This invention relates to new fluorocarbofunctional silsesquioxanes containing other reactive functional groups, and a method to obtain the same.

The physico-chemical properties of and a method to use functionalized silsesquioxanes depend on their spatial structure though, principally, on the number and type of functional groups present in their molecule. Such groups usually act as a factor which compatibilizes with the polymer matrix of the carrier of specific physico-chemical properties, or as active sites which interact chemically with the polymer or the substrate. The greatest interest is aroused by polyhedral silsesquioxanes having a regular cage structure (POSS), containing eight silicon atoms in the corners of their core (T ₈ ) and eight functional groups attached to them, which are the same in a majority of cases. The presence of eight reactive groups, in a majority of cases, leads to a considerable increase in the polymer crosslinking degree, which is undesirable. It is more desirable to use POSS with just one or several active groups, which has the effect of a more loose network or modifying the polymer by way of grafting in its side chain without forming lattice points

Several methods for the synthesis of silsesquioxanes, substituted in 8 corners (POSS T ₈ ) and containing more than one type of functional groups are known in the art.

Lickiss [1. P. D. Lickiss, F. Rataboul, monography Adv. Organomet. Chem. 2008, 57, 1-116] described a method to obtain POSS with T ₈ by hydrolytic co-condensation of two different organo-silicon monomers (trialkoxy- or trichlorosilanes), containing specified functional groups. The method is inefficient and rarely used because it is impossible to control the structure of the compounds being formed, both in respect of their spatial structure and the stoichiometry of the functional groups present in a molecule. The method is usually applied for obtaining octasilsesquioxanes containing one type of functional groups only. Moreover, the method is applied for the synthesis of POSS having the structure of an incompletely closed cage, containing three silanol groups. Another hydrolytic co-condensation of this type of silanetriols with a single molecule of organo-functional trialkoxy- or trichlorosilane (so-called corner capping reaction) leads to the obtaining of bifunctional silsesquioxanes. This reaction type is widely used and reported in the literature (1 ). The process is usually carried out in an anhydrous organic solvent environment (pentane, hexane) in the presence of amines (mainly triethylamine) at a reduced temperature, to obtain a high yield of products. The method is useful for obtaining POSS with the molar ratio of various functional groups equal to 7: 1 , where just one group is a reactive group. The number of reactive functional groups which are suitable for being introduced into the POSS structure is limited, which results from the poor availability of appropriate organo-silicon monomers containing reactive functional groups or degradation of reactive functional groups in a reaction environment. The method is usually applied for the synthesis of silsesquioxanes containing seven isobutyl, isooctyl or phenyl groups each, combined with a single vinyl group, a hydrogen atom, dimethylsilyl group, dimethylvinylsilyl, or chlorine atom. These are derivatives which enable further modification, though within that single group only.

Disclosed in the U.S. Patent Application No. US2010/222503 is a method for the synthesis of silsesquioxanes which contain two functional group types in a molecule, by way of degradation and recombination of a mixture of two silsesquioxanes containing desirable functional groups. The reaction is catalyzed by tetrabutylammonium fluoride (TBAF). The reaction product is a mixture of two compounds with different core structures (T ₈ , Ti ₀ ) and ratios of functional groups in a molecule, which is an important drawback of the method. The substrates used in this type of conversions included octavinyl- and octaphenyloctasilsesquioxanes, to obtain compounds having the structure Tg, Tio and T _i2 , containing both vinyl and phenyl groups at various stoichiometric ratios in a molecule.

The U.S. Patent Application No. US2009/012317 describes a method for the synthesis of POSS in which the stoichiometry of functional groups is 4:4, by way of degradation of an octafunctional POSS in the presence of NaOH and n-butanol, with the formation of cyclotetrasiloxane sodium salt with a high yield. In the next step, the resulting intermediate is subjected to co-condensation with tetracyclotetrasilanol which also contains appropriate functional groups. Instead of tetracyclotetrasilanol, also organo-functional chlorosilanes may be used which, as a result of substitution, esterification, and then condensation in an aqueous environment also form completely condensed POSS having a well-defined structure and the molar ratio of functional groups in a molecule equal to 4:4. This has enabled the obtaining of POSS with various combinations of stilbene, phenyl, iodophenyl, and vinyl groups. However, the ratios of their functional groups were 4:4 in each case.

