directly attached to the Si atom in the incompletely condensed cage, because only aryltrihydrogen silanes are the substrates subject to this catalytic reaction.

Hreczeo et al. (G. Hreczycho, K. Kuciński, P. Pawluć, B. Marciniec, Organometallics, 2013, 32, 5001-5004) described a method of O-silylation of silanediols substituted with a simple isopropyl group with 2-methylallylsilanes in the presence of Sc (OTf) 3 as catalyst. The reaction allows the introduction of siloxy groups to compounds having an Si-OH bond and leads to the formation of a SiO-Si bond. Compounds having an OH group show high coupling reactivity with 2-methylallylsilanes in the presence of Sc (OTf) 3. The mechanism of this reaction consists in the activation of the OH group (O-H bond) by the catalyst, and then coupling with compounds containing the 2-methylallyl group (i.e. with 2-methylallylsilanes). The method, however, is limited to the coupling of silandiols with simple isopropyl substituents where inert alkyl groups are attached to the Si atom and the Si-OH group is not sterically blocked. Although the method allows the use of 2-methylallylsilanes with a maximum of one unsaturated substituent with a vinyl group, however, a greater number of unsaturated groups in the 2-methylallylsilane substituents may compete with the unsaturated 2-methylallyl group, which participates in the reaction mechanism and couples with gr OH.

In the described method for coupling silanols with 2-methylallylsilanes, the solvent is acetonitrile. In case the starting materials were not dissolved in pure acetonitrile, the reaction was carried out in acetonitrile with the addition of a small amount of THF, but not more than 1 part of THF to 9 parts of acetonitrile. A greater addition of THF as compared to acetonitrile deactivates the reaction catalyst. This method is not

PL 235 669 Β1 effective for substrates insoluble in acetonitrile or a mixture of acetonitrile with a small addition of THF.

The aim of the invention was to develop new non-closed cage disiloxysilsesquioxanes disiloxysilsesquioxanes and to develop a simple method for the synthesis of non-closed cage disiloxysilsesquioxanes.

The present invention relates to new disiloxysilsesquioxanes having an open-cage structure and general formula 2, wherein:

(2)

- R are equal and represent isobutyl

- R ¹ , R ² , R ³ are equal or different and are:

- when R ^1, R ^2, R ³ are equal, represent: -CH = CH 2 and / or Pr

- when two of them are equal and represent Me then the third is; H or CH = CH 2 or (CH _{2) 3} or Cl _(CH2) 3O _(CH2) 2OH

- when two of them are equal and mean / Pr then the third is H.

The compounds according to the invention are a group of new organosilicon systems - silsesquioxanes with the structure of incompletely condensed open cage with siloxyl substituents. These compounds show application potential and can be used in materials chemistry in the synthesis of new functional inorganic-organic hybrid materials with unique properties. Due to the presence of siloxyl functional groups, the novel functionalized silsesquioxanes disclosed in the invention can have good affinity for polymers and serve as building blocks and precursors of nanocomposites. Nanocomposites containing POSS particles are characterized by better mechanical and thermal properties than polymers due to the thermal stability of silsesquioxanes. Silsesquioxane modified polymers are characterized by thermal and photochemical stability, durability, good optical and electrical properties, therefore they are widely used in microelectronics, the synthesis of optical materials, insulators, elastomers and matrices in OLED devices. They are also used in the cosmetics industry and in biomedical engineering to produce biomedical materials.

Moreover, the group of novel silsesquioxane derivatives disclosed in the present invention has reactive groups, e.g. OH group, (CH2) 3Cl group, which can further be nucleophilically displaced, and we can obtain POSS derivatives with a new substituent in place of the Cl atom. The new compounds also have Si-H groups and vinyl groups situated on the silicon atom of the siloxyl group introduced into the block, which can be further modified, e.g. by hydrosilylation, silylation coupling or metathesis reactions, which makes them potential precursors for many functional materials. They can be further used in the synthesis of inorganic-organic hybrid materials.

