WO2006125708A1

WO2006125708A1 - Composition comprising functionalised polyhedral oligomeric silasesquioxane and method for its production

Info

Publication number: WO2006125708A1
Application number: PCT/EP2006/061838
Authority: WO
Inventors: Adolf KÜHNLE
Original assignee: Degussa; Kuehnle Adolf
Priority date: 2005-05-27
Filing date: 2006-04-26
Publication date: 2006-11-30

Abstract

The invention relates to a method for producing a composition comprising functionalised silasesquioxane. Said method is characterised in that it uses one or more amino silanes of formula AmSiYn, which have previously been modified by an acid and one or more silanes of formula (RaXb)mSiYn, in addition to functionalised polyhedral, oligomeric silasesquioxane of formula [(RaXbA'rSiO1,5)m (RcXdA'sSiO)n], in which A' represents an amino group, ammonium group or at least one substituent comprising an amino group or ammonium group. The invention also relates to a composition comprising said functionalised polyhedral oligomeric silasesquioxane and to the use of said composition.

Description

Functionalized polyhedral oligomeric silsesquioxane containing composition and method for their

manufacturing

The invention relates to a composition comprising functionalized polyhedral oligomeric silsesquioxanes, a process for their preparation and their use.

Functionalized polyhedral oligomeric silsesquioxanes can be used to synthesize and modify polymers in a wide range of applications. The resulting polymers can be used, for example, in coatings, adhesives, plastic moldings, fibers or in packaging materials. In this way, the properties of these polymers can be influenced over a wide range. Numerous thermal and mechanical properties of polymers, such as different moduli, temperature stability, adhesion properties to a variety of materials, oxidation stability, scratch and tear resistance, can be improved by blending, grafting, grafting, copolymerization or copolycondensation with functionalized polyhedral oligomeric silsesquioxanes.

Lichtenhan et al. describe in US 5,484,867; Comments Inorg. Chem. 17 (1995), 115-130; Macromolecules 29

(1996), 7302-7304 and in Macromolecules 28 (1995), 8435-8437 the synthesis of functionalized polyhedral oligomeric silsesquioxanes according to structure 1 by "corner capping" of the respective trisilanol precursor according to structure 2 with trichlorosilanes, such as XSiCl ₃ , using an amine as the base, whereby via the functional group X of the trichlorosilane silanol, silane, acrylic, olefin, epoxide, halogen, alcohol, amine or Isocyanate groups are introduced into the polyhedral oligomeric silsesquioxane.

WO 03/064490 also describes a process for the preparation of functionalized polyhedral oligomeric silsesquioxanes by "corner capping", however, using alkoxysilanes, which in terms of

Production and the cost of production represent an attractive option.

It was therefore an object of the present invention to provide an efficient process which enables the production of functionalized polyhedral oligomeric silsesquioxanes in a one-step reaction. In particular, it was of interest to dispense with a use of bases, since these must be separated in a subsequent process step. Furthermore, the method according to the invention should make it possible to produce functionalized polyhedral oligomeric silsesquioxanes which have at least two different functional groups on the silicon-oxygen cluster.

Surprisingly, it has been found that the inventive method, the preparation of a

Composition, the functionalized polyhedral having oligomeric silsesquioxanes, made possible in only one process step, without that in a subsequent process step, the base has to be removed from the product mixture. In the process according to the invention, this is achieved by reacting the silanes used, where at least one of the silanes used is an aminosilane, at a neutral to acidic pH without the use of a basic catalyst to give the desired functionalized polyhedral oligomeric silsesquioxanes. The process according to the invention is carried out using an acid, and it must be ensured in the case of the silanes used that the rate constants of the silanes and modified aminosilanes used in the reaction to the functionalized polyhedral oligomeric silsesquioxanes are of the same order of magnitude. Furthermore, the process according to the invention has the advantage that it is possible to dispense with the preparation of an incompletely condensed polyhedral oligomeric silsesquioxane as intermediate in the preparation of functionalized polyhedral oligomeric silsesquioxanes. For the preparation of these incompletely condensed polyhedral oligomeric silsesquioxanes large amounts of base are necessary, for example, this is necessary for a process according to the prior art about 10 wt .-% of lithium hydroxide based on the silane used, further then neutralization with corresponding large amount of acid necessary. The functionalized polyhedral oligomeric silsesquioxanes prepared by the process according to the invention are distinguished by their ionic character, which is why they are generally soluble in protic solvents, such as, for example, water or alcohols. In addition to the substituents which have the ionic group, the cages of the functionalized polyhedral oligomeric silsesquioxanes may contain further substituents with functional groups, such as for example, methacrylic and / or epoxy groups. By the presence of these further functional groups in the functionalized polyhedral oligomeric silsesquioxanes, these products can be converted into further interesting functionalized polyhedral oligomeric silsesquioxanes. In accordance with the process of the invention, functionalized polyhedral oligomeric silsesquioxanes having tailor-made properties can now be prepared, which in turn make it possible to produce catalysts, ceramic compositions and polymers having particular properties, for example hydrophobicity, increased hardness or increased scratch resistance. The solution of the problem was all the more surprising, especially since it was found that an increased compatibility of the functionalized polyhedral oligomeric silsesquioxanes according to the invention in ceramic compositions, polymers or solvent systems can be observed. Furthermore, it has been shown that the functionalized polyhedral oligomeric silsesquioxanes prepared according to the process of the invention have a lower reactivity and, associated therewith, a higher stability than completely functionalized polyhedral oligomeric silsesquioxanes according to structure 3. Fully functionalized polyhedral oligomeric silsesquioxanes according to structure 3 with X =

