AT509428B1 - PROCESS FOR THE PREPARATION OF POLYEDRIC SILSESQUIOXANE - Google Patents

Abstract

The present invention comprises a general process for the preparation of polyhedral silsesquioxanes. The process is characterized in that a precursor selected from the group of silanes and silsesquioxane resins for the synthesis of polyhedral silsesquioxanes in an organic solvent or in a solvent mixture is optionally added to the solution with an organic or inorganic hydrogendifluoride acid catalyst for the preparation of the polyhedral silsesquioxanes is added to a polyether and / or water, and then the resulting mixture is refluxed for between one hour and 10 days before isolating the silsesquioxanes and washing away the catalyst residues with water.

Description

Austrian Patent Office AT509 428B1 2014-09-15

Description: The subject of the present invention is a new, effective process for the preparation of polyhedral silsesquioxanes.

Polyhedral silsesquioxanes are compounds which were invented at the end of World War II and have been the subject of several original scientific publications to date: F. E. Rikowski and H. C. Marsmann, Polyhedron 1997, 16, 3357; U. Dittmar, B.J. Hendan, U. Floerke and H.C. Marsmann, J. Organometal. Chem. 1995, 489, 185, reviews: M. G. Voronkov, and V. I. Lavrent'yev, Top. Curr. Chem. 1982, 102, 199; Y. Abe, T. Gunji, Prog. Polym. Be. 2004, 29, 149; Feher, in Silicon Compounds: Silanes and Silicones, Gelest, Inc., Morrisville, PA, 2004, pp. 55-71; P. Lickiss, F. Rataboul, Adv. Organomet. Chem, 57, 1, and significant patents: R. Weidner, N. Zeller, B. Deubzer, V. Frey, US 5,047,492; J.D. Lichtenhahn, J.J. Schwab, Y.-Z. An, W. Reinerth, MCCarr, FJ Feher, R. Terroba and Q. Liu, US Pat. No. 6,972,312, 2005. Most processes for the manufacture include the use of at least one of the acid or base catalysts in the phase of Synthesis of polyhedral silsesquioxanes. When the acid processes are used for the synthesis of silsesquioxanes, they are very time consuming, even several weeks are required and moreover the work is required in very dilute solutions and usually at room temperature, therefore the utility of such synthesis for industrial purposes is very questionable , On the other hand, basic conditions are those under which polyhedral silsesquioxanes can be generated rapidly. Thus, organic bases are used, which are mostly quaternized ammonium hydroxides, or inorganic bases such as alkali metal hydroxides. The amount of bases used is quite large and also exceeds 10 mol%. In isolation, it is often necessary to remove bases by neutralization with an acid, which makes the manufacturing process more expensive. The hydrofluoric acid specifically catalyzes the condensation of the siloxane species since reactive Si-F species are formed in the reaction, which are reacted with other Si-O species, such as silano, described in E.J.A. Pope, J.D. Mackenzie, J. Non-Cryst. Solids. 1986, 87, 185, condense quickly. It has also been published that potassium fluoride is effective for the production of some silsesquioxanes; the publication M. Kozelj, B. Orel, Dalton Trans. 2008, 5072, but the co-use of the fairly expensive phase transporters is needed and the reactions described in some cases do not yield sufficiently high yields in short reaction times to easily incorporate them into industrial processes to be able to transfer.

A process for preparing block copolymers consisting of a polysiloxane unit and a polyether unit is described in EP 1 460 099 A1. The reagent used is hydrosilane (with the group Si-H) -terminated polysiloxanes on one side and OH-terminated polyethers. The polyethers in this reaction mixture play the role of a reagent used in equimolar amounts. The catalysts used are organically substituted boranes containing fluorinated organic groups.

The aim of this invention is to develop new processes for the production of polyhedral silsesquioxanes which have higher yields and are characterized by the use of novel catalytic systems which have no basic properties but will act as acids.

SUMMARY OF THE INVENTION

The invention solves this problem in that a selected from the group of silanes and silsesquioxane resins precursor for the synthesis of polyhedral silsesquioxanes is dissolved in an organic solvent or in a solvent mixture that the solution an organic or inorganic hydrogendifluoride as an acidic catalyst for the preparation of the polyhedral silsesquioxanes optionally with a polyether and / or water is added and that then the resulting mixture is refluxed for between one hour and 10 days before the silsesquioxanes isolated and the catalyst residues with 1/21 Austrian Patent Office AT509 428B1 2014- 09-15 are washed off. Advantageous developments of the invention are characterized in the subclaims.

The process involves the use of inorganic or organic hydrogendifluorides and polyethers, which has not yet been used for the preparation of polyhedral silsesquioxanes under the reflux conditions, and which gives higher yields at lower concentrations of the catalysts than some previous methods. Hydrogen difluorides are acidic catalysts, which is a significant difference to previously published methods where only basic catalysts have been used.