Disclosed in the same patent application is also a different method to obtain silsesquioxanes containing functional groups with the ratio of 4:4, by way of allyl-glycidyl ether and allyl chloride hydrosilylation with silsesquioxane in the presence of platinum catalysts. Such compounds had 4 epoxy or chloro groups each in combination with propyl groups.

In the available scientific and patent literature, there are no reports about POSS synthesis with mixed functional groups having a predetermined molar ratio of their functional groups, other than 4:4. It was the purpose of this invention to synthesize new silsesquioxanes containing two functional group types with different stoichiometric ratios, specifically those containing fluorocarbofunctional groups and other reactive organic groups, and to develop an efficient method for the synthesis of such compounds.

This invention relates to new silsesquioxane derivatives, containing two functional group types having the general formula 1,

[R ¹ (SiR ³ ₂ 0) _m ] _n [R ² (SiR ³ ₂ 0) _m ] _8-n [(Si0 ₁ . ₅ )8] (l) in which

• R ¹ denotes the group HCF ₂ (CF ₂ ) _x (CH ₂ ) _y O(CH ₂ )3- or CF3(CF ₂ ) _Z CH ₂ CH ₂ -;

• R ² denotes a glycidoxypropyl, triethoxysilylethyl functional group;

• R ³ are equal and denote a methyl or phenyl group;

• m - are equal and take the value 0 or 1, n=l-7, x=l-12, y=l-4, z=0-12.

In its second aspect, this invention relates to a method to obtain new and conventional silsesquioxane derivatives containing two functional group types having the general formula 1,

[R ¹ (SiR ³ ₂ 0) _m ] _n [R ² (SiR ³ ₂ 0) _m ] _8-n [(Si0 ₁ . ₅ )8] (l) in which

• R ¹ denotes the group HCF ₂ (CF ₂ ) _x (CH ₂ ) _y O(CH ₂ ) ₃ - or CF ₃ (CF ₂ ) _Z CH ₂ CH ₂ -;

• R ² denotes any organic functional group, specifically glycidoxypropyl, epoxycyclohexylethyl, triethoxysilylethyl, alkyl (C ₅ -C ₂₅ ), methacryloxypropyl, hydroxypropyl, aminopropyl;

• R ³ denotes a methyl or phenyl group;

• m - are equal and take the value 0 or 1, n=l-7, x=l-12, y=l-4, z=0-12;

by two-step hydrosilylation.

In the first step of the reaction, a fluorinated olefin having the general formula 2 or 3 is hydrosilylated,

HCF ₂ (CF ₂ ) _x (CH ₂ ) _y OCH ₂ CH=CH ₂ (2)

where x=l-12, y=l-4

CF ₃ (CF ₂ ) _Z CH=CH ₂ (3)

where z=0-12

with a hydridosilsesquioxane having the general formula 4,

Q ₈ [(SiO _L5 ) ₈ ] (4)

in which

- Q are equal or different and denote H-, the group HSi(CH ₃ ) ₂ 0 or the group HSi(C ₆ H ₅ ) ₂ 0, and then, in the second step, a functional olefin having the general formula 5 is hydrosilylated,

ZCH=CH ₂ (5)

where - Z denotes a glycidoxy, epoxycyclohexyl, triethoxysilyl, alkyl (C3-C23), methacryloxy, hydroxymethylene, amino group,

with a partly substituted hydridosilsesquioxane from the first step, in the presence of conventional catalysts for hydrosilylation processes, particularly transition metal complexes.

The first step is carried out at a 1 :1 molar ratio of the fluorinated olefin to a mole of the SiH groups to be substituted in hydridosilsesquioxane. For instance, if one SiH group is to be substituted in hydridosilsesquioxane then 1 mole of olefin is used for one mole of hydridosilsesquioxane, if two - then two moles are used.

In the second step an excess of the olefin relative to the partly substituted hydridosilsesquioxane is used in an amount of up to 10% relative to the other SiH groups to be substituted.