In a second aspect, the invention relates to a process for the preparation of disiloxysilsesquioxanes having an open-cage structure and general formula 2, wherein:

PL 235 669 Β1 • R are equal and represent isobutyl • R ¹ , R ² , R ³ are equal or different and mean:

- when R ^1, R ^2, R ³ are equal, they represent: CH = CH 2 or Me or Et and / or Pr.

- when two of them are equal and represent Me then the third is; H or CH = CH 2 or (CH 2) 3 Cl, or _(CH2) 3O _(CH2) 2OH

- when two of them are equal and mean / Pr then the third is H.

In the course of the research, it was unexpectedly found that after the use of a specific solvent system in the synthesis phase as well as the isolation of products, it is possible to synthesize compounds of the general formula 2 by catalytic coupling reaction of the disilanol POSS molecule with the structure of an incompletely condensed cage with the formula 1 having two groups Si-OH:

with 2-methylallylsilanes of formula 3 as silylating agents:

R ³ (3) wherein R ¹ , R ² , R ³ are as defined above, in the presence of a Lewis acid catalyst from the group of triflates, the reaction being carried out in a non-polar aromatic solvent.

The catalytic method of O-silylation of silsesquioxane molecules with an open, incompletely condensed cage structure containing two Si-OH groups with 2-methylallylsilanes in the presence of a Lewis acid from the triflate group, e.g. Sc (OTf) 3 is shown in the diagram:

PL 235 669 Β1

Sc (OTf) ₃

where - R ¹ , R ² , R ³ are as defined above.

The reaction according to the invention is carried out in the medium of anhydrous non-polar aromatic solvents selected from the group of benzene, toluene, xylene or their mixtures. It is preferable to carry out the reaction in anhydrous toluene.

The reaction catalyst is a Lewis acid from the triflate group, most preferably the Sc (OTf) catalyst of scandium (III) 3-triflate is used in an amount of not less than 2 mol% with respect to the compound of formula 1, preferably in an amount of 4 mol%. The synthesis solvent must be dried (e.g. over molecular sieves) to get rid of traces of moisture. This is a necessary condition because the triflate catalyst is sensitive to moisture.

An excess of POSS disilanol reagent of Formula I should not be used as it is difficult to separate unreacted silsesquioxane from the product. The reaction takes place with a minimum 2-fold excess of 2-methylallylsilane of formula 3 relative to the starting material of formula 1. It is preferable to carry out the reaction with a 1: 4 molar ratio of POSS disilanol of formula 1 to 2-methylallylsilane of formula 3 because this increases the yield and shortens the synthesis time or for any excess 2-methylallylsilane greater than 1: 4.

In the process of the invention, the compound of formula 1 is dissolved in an anhydrous non-polar aromatic solvent, and the compound of formula 3 is then introduced into the solution, followed by addition of the catalyst. The catalyst is most preferably added in an amount of 4 mol% with respect to compound 1. The reaction mixture is stirred at room temperature, without the need for heating. Elevated temperatures could adversely affect the stability of the compounds and catalyst. The duration of the synthesis is 30 min - 2 h, during which time the mixture is stirred all the time. After completion of the reaction, the solvent is evaporated off, then the catalyst is removed from the product with a solvent from the group of: chain saturated hydrocarbons with 5-7 carbon atoms in the molecule or their mixtures. This solvent dissolves the product and unreacted substrates and does not dissolve the catalyst. After separating the catalyst precipitate from the product solution, the solvent is evaporated and acetonitrile is added to the resulting residue to dissolve excess 2-methylallylsilane silylating reagent. Acetonitrile dissolves silanes well, but does not dissolve silsesquioxanes, therefore, after separating the acetonitrile layer, we obtain a reaction product, which is the appropriate disiloxysiloxysilsesquioxane. In the case where an excess of POSS disilanol was used in the reaction, the product would be contaminated with unreacted POSS disilanol. Due to the difficulties in removing unreacted disilanol POSS, it is advisable to use appropriate stoichiometric amounts.

In the course of the research, it turned out that on the one hand, the appropriate choice of the reaction medium enables the synthesis and the introduction of siloxyl groups with reactive groups, i.e. 3 unsaturated groups, OH group into POSS with Si-OH groups. Then, thanks to the specific sequence of separation with the use of different but precisely selected solvents, it is possible to isolate the product.