DESCRIPTION OF PICTURES

[0008] Image 2 [0009] Image 3 [0010] Image 4 [0011] Image 5 [0012] Image 6 [0013] Image 7 [0014] Image 8 [0015] Image 9

Scheme of the phenyl-octameric silsesquioxane molecule (Ph-T8)

Schematic representation of the most common polyhedral silsesquioxanes

The 29Si MAS NMR spectrum of Ph-T8

The MS-EI spectrum of Ph-T8

The 29Si MAS NMR spectrum of Ph-T12

The 29Si NMR spectrum of iBu-T8

The 29Si NMR spectrum of iOc-T8

The 29Si NMR spectrum of MAP-Tn

The 29Si-NMR spectrum of AP2iBu6-Tn

DETAILED DESCRIPTION OF THE INVENTION

Polyhedral silsesquioxanes are compounds composed of the network of silicon and oxygen atoms, wherein the silicon and oxygen are in the ratio 2: 3 and are arranged to form a polyhedral skeleton, and the free valence on the Silicon is substituted with an organic substituent. In many cases, the inorganic network of silicon and oxygen is not completely closed; it lacks in the Polieder the side parts - siloxane bonds and corners - silicon atoms. Most often, polyhedral silsesquioxanes have the shape of the regular prisms, in short, they are denoted by the capital letter T, which is inscribed in the lower back index with the number of silsesquioxane units. T8 thus designates the fully condensed / closed cube-like structure, composed of 8 evenly spaced silsesquioxane units. However, T12 does not usually have the shape of a regular prism, but it has the D2d symmetry. Figure 1 shows the structure of Ph-T8; and Figure 2 is a schematic representation of the most common types of polyhedral silsesquioxanes.

On the free valence of the silicon atom, however, the radical R is bound, which can be selected from the following substituents, but in no way limited only to these: alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, isobutyl , Isooctyl ...; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls ...; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl ...; substituted aryls such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenyls, hydroxyphenyls; Heteroaryls such as 2-phenyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-iso-nolyl ... substituted Heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls ...; polymeric chains, such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains ...

R can be selected arbitrarily, on a polyhedron can namely only be similar R; in this case one speaks of monofunctional polyhedral silsesquioxanes. But if different substituents on the same polyhedron, i. h., two or more are present, one speaks of polyfunctional silsesquioxanes. The multi-functionality allows for better mixing in the polymers and also the covalent bonds when at least one of the substituents is such that it can react with the polymeric environment. A typical example is the amino group which can react with isocyanate, which is a curing agent in the production of many polyurethanes. However, it is highly desirable that polyhedral silsesquioxanes also have such substituents which also impart other properties to the polymer. Particularly interesting are hydrophobic and oleophobic properties, which are achieved with long branched aliphatic chains and in particular with perfluoroalkane chains. Thus, with simultaneous substitution of the polyetheric silsesquioxane with a reactive group such as an amine group with a hydrophobic such as an isooctyl group and with an oleophobic such as a perfluorooctyl group, multifunctional silsesquioxane which binds to the polymeric matrix is obtained and the polymer simultaneously imparts hydrophobic and oleophobic properties. Thus, with the selection of suitable substituents on polyhedral silsesquioxane, multifunctional materials can be obtained which can substantially improve the properties of the polymers or solve a specific problem associated with polymers.

Analytical methods which most easily control the structure of polyhedral silsesquioxanes are silicon nuclear magnetic resonance - 29Si NMR in the solution or, if the samples are too poorly soluble, MAS magic spin spin 29 Si NMR. Chemical shifts of the differently substituted silicon atoms are at the different values. Symmetric monofunctional silsesquioxanes are expected to have a peak in the T3 range (-65 to -90 ppm) which is characteristic of each substituent. In the case of T12-D2d, two signals are obtained in the ratio 2: 1 due to the unevenness of silicon. But when it comes to multifunctional silsesquioxanes, besides the different chemical shifts due to the substitution of silicon, one also has to deal with different shifts due to the different positions of silicon in the silsesquioxane molecule, because they are different isomers. So you get many signals in the T3 range and not just a single signal, as in the case of monofunctional polyhedral silsesquioxanes.

A good indicator of the mode of connection of silicon is also the infrared spectroscopy - FTIR. In the infrared spectra, the most intense peak for the silsesquioxane skeleton can be detected at values above 1100 cm-1, without the presence of other siloxane peaks near this frequency (1060 and 1040 cm-1). The other peaks belonging to the siloxane vibrations are typical at 500, 700 and 750 cm-1.

Described are three variants of the same process for the production of polyhedral silsesquioxanes, which is based on the use of hydrogen difluoride salts. All variants, however, differ significantly from the known methods.

DESCRIPTION OF THE PROCEDURE

In the known processes for the preparation of polyhedral silsesquioxanes under reflux, bases are used, wherein the pH of their solutions is 7.1-14, but in this patent the catalyst is the hydrogendifluoride anion, which is an acid the pH of the solution of 100 mg KHF 2 in 1300 mg water, estimated with universal indicator paper, is about 3. In combination with the reaction under reflux, this procedure is significantly different than the previously published methods.

The general process for the preparation of polyhedral silsesquioxanes is characterized by dissolving the precursor for the synthesis of polyhedral silsesquioxanes in an organic solvent or solvent mixture, optionally by pre-treating the precursor and adding a polyether, an acidic catalyst for polyhedral production Silsesquioxanes to the solution, and optionally water, by refluxing the resulting mixture for a period of time, between 1 hour and 7 days, by isolating the silsesquioxanes and washing the product with water to remove the catalyst residues.