The following are used as catalysts: platinum catalysts with platinum in the oxidation states 0, II or IV, and rhodium catalysts with rhodium in the oxidation states 0, I or III. Preferably, the catalysts used are siloxy-rhodium complexes, specifically

The reaction is carried out in the temperature range from 50-120°C until the process is completed, generally for 0.5-4 hours, in the environment of a solvent selected from the group: aromatic compounds, aliphatic compounds, ethers, particularly in toluene, in an open system, at a normal pressure. Preferably, the process is carried out without isolating the product obtained in the first step, by adding the respective olefins consecutively so that the fluorinated olefin is added first.

The synthesis may be carried out with intermediate isolation of the product obtained in the first step, though this is unduly labour consuming and too much energy and raw materials are required for the isolation of the product obtained in the first step. The procedure requires the use of more solvent and catalyst. In this case, the time required for obtaining the final product is longer because of the necessity to carry out the extra operations and also because of the longer reaction time. Although yield in the synthesis step II is high, efficiency is lower after the first step because of isolation of the intermediate product, therefore, the final product yield is always lower, compared with that obtained in a single-step process.

It is also useful though not required to use an excess of the organo-functional olefin which is added in the second step, so as to cause a complete conversion of the SiH groups in hydridosilsesquioxane. Preferably, such excess is in the range from 1.1 to 1.4 mole, most preferably, 1.1 of the olefin for every mole of Si-H.

The catalyst is used in an amount in the range 10 ^"4 -10 ^"6 mole of methane for 1 mole of the Si-H groups present in the hydridosilsesquioxane used for the synthesis, most preferably in the amount of 2.5xl0 ^~6 mole.

In the method of the invention, the reactor is filled with a mixture comprising a suitable stoichiometric ratio of hydridosilsesquioxane and fluorinated olefin having the general formula 2 or 3, dissolved in a solvent. A suitable amount of the catalyst is added to the resulting solution. The whole mixture is then mixed with heating to a temperature in the range 50-120°C, until a complete conversion of the entire fluorinated olefin (to be controlled by means of FT-IR). The completion of the first step of the reaction is followed by the addition of a suitable amount of the second olefin having the general formula 5 and heating is continued until the conversion of all the Si-H groups. After the process is completed the product is isolated by evaporation of the solvent and any excess olefin.

The use, in the method of the invention, of the hydrosilylation process has enabled, in the "one pot" process, the synthesis of silsesquioxanes containing two functional group types, having various contents of such groups, with high yield and selectivity.

The starting raw material is a strictly defined molecule of hydridosilsesquioxane, which eliminates any chance of obtaining compounds with different cage sizes or different topologies. Moreover, introduction of fluorocarbofunctional groups in the silsesquioxane structure in the first step, owing to their chemical inertness and hydrophobic properties, facilitates addition of subsequent olefins and enables their addition in a desirable stoichiometric ratio.

The presence of two different types of functional groups in a POSS molecule enables, owing to the use of their reactivity, among other things, the formation of bonds with the polymer matrix and the obtaining of specific properties in the resulting composite. One example is silsesquioxanes containing reactive organic groups, which interact with the polymer, and fluorocarbofunctional groups, which are non-reactive from the chemical point of view although they noticeably affect changes in the surface properties of the resulting material.

The method of the invention is illustrated by way of the examples below, which are not intended to limit the scope of use of the invention.

Example 1.

Synthesis of tetrakis( {1,1 ,2,2,3,3,4,4-octafluoropentyloxypropyl} dimethylsiloxy)-tetrakis ( {3-glycidoxypropyl} dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 6 g (19.6 mmole) of octafluoropentyl-allyl ether, 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, and 50 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy-rhodium complex [ was added. The flask was heated to 110°C and was maintained at that temperature, with mixing, for 4 hours. After that time, 2.3 mL (21.5 mmole) of allyl-glycidyl ether (10% excess) was added to the reaction mixture and the reaction was continued for another 4 hours. After that time, the reaction mixture was cooled down and, at a reduced pressure, the solvent was evaporated along with any excess of unreacted olefin. The product was 12.2 g of tetrakis( { l , 1 ,2,2, 3,3,4, 4-octafluoropentyloxy-propyl}dimethylsiloxy)- tetrakis ( {3-glycidoxypropyl}dimethylsiloxy)octasilsesquioxane in the form of a viscous oil, obtained with a yield of 97%.