Methacrylic group are highly reactive and usually do not have the desired stability.

The present invention therefore provides a process for the preparation of a composition comprising functionalized polyhedral oligomeric silsesquioxanes, which is characterized in that

I. one or more aminosilanes according to the formula A _1n SiY _n , which are previously modified with an acid, and

II. One or more silanes according to the formula (R ₃ Xb) mSiY _n

with a, b = 0, 1; m, n = 1, 2 or 3; a + b = 1 and m + n = 4,

A = amino or at least one amino group-containing substituents of the R type,

R, R ^f = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, which are each substituted or unsubstituted,

X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl blocked, isocyanate, acrylate, methacrylate, mercapto, nitrile, phosphine group or at least one such type X substituent of type R,

Y = OH, ONa, OK, OR \ OCOR \ OSiR ^Λ ₃ , Cl, Br, I or NR ^Λ ₂ ,

wherein both the substituents of the type R, type R ^f and type A and the type X are the same or different and the rate constants of the modified aminosilanes and silanes used in the reaction to form functionalized polyhedral oligomeric silsesquioxanes in the same order are used. Likewise, subject of the present invention are functionalized polyhedral oligomeric silsesquioxanes according to the formula

[(R _a X _b A ' _r Si0i, ₅ ) m (R ₀ XdA' _s SiO) _n ] with:

a, b, c, r = 0-1; d, s = 0-2;

m + n + o + p = 4-14; a + b + r = 1; c + d + s = 2; r + s> 1

R = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, which are each substituted or unsubstituted,

X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl blocked isocyanate,

Acrylate, methacrylate, mercapto, nitrile, phosphine or at least one such type X substituent of type R,

A '= amino, ammonium or at least one amino or ammonium group-containing substituents of type R,

wherein both the substituents of type R and type A 'and of type X are the same or different and have at least one substituent of type A', and a composition comprising these functionalized polyhedral oligomeric silsesquioxanes.

The invention further relates to the use of the composition according to the invention or the silsesquioxanes according to the invention for the synthesis of catalysts and their starting compounds, for stabilizers and for the synthesis or modification of ceramic compositions and polymers. The inventive method for producing a composition having functionalized polyhedral oligomeric silsesquioxanes, characterized in that

II. One or more silanes according to the formula (R ₃ Xb) mSiY _n

with a, b = 0, 1; m, n = 1, 2 or 3; a + b = 1 and m + n = 4,

A = amino or at least one amino group-containing substituents of the R type,

Y = OH, ONa, OK, OR \ OCOR \ OSiR ^Λ ₃ , Cl, Br, I or NR ^Λ ₂ ,

wherein both the substituents of the type R, type R ^f and type A and the type X are the same or different and the rate constants of the modified aminosilanes and silanes used in the reaction to form functionalized polyhedral oligomeric silsesquioxanes in the same order are used. It is important for the process according to the invention that the silanes used as starting material and modified aminosilanes are matched in terms of their saponification rate, this means that the rate constants are related to the saponification reaction of the silane and the modified aminosilanes in a similar order. In this way it can be achieved that the functionalized polyhedral oligomeric silsesquioxanes have a substituent distribution in accordance with the educt composition of the silanes. If, for example, the aminosilane ASiY ₃ and the silane RSiY _{3 are used} in a molar mixing ratio of 1: 1 in the process according to the invention, the result is a composition which predominantly contains a functionalized, fully condensed polyhedral oligomeric silsesquioxane type A ₄ R ₄ Si ₈ θi2. In different

Parts by weight, but in parts by weight less than the Silsesquioxan type A ₄ R ₄ SisOi2, the composition also silsesquioxanes of the type A ₃ R ₅ Si _S Oi ₂ , A ₂ R6Sis0i2, A ₅ R ₃ Si8θi2 and A ₆ R ₂ SiSOi ₂ on , Information on the rate constants regarding the

Saponification reactions of various trialkoxysilanes are reported in Z. Naturforsch. 54 b (1999), 155-164, so that the pH during the course of the reaction exerts an influence on the reaction rate.