As the precursors for the preparation of silsesquioxanes, the silanes or else the already hydrolyzed silanes, ie. that is, silsesquioxane resins are used. The reactions are best carried out in solutions in an organic solvent or in a mixture of the organic solvents selected from, but not limited to: aromatic hydrocarbons, alkanes, alkenes, alkynes, heteroaromatic compounds, gasolines, fractions of naphtha, amines , Alcohols, esters and ketones. The solvent is selected mainly with regard to the solubility of the precursors in which, but it is necessary to point out that the choice of solvent often also depends on the form and purity of the product and the yield of the reaction itself.

With regard to what is used as the precursor, three variants of the method can be used, with the common characteristic that hydrogendifluorides are used as the acidic catalyst for the preparation of polyhedral silsesquioxanes. Inorganic hydrogendifluorides such as NH4HF2, LiHF2, NaHF2, KHF2, CsHF2 and organic ionic compounds where the anion is hydrogendifluoride are relatively inexpensive reagents, the advantage over other reagents such as alkali metal hydroxides being that they contain a very silicophilic hydrogendifluoride anion which crucially influences the rate of the reactions between individual silsesquioxane components and catalyzes outstandingly the production of polyhedral silsesquioxanes, and further that the dihydrogen difluorides are acids, and it is therefore impossible for the salts of the silanoate silanolates to be formed Problem is especially with the use of hydroxides, since the formation of silanolates often makes the complete condensation impossible, so that in this case also incomplete polyhedra arise during the processes. The hydrogendifluoride anion strongly attacks siloxane bonds of all types and cleaves them, which can also be seen from the fact that the solutions of hydrogendifluoride even eat the glass. Therefore, only a very small amount of catalyst should be added - typically below 25 mol%, in particularly favorable situations even less than 1 mol%.

Since the solubility of inorganic fluorides and hydrogendifluorides in organic solvents is low, it is necessary to prepare compounds or complexes of these compounds with organophilic groups. The best way to prepare the hydrogendifluoride solution is to dissolve in polyether reagents, such as polyethylene glycols and their derivatives, which are very inexpensive and thus particularly suitable for use in industrial processes. The polyethers complex metallic cations and thus increase the solubility of these salts in all non-polar solvents, but especially in arenes and alkanes. For particularly difficult solvents, however, it makes sense to use copolymers which, in addition to the polyether chain, also contain alkyl chains, because these increase the lipophilicity of the resulting complexes. Due to the large reactivity of this catalytic system, a smaller amount of the reagent is required and, in some cases, a shorter reaction time compared to other previously published methods. The reactions are selective in many cases, which means that only one polyhedron is formed. Therefore, the method described is still particularly suitable for the production of pure polyhedral silsesquioxanes.

The reflux time is dependent on the type of polyhedral silsesquioxanes which one wishes to produce, but this time is always longer than 1 hour and shorter than 10 days.

Polyhedral silsesquioxanes are isolated from the reaction mixture, depending on the state of matter. Solid precipitates are isolated by filtration and washing with water to remove catalyst residue and finally washed off with a volatile organic solvent in which polyhedral silsesquioxanes are not soluble, to allow them to dry faster. However, when the polyhedral silsesquioxanes are still dissolved in the solvent after the reaction, the extraction is used so that the organic phase is washed off thoroughly with water to remove the residues of the catalysts and then the organic phase is evaporated to give a product which does not contain solvents. I) As precursors for the preparation of the silsesquioxanes silanes can be used, which can be described by the general formula: R-SiX3, where X can be any group, which participate in sol-gel processes - d. h., in reactions of hydrolysis and condensation, but especially halo groups - fluoro, chloro, bromo and iodo, various alkoxy and aryloxy groups - methoxy, ethoxy, propoxy, isopropoxy, Butoxy, phenoxy, various alkylsilyl groups - trimethylsilyloxy, triethylsilyloxy, acyloxy groups such as acetoxy, and silanol groups - OH; however, the substituent R may be selected from, but in no way limited to, the following groups: hydrogen -H, alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, iso-octyl ...; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl; substituted aryls such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenyls, hydroxyphenyls; Heteroaryls such as 2-thylbenzyl, 3-thynyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl; substituted heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls; polymeric chains such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains.

If you want to use silanes, a pretreatment is required in this variant, because for this method, the already hydrolyzed silanes are particularly suitable, of course, in this process, nevertheless, an unhydrolysed silane can be used which hydrolyzed in the first stage of the process is best, under acidic conditions, since the hydrolysis proceeds fastest under these conditions. Halosilanes, alkoxysilanes and acyloxysilanes pretreated with the hydrolysis may be used, wherein the hydrolysis is catalyzed with an acid or, in the case of the halosilanes, is spontaneous. However, this step can be avoided if alkoxysilanes are used for starting silanes; this variant is described under ii).