Spectroscopic analysis.

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.15(s, 48H, Si(CH ₃ ) ₃ ); 0.60(t, 16H, SiCH ₂ ); 1.63 (qui, 16H, CH ₂ ); 3.53 (t, 8H, CH ₂ 0); 3.43 (m, 8H, CH ₂ 0); 3.89 (t, 8H, OCH ₂ ); 3.34 (m, 4H, OCH ₂ ); 3.71 (d, 4H, OCH ₂ ); 6.06 (t, 4H, CF ₂ H); 3.1 1 (m, 4H, CH); 2.57 (t, 4H CH ₂ 0 _oxi ); 2.76 (t, 4H, CH ₂ 0 _oxi )

¹³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -0.64 (Si(CH ₃ ) ₂ ); 13.60 (SiCH ₂ ); 23.07 (CH ₂ ); 43.98 (CH ₂ 0 _oxi ); 50.68 (CH); 67.33 (OCH ₂ ); 71.36 (OCH ₂ ); 73.96 (CH ₂ 0); 75.47 (CH ₂ 0); 104.27 (CF ₂ ); 107.62 (CF ₂ ); 110.98 (CF ₂ H); 115.5 (CF ₂ ) ppm.

²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 13.07 (Si(CH ₃ ) ₂ ); -109.06 (SiOSi) ppm.

Example 2

Synthesis of hexakis ({ 1,1, 2,2,3, 3,4,4-octafluoropentyloxypropyl} dimethylsiloxy)-bis ({3- glycidoxypropyl} dimethylsiloxy)octasilsesquioxane.

The synthesis was carried out as in Example 1 , except that the substrates, fluorine olefin : glycidyl olefin, were used at a stoichiometric ratio of 6:2 in contrast to the ratio 4:4 in Example 1. The product was 13.8 g viscous oil, obtained with the yield of 98%.

Spectroscopic analysis

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.14(s, 48H, Si(CH ₃ ) ₃ ); 0.59(t, 16H, SiCH ₂ ); 1.62 (qui, 16H,

CH ₂ ); 3.53 (t, 12H, CH ₂ 0); 3.43 (m, 4H, CH ₂ 0); 3.89 (t, 12H, OCH ₂ ); 3.34 (m, 2H, OCH ₂ ); 3.69 (d, 2H, OCH ₂ ); 6.05 (t, 6H CF ₂ H); 3.1 1 (m, 2H, CH); 2.58 (t, 2H, CH ₂ 0 _oxi ); 2.77 (t, 2H, CH ₂ 0 _oxi )

¹³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -0.56 (Si(CH ₃ ) ₂ ); 13.34 (SiCH ₂ ); 22.99 (CH ₂ ); 44.15

(CH ₂ 0 _oxi ); 50.80 (CH); 67.44 (OCH ₂ ); 71.47 (OCH ₂ ); 74.07 (CH ₂ 0); 75.57 (CH ₂ 0); 105.12 (CF ₂ ); 107.64 (CF ₂ ); 110.17 (CF ₂ H); 115.55 (CF ₂ ) ppm.

²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 13.02 (Si(CH ₃ ) ₂ ); -108.97 (SiOSi) ppm.

Example 3

Synthesis of heptakis ({l,l,2,2,3,3,4,4-octafluoropentyloxypropyl} dimethylsiloxy)-({3- glicyd-oxypropyl} dimethyls iloxy)octasilsesquioxane.

The synthesis was carried out as in Example 1 except that the stoichiometric ratio of the substrates was 7:1 in contrast to the ratio of 4:4 in Example 1.

The product was 14.7 g viscous oil, obtained with the yield of 99%.