The process of the invention for the preparation of new disiloxysilsesquioxanes by O-silylation of a silsesquioxane having 2 Si-OH groups with an incompletely condensed open cage structure using 2-methylallylsilanes as silylating reagents in the presence of triflates has a number of advantages:

• takes place under mild conditions - at room temperature, without the need for heating • short reaction time - 2 h • synthesis is efficient and effective - yields of isolated products are in the range of 76-96% • no harmful by-products are formed as a result of the reaction • the reaction is selective - the only by-product of this process is isobutene - a neutral olefin that is easy to remove

PL 235 669 Β1 • a small amount of catalyst is used - 2 mol% • the synthesis enables the introduction of substituents with functional groups - eg OH.

The invention is illustrated by the following examples which do not exhaust all variants of the structure of the compounds of formula 2. The structure of the obtained organosilicon compounds was confirmed by the following techniques: nuclear magnetic resonance spectroscopy (NMR using Varian Gemini 300 and Varian Mercury XL 300 spectrometers) and EI-MS techniques ( using a 320 MS / 450 GC Bruker apparatus).

Example 1

To the flask containing the magnetic stirrer, 0.200 g of the compound of formula 1 (octaisobutyl disilanol POSS) (2.25x10 ^-4 mol, 1 eq), 0.147 g of trivinyl (2-methylallyl) silane (9.0x10 ^-4 mol, 4 eq) were added, and 2 ml of anhydrous toluene. Was then added 4,43x10 ^-3 g of Sc (OTf) 3 (9x10 ^-6 mol, 0.04 eq = 4 mol%) and the mixture was stirred for 2 h. After completion of the reaction the solvent was evaporated, followed by addition of n-hexane, to separate product from catalyst sediment.

The solvent was evaporated and acetonitrile was added to the obtained residue to dissolve excess 2-methylallylsilane silylating reagent. After separation of the acetonitrile layer and evaporation of the solvent, the reaction product of bis (trivinylsiloxy) octa (isobutyl) silsesquioxane was obtained in 93% yield.

¹ NMR (400 MHz, C ₆ D ₆ ) δ (ppm) = 0.91 (d, 16H, J = 7.0 Hz, SiCH 2 CH (CH 3) 2); 1.13 (d, 48H, J = 6.6Hz, SiCH2CH (CH3) 2; 2.00-2.13 (m, 8H, 5ίΟΗ ₂ ΟΗ (ΟΗ ₃ ) 2); 6.05 (dd, 6H , J = 20.2; 3.9 Hz CH = CH ₂ ); 6.14 (dd, 6H, J = 14.9; 3.9 Hz, CH = CH ₂ ); 6.38 (dd, 6H, J = 20.2, 14.9 Hz, CH = CH ₂ ).

¹³ C NMR (101 MHz, C ₆ D ₆ ) δ (ppm) = 22.7; 23.8; 24.0; 24.0; 24.1; 25.2; 25.6; 25.8; 25.9; 26.0; 135.0; 135.3.

²⁹ Si NMR (79 MHz, C ₆ D ₆ ) δ (ppm) = -25.2; -65.5; -67.6.

MS (EI) m / z (int. Rei): 999 (5%), 997 (25), 994 (50), 914 (10), 828 (2), 713 (2), 629 (2), 561 (2), 476 (2), 413 (20), 329 (10), 109 (100), 110 (20), 43 (50), 42 (10), 41 (25).

Example 2

0.200 g of the compound of formula 1 (octaisobutyl disilanol POSS) (2.25x10 ^-4 mol, 1 eq), 0.191 g triisopropyl (2-methylallyl) silane (9.0x10 ^-4 mol, 4 eq) were added to the flask containing the magnetic stirrer. and 2 ml of anhydrous toluene. Was then added 4,43x10 ^-3 g of Sc (OTf) 3 (9x10 ^-6 mol, 0.04 eq = 4 mol%) and the mixture was stirred for 2 h. After completion of the reaction the solvent was evaporated, followed by addition of n-hexane, to separate product from catalyst sediment. The solvent was evaporated and acetonitrile was added to the obtained residue to dissolve excess silylating reagent.