The pretreatment of the silanes is carried out by dissolving a silane or a silane mixture, but not necessarily, in an organic solvent or in a mixture of the organic solvents selected from, but not limited to: aromatic hydrocarbons , Alkanes, alkenes, alkynes, heteroaromatic compounds, gasolines, fractions of naphtha, amines, alcohols, esters and ketones. To this mixture, while stirring, is added an appropriate amount of water and an acid as a catalyst; it is best if one or more of a molecule of hydrolyzable group comes so that a typical molar ratio of silane / water is 1: 3. The acid used as the acid catalyst is any compound which gives a pH between 0-6.9 in the aqueous solution and is selected from the group of acids containing at least HF, HCl, HBr, Hl, HNO 3, H2S04, H3P04, formic, acetic, propane, butane, salicylic, trifluoroacetic, trichloroacetic, triflic, methanesulfonic acid; so that the final concentration is from 1 M to 10 M The mixture is stirred until the hydrolysis is complete, which can be followed excellently with the use of FTIR spectroscopy. After the end of the reaction, acidic products of the hydrolysis can be removed, i. h., acids which are formed during the hydrolysis of the halosilanes; Volatile components can be evaporated and the resin is dissolved in another solvent which is more suitable for the preparation of the silsesquioxanes, which means that it tolerates better acidic conditions of the reaction; or else the cause of the replacement of the solvent is that the hydrolysis of the silanes in non-polar aprotic solvents, such as alkanes and arenes, is poor due to the biphasic system with the acidified water; or the selectivity of preparation in a nonpolar solvent is better, for example, the phenyltrimethoxysilane hydrolyzes only slowly in toluene, therefore it is more convenient to prepare the resin in alcohol or THF, but since these solvents are not suitable for the production of Ph-T8 It is necessary to evaporate these out, and to dissolve in toluene. Of course, but the reaction mixture can be used immediately without further processing. To the solution of the pretreated precursor is then added 0.01-25 mol% of catalyst for the preparation of polyhedral silsesquioxanes, which is an inorganic or organic hydrogendifluoride selected from the group of US Pat. Nos. 5,211,074 NH4HF2, LiHF2, NaHF2, KHF2, CsHF2, (Bu) 4NHF2 and a suitable amount of the linear polyether selected from, but not limited to, the following: oligoethylene glycols, polyethylene glycols, oligopropylene glycols, polypropylene glycols, Copolymers of ethylene glycol, propylene glycol and block copolymers of ethylene glycol, propylene glycol with ethene, propylene and other monomers. When organic ionic hydrogendifluorides are used, the addition of the polyether is not necessary because they are soluble in organic solvents, if only appropriately substituted. Thereafter, the mixture is heated in a suitable reactor at boiling point temperature for a period of time from 1 hour to 10 days and then the mixture is cooled and the crystalline product is filtered off or the product somehow isolated otherwise if it is not solid, especially the extraction is meant.

Ii) The simplest variant of the method is a one-pot synthesis for the production of polyhedral silsesquioxanes, which a special pretreatment, d. h., does not include a separate hydrolysis step. In this variant, precursors for the preparation of polyhedral silsesquioxanes are only trialkoxysilanes, which can be described by the general formula: R-SiX3, where X can be any alkoxy group, but especially methoxy, ethoxy, propoxy, isopropoxy, Butoxy, phenoxy; however, the substituent R may be selected from, but in no way limited to, the following groups: hydrogen -H, alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, iso-octyl ...; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl; substituted aryls such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenyls, hydroxyphenyls; Heteroaryls such as 2-thylbenzyl, 3-thynyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl; substituted heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls; polymeric chains such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains.

From the precursor or from a mixture of the precursors, d. a trialkoxysilane or a mixture of the trialkoxysilanes is, but is not limited to, a suitable solvent selected from the following organic solvents such as: aromatic hydrocarbons, alkanes, alkenes, alkynes, heteroaromatic compounds, gasolines, Fractions of naphtha, amines, alcohols, esters, lactones, amides, lactams and ketones, prepared a suitably concentrated solution which is 0.001M to 3M. To this solution is added 0.01-25 mol% of an acidic catalyst for the preparation of polyhedral silsesquioxanes, which in this case is an inorganic or organic hydrogendifluoride selected from the following, but not limited to: NH4HF2, LiHF2, NaHF2, KHF2, CsHF2, (Bu) 4NHF2 and a suitable amount of a linear polyether selected from, but not limited to: oligoethylene glycols, polyethylene glycols, oligopropylene glycols, polypropylene glycols, copolymers of ethylene glycol, propylene glycol and block copolymers of ethylene glycol, propylene glycol with Athens, propylene and other monomers. When organic ionic hydrogendifluorides are used, the addition of the polyether is not necessary because they are soluble in organic solvents, if only appropriately substituted. An appropriate amount of water is also added such that an alkoxy group will have between 0.1 to 10 equivalents of water, but more preferably one equivalent of water to an alkoxy group. The mixture is stirred, and since the catalysts for the production of polyhedral silsesquioxanes are acidic, the hydrolysis proceeds first, such a mixture is stirred for a correspondingly long time, from 1 minute to 48 hours at room temperature; then the mixture is heated to boiling and the resulting mixture is refluxed for a period of time between 1 hour and 10 days. The silsesquioxanes are isolated by a suitable method and the product is washed off with water to remove the catalyst residues.