Spectroscopic analysis

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.14(s, 48H, Si(CH ₃ ) ₃ ); 0.60(t, 16H, SiCH ₂ ); 1.62 (qui, 16H,

CH ₂ ); 3.53 (t, 14H, CH ₂ 0); 3.43 (m, 2H, CH ₂ 0); 3.89 (t, 14H, OCH ₂ ); 3.34 (m, 1H, OCH ₂ ) ; 3.69 (d, 1 H, OCH ₂ ); 6.05(t, 7H, CF ₂ H); 3.11 (m, 1H, CH); 2.58 (t, 1H, CH ₂ 0 _oxi ); 2.77 (t, 1H, CH ₂ 0 _oxi )

¹³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -0.58 (Si(CH ₃ ) ₂ ); 13.37 (SiCH ₂ ); 23.02 (CH ₂ ); 44.02

(CH ₂ 0 _oxi ); 50.82 (CH); 67.44 (OCH ₂ ); 71.5 (OCH ₂ ); 74.1 (CH ₂ 0); 75.61 (CH ₂ 0); 104.35 (CF ₂ ); 107.72 (CF ₂ ); 111.82 (CF ₂ H); 115.62 (CF ₂ ) ppm.

²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 13.07 (Si(CH ₃ ) ₂ ); -109.58 (SiOSi) ppm. Example 4

Synthesis of tetrakis( {1,1 ,2,2,3, 3,4,4-octafluoropentyloxypropyl} dimethylsiloxy)- tetrakis( {2-trimethoxysilylethyl} dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, 5.35 g (19.6 mmole) of octafluoropentyl-allyl ether and 30 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy-rhodium complex [ {Rh^-OSiMe ₃ )(cod)} ₂ ] was added. The flask was heated to 110°C and was maintained at that temperature, with mixing, for 1 hour. The course of the process and the time of its completion were determined based on measurements with the use of FT-IR. Then 2.9 g (2.8 mmole) of vinyltrimethoxysilane (10% excess) was added to the reaction mixture and the reaction was continued for one more hour while monitoring its course with the use of FT-IR. After that time, the reaction mixture was cooled down and, at a reduced pressure, the solvent was evaporated along with any excess olefin. The product was 13.25 g tetrakis({ 1,1, 2,2,3, 3,4,4-octafluoropentyloxy- propyl} dimethylsiloxy)tetrakis -( {2-trimethoxysilylethyl} dimethylsiloxy)octasilsesquioxane in the form of a viscous oil, obtained with a yield of 97%.

Spectroscopic analysis.

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.12(s, 24H, Si(CH ₃ ) ₂ ); 0.51 (t, 24H, SiCH ₂ ); 1.51 (qui, 8H, CH ₂ ); 3.21 (t, 16H, OCH ₂ ); 3.43 (s, 36H, OCH ₃ ); 5.54 (t, 4H, CF ₂ H);

¹³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -0.58 (Si(CH ₃ ) ₂ ); 13.59 (SiCH ₂ ); 23.29 (CH ₂ ); 50.28 (OCH ₃ ); 67.58 (OCH ₂ ); 75, 45 (OCH ₂ ); 104.84 (CF ₂ ); 108.20 (CF ₂ ); 111.55 (CF ₂ H); 116.03 (CF ₂ ) ppm.

²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 15.19 (Si(CH ₃ ) ₂ ); -107.06 (SiOSi) ppm.

Example 5

Synthesis of hexakis( {1,1 ,2,2,3, 3,4,4-octafluoropentyloxypropyl} dimethylsiloxy)-bis( {2- trimeth-oxysilylethyl} dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, 8.02 g (29.5 mmole) of octafluoropentyl -allyl ether and 30 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy-rhodium complex [ {Rh^-OSiMe ₃ )(cod)} ₂ ] was added. The flask was heated to 110°C and was maintained at that temperature, with mixing, for 1 hour. The course of the process and the time of its completion were determined based on measurements with the use of FT-IR. Then 1.46 g (1.4 mmole) of vinyltrimethoxysilane (10%> excess) was added to the reaction mixture and the reaction was continued for one more hour while monitoring its course with the use of FT-IR. After that time, the reaction mixture was cooled down and, at a reduced pressure, the solvent was evaporated along with any excess olefin. The product was 14.48 g hexakis ({1,1,2,2,3,3,4,4- octafluoropentyloxypropyl} dimethylsiloxy))bis -( {2- trimethoxysilylethyl} dimethylsiloxy)octasilsesquioxane in the form of a viscous oil, obtained with a yield of 92%.

Spectroscopic analysis.