PL 235 669 Β1

- 2-methylallylsilane. After separating the acetonitrile layer and evaporating the solvent, the reaction product of bis (triisopropylsiloxy) octa (isobutyl) silsesquioxane was obtained in 81% yield.

¹ H NMR (400 MHz, C ₆ D ₆ ) δ (ppm) = 0.81 (d, 16H, J = 7.0 Hz, SiCH ₂ CH (CH ₃ ) ₂ ); 1.08 (d, 48H, J = 6.6Hz, SiCH ₂ CH (CH 3) ₂ ); 1.22 (d, 36H, J = 6.7Hz, SiCH (CH3) ₂ ); 1.35-1.41 (m, 6H, SiCH (CH ₃ ) ₂ ); 2.01-2.16 (m, 8H, SiCH ₂ CH (CH ₃ ) ₂ ).

¹³ C NMR (101 MHz, C ₆ D ₆ ) δ (ppm) = 12.6; 18.0; 22.8; 23.3; 24.1; 25.7; 25.8.

²⁹ Si NMR (79 MHz, C ₆ D ₆ ) δ (ppm) = 9.4; -67.5; -68.1.

Example 3

To the flask containing the magnetic stirrer, 0.200 g of the compound of formula 1 (octaisobutyl disilanol POSS) (2.25x10 ^-4 mol, 1 eq), 0.126 g of dimethylvinyl (2-methylallyl) silane (9.0x10 ^-4 mol, 4 eq) were added, and 2 ml of anhydrous toluene. Was then added 4,43x10 ^-3 g of Sc (OTf) ₃ (9x10 ^-6 mol, 0.04 eq = 4 mol%) and the mixture was stirred for 2 h. After completion of the reaction the solvent was evaporated, followed by addition of n-hexane, to separate product from catalyst sediment. The solvent was evaporated and acetonitrile was added to the obtained residue to dissolve excess 2-methylallylsilane silylating reagent. After separating the acetonitrile layer and evaporating the solvent, the reaction product of bis (dimethylvinylsiloxy) octa (isobutyl) silsesquioxane was obtained in 96% yield.

¹ H NMR (400 MHz, C ₆ D ₆ ) δ (ppm) = 0.43 (s, 12H, SiCl 3); 0.83 (d, 16H, J = 7.0 Hz, SiCHzCH (CH _{3) 2);} 1.09 (d, 48H, J = 6.6Hz, SiCH ₂ CH (CH 3) ₂ ); 2.01-2.20 (m, 8H, SiCH ₂ CH (CH ₃ ) ₂ ); 5.90 (dd, 2H, J = 20.4, 3.8Hz, CH = CH2); 6.02 (dd, 2H, J = 14.9; 3.8 Hz, CH = CH ₂ ): 6.37 (dd, 2H J = 7 = 20.4; 14.9 Hz, CH = CH ₂ ) .

¹³ C NMR (101 MHz, C ₆ D ₆ ) δ (ppm) = 0.4; 22.7; 23.8; 24.0; 24.1; 24.2; 25.2; 25.6; 25.7; 25.8; 26.0; 132.0; 139.0.

²⁹ Si NMR (79 MHz, C ₆ D ₆ ) δ (ppm) = -2.0; -65.5; -67.6.

MS (EI) m / z (int. Rei): 1058 (5%, M ⁺ ), 1007 (15), 1005 (30), 1002 (55), 948 (70), 946 (90), 933 ( 25), 890 (40), 817 (15), 663 (10), 563 (15), 480 (10), 410 (25), 309 (2), 304 (20), 127 (5), 85 ( 100), 56 (15), 41 (30), 43 (50).