The residues of the hydrogendifluorides are simply washed away from the products with water, since the hydrogendifluorides are perfectly soluble in water; but for better drying of the product it is good to wash it off with a volatile organic solvent, preferably methanol.

Iii) The third variant of the production of polyhedral silsesquioxanes is their preparation from the isolated silsesquioxane resins, which can be obtained from other manufacturers. One such example is a phenyl silsesquioxane resin. For the synthesis of the polyfunctional silsesquioxanes it is also possible to use a plurality of differently substituted resins, which are mixed in the solution before the reaction. When using the silsesquioxane resins for the precursors, pretreatment is not required.

The silsesquioxane resin can be represented by the following general formula: (R-SiO3 / 2) mx (R-SiO (OH)) n x (R-Si01 / 2 (0H) 2) p.

The designation of the individual moiety: T3 T2 T1 wherein R is any radical selected from the following groups, but in no way limited thereto: hydrogen -H, alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, Isobutyl, isooctyl; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl; substituted aryls such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenyls, hydroxyphenyls; Heteroaryls such as 2-thylbenzyl, 3-thynyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl; substituted heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls; polymeric chains such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains. Only one residue may be present, but different residues may be present in the same resin, m, n, p are natural numbers, where m > n > p and m is usually greater than 10. If n = p = 0, then one speaks about the fully condensed system, the 29Si NMR spectrum shows only signals in the T3 range, but are usually also present T2 and possibly T1 in one much lower proportion.

For the preparation of polyhedral silsesquioxanes is in a suitable solvent, selected from the following organic solvents, but not limited thereto, such as: aromatic hydrocarbons, alkanes, alkenes, alkynes, heteroaromatic compounds, gasolines, fractions of naphtha, amines, alcohols , Esters, lactones, amides, lactams and ketones, as a precursor, a silsesquioxane resin or a mixture of the silsesquioxane resins dissolved so that the concentration of the resin with respect to a silsesquioxane unit is from 0.001 M to 3 M into this mixture 0.01-25 mole% catalyst for the preparation of polyhedral silsesquioxanes, which in this case is an inorganic or organic hydrogendifluoride selected from, but not limited to: NH4HF2, LiHF2, NaHF2, KHF2, CsHF2, (Bu ) 4NHF 2 and an appropriate amount of the linear polyether selected from the following group, but not limited thereto: Oligoethylene glycols, polyethylene glycols, oligopropylene glycols, polypropylene glycols, copolymers of ethylene glycol, propylene glycol and block copolymers of ethylene glycol, propylene glycol with ethene, propylene and other monomers. When organic ionic hydrogendifluorides are used, the addition of the polyether is not necessary because they are soluble in organic solvents, if only appropriately substituted. Thereafter, the mixture is heated in a suitable reactor at boiling point temperature for a period of time of 1 hour to 10 days, then the mixture is cooled and the crystalline product is filtered off or the product isolated in another way if it is not solid, which is especially the extraction is meant. The product is washed off only with water; a 7/21 Austrian Patent Office AT509 428B1 2014-09-15

Neutralization with an acid is not required, as in the case when hydroxide bases are used for the catalyst. In the filtrate, another portion of the silsesquioxane resin may be redissolved and then further refluxed, without the need for adding new catalysts, which may be a basis for a continuous process of producing polyhedral silsesquioxanes. Some reactions are selective, which means that only one type of product is obtained, but the situation where a mixture of products is obtained is more common. However, the mixture of polyhedral products is also suitable for use in polymeric systems.

Example 1 Preparation of the phenyl silsesquioxane resin from phenyltrichlorosilane 505 g of PhSiCl 3 and 1 liter of toluene are mixed in a 2 liter 1-necked flask, into which mixture 150 ml of water are added within two hours which requires much attention, since the reaction produces gaseous HCl, which must be removed in a safe manner, preferably with the introduction into a lime suspension in the water. The mixture is then stirred for a day, then washed with 3 x 200 ml of water, evaporated, and the residue is a friable transparent to white substance.

The preparation of Ph-T8 In the solution of the phenyl silsesquioxane resin, prepared according to Example 1, in 1.8 l of toluene, 10 g of KHF 2 and 10 g of PEG 400 are added, the mixture is added under strong Stirred for 40 hours and then cooled, the fine crystalline precipitate of Ph-T8 is filtered off and washed with toluene, water and methanol and dried. The filtrate is concentrated to one third of the starting volume and refluxed again for 24 hours and refiltered. In the first fraction 220 g of the product is obtained, which is 71%, in the second but still 65 g, which together 285 g of Ph-T8, d. h., 92%. The 29Si-MAS NMR spectrum shows a single peak at -77.7 ppm, which can also be seen in Figure 3. The mass spectrum shows a molecular peak at about 1032 amu, Figure 4.

Example 2 Preparation of Ph-T12 400 g of phenyltrimethoxysilane are weighed into a 2 liter flask, the flask is supplemented with THF and 108 g of water and 10 drops of concentrated sulfuric acid are added, and the mixture is stirred overnight and the next morning 10g of KHF2 and 10g of PEG 300 are added and all together refluxed for 2 days. The mixture is cooled, the fine crystalline precipitate of Ph-T12 filtered off, washed with fresh THF, water and methanol and dried at 150 ° C for 15 h. The filtrate is concentrated to one third and refluxed again for one day and filtered off. In the first fraction 170 g of the product (66%) are obtained, in the second but still 47 g, together 217 g of Ph-T12, which is 84%. The 29Si-MAS NMR spectrum shows two peaks at -77.1 ppm and -80.3 ppm, Figure 5.