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.16(s, 24H, Si(CH ₃ ) ₂ ); 0.54(t, 20H, SiCH ₂ ); 1.55 (qui, 12H,

CH ₂ ); 3.22 (t, 24H, OCH ₂ ); 3.48 (s, 18H, OCH ₃ ); 5.46 (t, 6H, CF ₂ H);

¹³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -0.54 (Si(CH ₃ ) ₂ ); 13.60 (SiCH ₂ ); 23.29 (CH ₂ ); 50.32

(OCH ₃ ); 67.59 (OCH ₂ ); 75, 48 (OCH ₂ ); 104.83 (CF ₂ ); 108.18 (CF ₂ ); 1 1 1.54 (CF ₂ H); 116.06 (CF ₂ ) ppm.

²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 15.33 (Si(CH ₃ ) ₂ ); -107.03 (SiOSi) ppm. Example 6

Synthesis of heptakis ({l,l,2,2,3,3,4,4-octafluoropentyloxypropyl} dimethylsiloxy)-({2- trimethoxysilylethyl} dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, 9.36 g (34.4 mmole) of octafluoropentyl- allyl ether and 30 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy-rhodium complex [ {Rh^-OSiMe ₃ )(cod)} ₂ ] was added. The flask was heated to 110°C and was maintained at that temperature, with mixing, for 1 hour. The course of the process and the time of its completion were determined based on measurements with the use of FT-IR. Then 0.73 g (7.7 x 10 ^"4 mole) of vinyltrimethoxysilane (10% excess) was added to the reaction mixture and the process was continued for another hour while monitoring its course by FT-IR. After that time, the reaction mixture was cooled down and, at a reduced pressure, the solvent was evaporated along with any excess olefin. The product was 15.09 g viscous oil, obtained with the yield of 90%>.

Spectroscopic analysis of product

JH NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.16(s, 24H, Si(CH ₃ ) ₂ ); 0.53(t, 18H, SiCH ₂ ); 1.55 (qui, 14H,

CH ₂ ); 3.23 (t, 28H, OCH ₂ ); 3.48 (s, 9H, OCH ₃ ); 5.48 (t, 7H, CF ₂ H);

1 ³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -0.55 (Si(CH ₃ ) ₂ ); 13.60 (SiCH ₂ ); 23.30 (CH ₂ ); 50.46

(OCH ₃ ); 67.59 (OCH ₂ ); 75, 48 (OCH ₂ ); 105.66 (CF ₂ ); 108.48 (CF ₂ ); 1 1 1.26 (CF ₂ H);

115.76 (CF ₂ ) ppm.

²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 15.33 (Si(CH ₃ ) ₂ ); -107.03 (SiOSi) ppm. Example 7

Synthesis of tetrakis( {3,3,4,4,5,5,6,6,7,7,8,8,9,9, 10, 10, 10-heptadecafluorodecyl} dimethylsiloxy)-tetrakis ( {2-trimethoxysilylethyl} dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, 8.76 g (19.6 mmole) of perfluorodecene and 30 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy- rhodium complex [ {Rh^-OSiMe ₃ )(cod)} ₂ ] was added. The flask was heated to 110°C and was maintained at that temperature, with mixing, for 1 hour while monitoring the course of the process by means of FT-IR. Then 2.9 g (2.8 mmole) of vinyltrimethoxysilane (10% excess) was added to the reaction mixture and the reaction was continued for another hour with continued monitoring of its course by means of FT-IR. After the process was completed the reaction mixture was cooled down and, at a reduced pressure, the solvent was evaporated along with any excess olefin. The product was 10.41 g viscous oil, obtained with the yield of 95%.

Spectroscopic analysis

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.17(s, 24H, Si(CH ₃ ) ₂ ); 0.78(t, 8H, SiCH ₂ ); 1.28 (qui, 16H,

CH ₂ Si); 2.13 (t, 8H, CH ₂ ); 3.48 (s, 36H, OCH ₃ );

1 ³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -1.12 (Si(CH ₃ ) ₂ ); 7.21 (SiCH ₂ ); 8.99 (CH ₂ Si) 25.34 (CH ₂ );

50.34 (OCH ₃ ); 111.85 (CF ₂ ); 115.66 (CF ₃ ); 119.48 (CF ₂ )125.63 (CF ₂ ); 128.00 (CF ₂ ) ppm. ²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 15.52 (Si(CH ₃ ) ₂ ); -107.56 (SiOSi) ppm.