Example 4

To the flask containing the magnetic stirrer was added 0.200 g of the compound of formula 1 (octaisobutyl disilanol POSS) (2.25x10 ^-4 mol, 1 eq), 0.171 g [(3-chloropropyl) dimethyl] (2-methylallyl) silane (9.0x10 ^{- 4} mol, 4 eq), and 2 ml of anhydrous toluene. Was then added 4,43x10 ^-3 g of Sc (OTf) ₃ (9x10 ^-6 mol, 0.04 eq = 4 mol%) and the mixture was stirred for 2 h. After completion of the reaction the solvent was evaporated, followed by addition of n-hexane, to separate product from catalyst sediment. The solvent was evaporated and acetonitrile was added to the obtained residue to dissolve excess od

PL 235 669 Β1 of the silylating agent - 2-methylallylsilane. After separating the acetonitrile layer and evaporating the solvent, the reaction product of bis [(3-chloropropyl) dimethylsiloxy] octa (isobutyl) silsesquioxane was obtained in a yield of 76%.

¹ H NMR (400 MHz, C ₆ D ₆ ) δ (ppm) = 0.29 (s, 12H, SiCHa); 0.69-0.75 (m, 4H, SiO 3); 0.83 (d, 16H, J = 7.0 Hz, SiCH2CH (CH _{3) 2);} 1.08 (d, 48H, J = 6.6Hz, SiCH ₂ CH (CIH3) ₂ ); 1.78-1.84 (m, 4H, CH6); 2.02-2.20 (m, 8H SiCH ₂ CH (CH ₃ ) ₂ ); 3.35 (t, 4H, J = 6.9Hz, CH2Cl).

¹³ C NMR (101 MHz, C ₆ D ₆ ) δ (ppm) = 0.1; 15.8; 22.7; 23.8; 24.0; 24.1; 24.2; 25.2; 25.6; 25.7; 25.8; 25.9;

27.0.

²⁹ Si NMR (79 MHz, C ₆ D ₆ ) δ (ppm) = 9.2; -65.5; -67.4.

MS (EI) m / z (int. Rei): 1026 (2%), 1022 (20), 1020 (50), 867 (5), 791 (2), 671 (2), 559 (2), 435 (2), 315 (1), 209 (2), 137 (20), 135 (80), 59 (45), 45 (5), 42 (100), 41 (20).

Example 5

To the flask containing the magnetic stirrer, 0.200 g of the compound of formula 1 (octaisobutyl disilanol POSS) (2.25x10 ^-4 mol, 1 eq), 0.194 g (2-methylallyl) silane (9.0x10 ^-4 mol, 4 eq) were added, and 2 ml of anhydrous toluene. Was then added 4,43x10 ^-3 g of Sc (OTf) 3 (9x10 ^-6 mol, 0.04 eq = 4 mol%) and the mixture was stirred for 2 h. After completion of the reaction the solvent was evaporated, followed by addition of n-hexane, to separate product from catalyst sediment. The solvent was evaporated and acetonitrile was added to the obtained residue to dissolve excess 2-methylallylsilane silylating reagent. After separation of the acetonitrile layer and evaporation of the solvent, the reaction product was obtained in 78% yield.

¹ H NMR (400 MHz, C ₆ D ₆ ) δ (ppm) = 0.06-0.42 (m, 12H, S1CH3); 0.52-0.75 (m, 4H, SiCH ₂ CH ₂ ); 0.85 (d, 16H, J = 7.0 Hz, SiCH2CH (CH _{3) 2);} 0.98-1.16 (m, 48H, SiCH ₂ CH (CIH 3) ₂ ); 1.68-1.81 (m, 4H, S1CH2CH2); 2.03-2.20 (m, 8H SiCH ₂ CH (CH ₃ ) ₂ ); 3.24 (t, 2H, J = 6.8 Hz, CI ± O); 3.28 (t, 2H, J = 6.7 Hz, Cl 6 O); 3.33 (t, 2H, J = 6.7Hz, ClW); 3.37 (t, 2H, J = 6.8Hz, ClW); 3.56 (t, 2H, J = 6.8 Hz, Cl 6 O); 3.62 (t, 2H, J = 6.7Hz, CH2O).