Example 3 Production of Ph-T8 from the Commercially Available Silsesquioxane Resin 69 g of the commercially available phenyl silsesquioxane resin (Wacker) are weighed into a 250 ml flask, 230 ml of toluene are poured over; the resin is dissolved with stirring, 1 g of KHF 2 and 1 g of PEG 400 are added and refluxed for 30 hours, then the mixture is cooled, the fine crystalline precipitate of Ph-T8 is filtered off and washed with toluene, water and methanol and dried. The filtrate can be concentrated to one third of the starting volume and refluxed again for 24 h and then filtered again. In the first fraction 50 g of product are obtained, which is over 72%. The crystals show the same properties as in the embodiment 1. This experiment demonstrates the great utility of this method of synthesis and the availability of cheaper and safer raw materials for the production of polyhedral silsesquioxanes. Example 4 Preparation of iBu-T8 178 g of isobutyltrimethoxysilane are weighed into a 1 l flask, the flask is supplemented with THF, 55 g of water and 1 ml of acetic acid are added, the mixture is stirred overnight; the next morning, 5 g of NaHF 2 and 5 g of PEG 300 are added and all together is refluxed for 1 day. The mixture is cooled, large crystals of iBu-T8 are filtered off, washed with fresh THF, water and methanol and dried. The filtrate is concentrated to one third and refluxed again for one day and filtered off. In the first fraction, 45 g of the product and in the second still 18 g are obtained, together 63 g of iBu-T8, which is 60%. The 29Si NMR spectrum in CDCI3 shows a single peak at -67.9 ppm, Figure 6.

Exemplary Embodiment 5 Production of iOc-T8 23.4 g of isooctyltrimethoxysilane are weighed into a 100 ml flask, the flask is supplemented with THF, 5.4 g of water in which 0.5 g of KHF 2 and 0.5 g of PEG 550 monomethyl ether are dissolved is added. The mixture immediately becomes cloudy, at room temperature it is stirred for 2 h and then heated at the temperature of intensive reflux for 24 h. The mixture is evaporated and extracted from the system dichloromethane / water, the organic phase is dried with sodium sulfate and evaporated. Remaining 13.7 g (83% of 16.5 g) of the viscous colorless oil, which has a silsesquioxane peak in 29Si NMR in chloroform at - 68.2 ppm, Figure 7.

Example 6 Preparation of the mixture of HeD-T8 and HeD-T 10 Into a 100 ml flask are weighed 17.34 g of Heksadecyltrimethoxysilane, the flask is supplemented with THF, 5.4 g of water, 0.5 g of NaHF 2 and 0.5 g of PEG are added and stirred at room temperature for 2 h, then heated at the temperature of the intensive reflux for 36 h. After the reaction has ended, the mixture is evaporated, leaving 26.2 g (92% of 28.45 g) of the white brittle solid, which is washed off with water. Two silsesquioxane peaks were observed in 29Si NMR of the mixture for T8 at -66.6 ppm and about two times greater for T10 at -68.7 ppm.

Example 7 Preparation of MAP-Tn Into a 250 ml flask, weigh 31 g of (3-metacryloxy) propyltrimethoxysilane, dissolve in 200 ml of THF, add 6 g of water and one drop of 68% HNO 3 , It is stirred for one hour, and then added to 0.5 g of KHF2 and 1 g of tetraethylene glycol. It is refluxed overnight, and the following morning a viscous oil is isolated in which T8 (-66.4 ppm) and T10 (-68.4 ppm) predominate, but also contains T12 (-66.1 and -70.71) ppm), Figure 8.

Embodiment 8 The Preparation of Ap2iBu6-Tn In a 250 ml flask, weigh 26 g of isobutyltrimethoxysilane and 8.75 g of 3-aminopropyltrimethoxysilane, dissolve in THF, add 8 g of water and 1 drop of acetic acid the mixture is stirred for two hours, then 0.5 g of KHF 2 and 0.5 g of PEG 400 are added and refluxed for 24 hours; the mixture is cooled and the THF evaporated. The product is a lubricious substance. In 29Si NMR, there are a variety of narrow peaks in the T3 region, indicating complete condensation in the polyhedral products. Weigh out the isomers with 8-10 silsesquioxane units, Figure 9. Example 9 Preparation of Ap2pFOc2iOc4-Tn. The preparation of Ap2pFOc2iOc4-Tn [0068] 3 , 58 g of 3-aminopropyltrimethoxysilane, 10.20 g of (1H, 1H, 2H, 2H) perfluorooctyltriethoxysilane and 9.36 g of isooctyltrimethoxysilane weighed and dissolved in THF with 0.5 g of PEG 400; then the solution of 0.5 g of KHF 2 in 4 g of water and 3 g of EtOH is added, and it is refluxed for 24 h; the mixture is cooled and THF evaporated. The product is a colorless, very viscous oil. In 29Si NMR, there are a variety of narrow peaks in the T3 region, with the most intense peak at -68 ppm, indicating complete condensation in the polyhedral products.