Example 8

Synthesis of hexakis( {3,3,4,4,5,5,6,6,7,7,8,8,9,9, 10, 10, 10-heptadecafluorodecyl} dimethyl- siloxy)-bis ( {2-trimethoxysilylethyl } dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, 13.15 g (29.5 mmole) of perfluorodecene and 30 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy- rhodium complex [ {Rh^-OSiMe ₃ )(cod)} ₂ ] was added. The flask was heated to 1 10°C and was maintained at that temperature, with mixing, for 1 hour while monitoring the course of the process by means of FT-IR. Then 1.46 g (1.4 mmole) of vinyltrimethoxysilane (10%> excess) was added to the reaction mixture and the reaction was continued for one more hour while monitoring the course of the process by means of FT-IR. After the process was completed, the reaction mixture was cooled down and, at a reduced pressure, the solvent was evaporated along with any excess olefin. The product was 11.12 g viscous oil, obtained with the yield of 94%>.

Spectroscopic analysis of product

JH NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.16(s, 24H, Si(CH ₃ ) ₂ ); 0.79(t, 4H, SiCH ₂ ); 1.27 (qui, 16H,

CH ₂ Si); 2.11 (t, 12H, CH ₂ ); 3.55 (s, 18H, OCH ₃ );

1 ³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -1.18 (Si(CH ₃ ) ₂ ); 7.20 (SiCH ₂ ); 9.29 (CH ₂ Si) 25.34 (CH ₂ );

50.91 (OCH ₃ ); 111.52 (CF ₂ ); 116.22 (CF ₃ ); 119.42 (CF ₂ ); 121.96 (CF ₂ ); 128.24 (CF ₂ ) ppm. ²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 16.00(Si(CH ₃ ) ₂ ); -107.73 (SiOSi) ppm.

Example 9

Synthesis of heptakis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluor odecyl) ({2- trimethoxysilylethyl} dimethylsiloxy)octasilsesquioxane.

A three-necked flask, equipped with a magnetic stirrer, reflux condenser and thermometer, was filled with 5 g (4.9 mmole) of octakis(dimethylsiloxy)octasilsesquioxane, 15.34 g (34.4 mmole) of perfluorodecene and 30 mL of toluene. Then 0.75 mg (2.5 x 10 ^"6 mole of Rh) of the siloxy- rhodium complex [ {Rh^-OSiMe ₃ )(cod)} ₂ ] was added. The flask was heated to 110°C and was maintained at that temperature, with mixing, for 1 hour while monitoring the course of the process by means of FT-IR. Then 0.73 g (0.77 mmole) of vinyltrimethoxysilane (10% excess) was added to the reaction mixture and the reaction was continued for one more hour while constantly monitoring the course of the process with the use of FT-IR. After the process was completed, the reaction mixture was cooled down and, at a reduced pressure the solvent was evaporated along with any excess of unreacted olefin. The product was 11.33 g of solids, obtained with a yield of 94%.

Spectroscopic analysis

^J H NMR (C ₆ D ₆ , 298K, 300 MHz) δ = 0.14(s, 24H, Si(CH ₃ ) ₂ ); 0.82(t, 2H, SiCH ₂ ); 1.31 (qui, 16H,

CH ₂ Si); 2.14 (t, 14H, CH ₂ ); 3.49 (s, 9H, OCH ₃ );

1 ³ C NMR (C ₆ D ₆ , 298K, 75.5 MHz) δ = -1.20 (Si(CH ₃ ) ₂ ); 7.46 (SiCH ₂ ); 8.98 (CH ₂ Si) 25.29 (CH ₂ );

50.32 (OCH ₃ ); 108, 78 (CF ₂ ); 111.52 (CF ₂ ); 116.51 (CF ₃ ); 119.73 (CF ₂ ); 128.00(CF ₂ ) ppm. ²⁹ Si NMR (C ₆ D ₆ , 298K, 59.6 MHz) δ = 15, 34 (Si(CH ₃ ) ₂ ); -107.16 (SiOSi) ppm.