¹³ C NMR (101 MHz, C6D6) δ (ppm) = 0.3; 14.4; 22.8; 23.7; 23.9; 24.2; 25.4; 25.8; 26.1; 61.7; 72.4; 74.0. ²⁹ Si NMR (79 MHz, C6D ₆₎ δ (ppm) = 10.1; -65.4; -67.5.

Example 6

To the flask containing a magnetic stirrer, 0.200 g of the compound of formula 1 (octaisobutyl disilanol POSS) (2.25x10 ^-4 mol, 1 eq), 0.103 g of dimethyl (2-methylallyl) silane (9.0x10 ^-4 mol, 4 eq) were added, and 2 ml of anhydrous toluene. Was then added 4,43x10 ^-3 g of Sc (OTf) 3 (9x10 ^-6 mol, 0.04 eq = 4 mol%) and the mixture was stirred for 2 h. After completion of the reaction the solvent was evaporated, then

PL 235 669 Β1 n-hexane was added to separate the product from the catalyst slurry. The solvent was evaporated and acetonitrile was added to the obtained residue to dissolve excess 2-methylallylsilane silylating reagent. After separating the acetonitrile layer and evaporating the solvent, the reaction product of bis (dimethylsiloxy) octa (isobutyl) silsesquioxane was obtained in a yield of 94%.

¹ NMR (400 MHz, C ₆ D ₆ ) δ (ppm) = 0.39 (s, 12H, SiCH 3); 0.80 (d, 16H, J = 7.0Hz, SiCl 2 CH (CH ₃ ) ₂ ); 0.991.12 (m, 48H, SiCH ₂ CH (CH ₃ ) ₂ ); 2.01-2.13 (m, 8H, SiCH ₂ CH (CH ₃ ) ₂ ); 5.14 (s, 2H, SiH).

¹³ C NMR (101 MHz, C ₆ D ₆ ) δ (ppm) = 0.6; 22.7; 23.7; 24.0; 24.1; 24.2; 24.9; 25.6; 25.7; 25.8; 25.9.

²⁹ Si NMR (79 MHz, C ₆ D ₆ ) δ (ppm) = -5.0; -65.7; -67.8.

Claims (6)

Patent claims 1. New disubstituted disiloxysilsesquioxanes of open cage structure of general formula 2, wherein: • R are equal and represent isobutyl • R ¹ , R ² , R ³ are equal or different and represent: - when R ^1, R ^2, R ³ are equal, represent: -CH = CH 2 and / or Pr - when two of them are equal and represent Me then the third is; H or CH = CH 2 or (CH _{2) 3} or Cl (CH _{2) 3} O (CH 2) ₂ OH - when two of them are equal and mean / Pr then the third is H. 2. A method for obtaining two substituted disiloxysilsesquioxanes with an open-cage structure of the general formula 2, in which: • R are equal and represent isobutyl • R ¹ , R ² , R ³ are equal or different and represent: - when R ^1, R ^2, R ³ are equal, they represent: CH = CH 2 or Me or Et and / or Pr. - when two of them are equal and represent Me then the third is; H or CH = CH 2 or (CH ₂ ) ₃ Cl or (CH ₂ ) ₃ O (CH ₂ ) 2 OH - when two of them are equal and represent / Pr then the third one is H characterized in that it consists in the reaction of disilanol POSS with the structure of an incompletely condensed cage, with the formula 1 PL 235 669 Β1 (1) 2-metyloallilosilanami of formula ZR 3 = ¹ ^^ Si-R ² R ³ (3) wherein R ¹ , R ² , R ³ are as defined above, in the presence of a Lewis acid catalyst from the group of triflates, the reaction being carried out in a non-polar aromatic solvent. 3. The method according to p. 2. The process of claim 2, characterized in that the catalyst is used in an amount of not less than 2% relative to POSS disilanol. 4. The method according to p. A process according to claim 2 or 3, characterized in that scandium (III) trifluoromethanesulfonate is used in the reaction. 5. The method according to p. A process according to claim 2, 3 or 4, characterized in that the reaction is carried out in a medium of anhydrous non-polar aromatic solvents selected from the group of benzene, toluene, xylene or their mixtures. 6. The method according to p. The process of claim 5, wherein the reaction is carried out in toluene.