The process for the preparation of polyhedral silsesquioxanes is thus characterized by the dissolution of a precursor for the synthesis of polyhedral silsesquioxanes in an organic solvent or in a solvent mixture, optionally by the pre-treatment of the precursor in the solution and by the addition of a polyether, an acidic Catalyst for the production of polyhedral silsesquioxanes, optionally water, by refluxing the resulting mixture for a specific time, between 1 hour and 10 days, isolating the silsesquioxanes and washing the product with water to remove the catalyst residues. The dissolution of a silane or a mixture of the silanes, as the precursor for the production of polyhedral silsesquioxanes, proceeds in an organic solvent or in a solvent mixture, by the pretreatment; d. h., the addition of water and optionally an acid catalyst to this mixture, by stirring the resulting mixture until the hydrolysis of the silane, by the elimination, optionally, the acidic products of the hydrolysis; and by the addition of a polyether and the catalyst for the production of polyhedral silsesquioxanes, refluxing the resulting mixture for a period of between 1 hour and 10 days, isolating the silsesquioxanes and washing the product with water to remove the catalyst residues. Dissolution of a trialkoxysilane or a mixture of trialkoxylans, as the precursors for the preparation of polyhedral silsesquioxanes, proceeds in an organic solvent or in a solvent mixture, by the addition of a polyether, an acidic catalyst for the preparation of polyhedral silsesquioxanes and water to this mixture, by stirring the resulting mixture until hydrolysis of the silane and refluxing the resulting mixture for a period of time, between 1 hour and 10 days, isolating the silsesquioxanes and washing the product with water to remove the catalyst residues. The dissolution of a silsesquioxane resin or a mixture of the silsesquioxane resins, as the precursor for the production of polyhedral silsesquioxanes, proceeds in an organic solvent or in a solvent mixture, without pretreatment, and by the addition of a polyether and an acid catalyst for the production of polyhedral Silsesquioxanes, without adding water, by refluxing the resulting mixture for a period of time, between 1 hour and 10 days, isolating the silsesquioxanes and washing the product with water to remove the catalyst residues. The silane is selected from the group of compounds, but is not limited to those which can be described by the general formula: R-SiX 3, where X may be any group which can be used in sol-gel processes - i. h., may participate in the reactions of hydrolysis and condensation, but especially the halo groups - fluoro, chloro, bromo and iodo, various alkoxy and aryloxy groups - methoxy, ethoxy, propoxy, isopropoxy -, butoxy, phenoxy, various alkylsilyl groups - trimethylsilyloxy, triethylsilyloxy, acyloxy groups, such as acetoxy, and silanol groups - OH; however, the substituent R may be selected from, but in no way limited to, the following groups: hydrogen -H, alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl; substituted aryls, such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenols, hydroxyphenyls; Heteroaryls such as 2-thylbenzyl, 3-thynyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl; substituted heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls; polymeric chains such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains. The trialkoxysilane is selected from but not limited to the group of compounds which can be described by the general formula: R-SiX 3 where X may be any alkoxy group, but especially methoxy, ethoxy, propoxy , Isopropoxy, butoxy; however, the substituent R may be selected from, but in no way limited to, the following groups: hydrogen -H, alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl; substituted aryls such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenyls, hydroxyphenyls; Heteroaryls such as 2-thylbenzyl, 3-thynyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl; substituted heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls; polymeric chains such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains. A silsesquioxane resin is used, which can be described by the following general formula: (R-SiO3 / 2) mx (R-SiO (OH)) nx (R-Si01 / 2 (0H) 2) p, wherein R is any radical or radicals in a particular ratio, all of which are selected from, but in no way limited to: hydrogen -H, alkyls such as: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl ; substituted alkyls such as: 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, perfluoroalkyls; Aryls such as phenyl, benzyl, 1-naphthyl, 2-naphthyl; substituted aryls such as: tolyl, dimethylphenyls, trimethylphenyls, aminophenyls, hydroxyphenyls; Heteroaryls such as 2-thylbenzyl, 3-thynyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl; substituted heteroaryls such as aminopyridyl, nitropyridyls, hydroxypyridyls, halopyridyls; polymeric chains such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains; m, n, p are natural numbers, where m > n > p. Organic solvents or mixtures of solvents are used selected from, but not limited to: aromatic hydrocarbons, alkanes, alkenes, alkynes, heteroaromatic compounds, gasolines, fractions of naphtha, amines, alcohols, esters, lactones, amides, lactams, ketones. The polyethers are selected from, but not limited to, the following: oligoethylene glycols, polyethylene glycols, oligoprene glycols, polypropylene glycols, copolymers of ethylene glycol, propylene glycol, and block copolymers of ethylene glycol, propylene glycol with ethene, propylene, and other monomers. As an acidic catalyst for the production of polyhedral silsesquioxanes, an inorganic or organic hydrogendifluoride is used, selected from, but not limited to: NH4HF2, LiHF2, NaHF2, KHF2, CsHF2, (Bu) 4NHF2. 11/21

Claims (9)

Austrian Patent Office AT509 428B1 2014-09-15 1. A process for producing polyhedral silsesquioxanes, characterized in that a selected from the group of silanes and silsesquioxane resins precursor for the synthesis of polyhedral silsesquioxanes in an organic solvent or in a solvent mixture is dissolved, in that an organic or inorganic hydrogendifluoride acid catalyst is added to the solution for the preparation of the polyhedral silsesquioxanes, optionally with a polyether and / or water, and then the resulting mixture is refluxed between one hour and 10 days before the silsesquioxanes are isolated and the catalyst residues Wash off water. 2. The method according to claim 1, characterized in that the silane or a mixture of silanes as a precursor for the production of polyhedral silsesquioxanes in the solvent or in the solvent mixture by adding water and optionally an acid catalyst with stirring the resulting mixture until hydrolysis pretreated is added before after any removal of the acidic products of the hydrolysis of the polyether and the hydrogen fluoride as an acidic catalyst for the preparation of the polyhedral silsesquioxanes. 3. The method according to claim 2, characterized in that is used as a precursor for the production of polyhedral silsesquioxanes, a trialkoxysilane or a mixture of Trialkoxyla-NEN. 4. The method according to claims 1 or 2, characterized in that the silane is selected from the group of compounds having the general formula R-SiX3, wherein X is one in sol-gel processes, d. H. in the reactions of the hydrolysis and the condensation, participating group, and in particular the halo groups, namely the fluorine, chlorine, bromine and iodine as well as various alkoxy and aryloxy groups, methoxy, ethoxy, propoxy , Isopropoxy, butoxy, phenoxy, various alkylsilyl groups, namely, trimethylsilyloxy, triethylsilyloxy and acyloxy groups, such as acetoxy and silanol groups, and OH; and wherein the substituent R is hydrogen -H, an alkyl, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, a substituted alkyl, such as 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatopropyl, Perfluoroalkyls, an aryl such as phenyl, benzyl, 1-naphthyl, 2-naphthyl, a substituted aryl such as tolyl, dimethylphenyl, trimethylphenyl, aminophenyl, hydroxyphenyl, a heteroaryl such as 2-thytenyl, 3-thynyl, 2-furyl, 3 Furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl, a substituted heteroaryl such as aminopyridyl, nitropyridyl, hydroxypyridyl, halopyridyl, a polymeric chain such as polyether, polyalkene Polydialkylsiloxane, polypyrrole, polytiophene chains. 5. The method according to claim 3, characterized in that the trialkoxysilane is selected from the group having the general formula: R-SiX3, where X is an alkoxy group, in particular a methoxy, ethoxy, propoxy, isopropoxy, butoxy Group, and wherein the substituent R is hydrogen -H, an alkyl such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, a substituted alkyl such as 3-aminopropyl, 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatepropyl , Perfluoroalkyls, an aryl such as phenyl, benzyl, 1-naphthyl, 2-naphthyl, a substituted aryl such as tolyl, dimethylphenyl, trimethylphenyl, aminophenyl, hydroxyphenyl; Heteroaryl, such as 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl, a substituted heteroaryl, such as aminopyridyl, Nitropyridyl, hydroxypyridyl, halopyridyl, a polymeric chain such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene chains. 12/21 Austrian Patent Office AT509 428B1 2014-09-15 6. The method according to claim 1, characterized in that as precursors a silsesquioxane resin having the general formula (R-Si03 / 2) mx (R-SiO (OH)) nx (R-Si01 / 2 (0H) 2 ) p, wherein R comprises one or more radicals in a particular ratio selected from hydrogen -H, an alkyl such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, a substituted alkyl such as 3-aminopropyl , 3-mercaptopropyl, 3-chloropropyl, 3-isocyanatepropyl, perfluoroalkyls, an aryl such as phenyl, benzyl, 1-naphthyl, 2-naphthyl, a substituted aryl such as tolyl, dimethylphenyl, trimethylphenyl, aminophenyl, hydroxyphenyl, a heteroaryl such as 2-thienyl, thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl, 1-isoquinolyl, a substituted heteroaryl such as aminopyridyl, nitropyridyl, hydroxypyridyl, halopyridyl , and a polymeric chain, such as polyether, polyalkene, polydialkylsiloxane, polypyrrole, polytiophene, containing groups, and wherein m, n, p are natural numbers, where m &gt; n &gt; p, and where m <= 10000. 7. The method according to any one of claims 1 to 6, characterized in that are used as the polyether oligoethylene glycol, polyethylene glycol, oligopropylene, polypropylene glycol and copolymers of ethylene glycol and propylene glycol and block copolymers of ethylene glycol and propylene glycol with ethene, propylene and other monomers. 8. The method according to any one of claims 1 to 7, characterized in that the hydro-gendifluorid as an acidic catalyst for the production of polyhedral silsesquioxanes from a NH4HF2, LiHF2, NaHF2, KHF2, CsHF2, (Bu) 4NHF2 group is selected. 9. Polyhedral silsesquioxanes or mixtures of polyhedral silsesquioxanes prepared by a process according to any one of claims 1 to 8. Hereto 8 sheet drawings 13/21