In the method according to the invention are silanes according to the formula

(R _a X _b ) _m SiY _n

with: a, b = 0, 1; m, n = 1, 2 or 3;

a + b = 1 and m + n = 4,

in which R, R ^f = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, which are each substituted or unsubstituted,

Y = OH, ONa, OK, OR \ OCOR \ OSiR ^Λ ₃ , Cl, Br, I or NR ^Λ ₂ and

wherein the substituents of the type R, type R ^f , type X and type Y are the same or different, used. Silanes are preferably used, the substituents of Y is selected from OH, OR comprise \ ^Λ OCOR or Cl.

Alkoxysilanes according to the formula are particularly preferred in the process according to the invention

with: a, b = 0, 1; m, n = 1, 2 or 3;

a + b = 1 and m + n = 4,

in which:

R, R ^f = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, which are each substituted or unsubstituted, X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl blocked, isocyanate, acrylate, methacrylate, mercapto, nitrile, phosphine group or at least one such type X substituent of type R,

used. Here, the substituents of the type R, R ^f and X may be the same or different.

For the purposes of this invention is the term

"Substituted" in the definition of the substituents of the type R and R 'understood that the substituents of the type R or R' in turn may be substituted by substituents of the type R or R '.

Trialkoxysilanes, in particular alkyltrialkoxysilanes RSi (OR ') _3, are particularly preferably used, the alkoxy group (OR') having from 1 to 4 carbon atoms, in particular methoxy or ethoxy group, and the alkyl group (R) having from 1 to 5 carbon atoms, in particular from 2 to 4 carbon atoms, but preferably has 3 carbon atoms. Examples of alkyltrialkoxysilanes of the formula RSi (OR ') ₃ are isobutyltrimethoxysilane (DYNASYLAN ^® IBTMO), isobutyltriethoxysilane, propyltrimethoxysilane (Dynasylan ^® PTMO) propyltriethoxysilane,

Ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane (DYNASYLAN ^® MTMS) or methyltriethoxysilane. In the process according to the invention it is also possible to use trialkoxysilanes having a substituent of the type X according to the formula XSi (OR ') ₃ , such as, for example, 3-chloropropyltrimethoxysilane (CPTMO), 3

Glycidyloxypropyltrimethoxysilane (DYNASYLAN ^® GLYMO), 3- mercaptopropyltrimethoxysilane (DYNASYLAN ^® MTMO), 3-methacryloxypropyltrimethoxysilane (DYNASYLAN ^® MEMO) are used. In a particular embodiment Alkenyltrialkoxysilanes such as vinyltrimethoxysilane (DYNASYLAN ^® VTMO) or vinyltriethoxysilane be used. For the preparation of functionalized polyhedral, oligomeric silsesquioxanes for hydrophobing, for example polymers, preferably fluoroalkyltrialkoxysilanes, preferably fluoroalkyltrialkoxysilanes according to the formula CF ₃ ((CF ₂ ) _o (CH ₂ ) p) Si (OR ') ₃ with o, p = 0-12, for example, 3,3,4,4,5,5,6,6,7,7,8,8,8- Trifluoroktyltriethoxysilan (DYNASYLAN ^® F 8261) was used as is.

In the method according to the invention is at least one aminosilane according to the formula

A _m oil Y _n

with: m, n = 1, 2 or 3;

m + n = 4,

in which

R, R '= hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, which are each substituted or unsubstituted,

A = amino or at least one amino group-containing substituents of the R type,

Y = OH, ONa, OK, OR \ OCOR \ OSiR ^Λ ₃ , Cl, Br or I

used, preferably aminosilanes are used which have substituents of the type Y selected from OH, OR \ OCOR ^Λ or Cl. Particularly preferred in the process according to the invention are aminosilanes according to the formula

A _m Si (OR ') _n

used. Here, the substituents of the type R ^f may be the same or different. Very particular preference is given to using aminosilanes in the process according to the invention as aminoalkyltrialkoxysilanes, the substituent of type A preferably having the amino group in the terminal position, the alkyl and alkoxy groups having from 1 to 10 carbon atoms, preferably from 2 to 5 carbon atoms and preferably from 3 have up to 4 carbon atoms. In a preferred embodiment, 3-aminopropyltriethoxysilane is used in the process according to the invention. The amino group may be a primary, secondary or tertiary amino group.

For the preparation of functionalized polyhedral oligomeric silsesquioxanes which have both substituents of the R, X and A ^f types on the silicon-oxygen cluster, one or more aminosilanes are first reacted with an acid and then the silanes of the formula (R ₃ Xb) mSiY _n was added to the reaction mixture. Here are preferably alkyltrialkoxysilanes according to the formula

RSi (OR ') ₃ together with aminotrialkoxysilanes ASi (OR') ₃ , wherein the substituent of type R is in particular an unsubstituted alkyl group. Particular preference is given to using three different silanes, selected from silanes according to the formula XSi (OR ') ₃ , an aminotrialkoxysilane ASi (OR') ₃ and a silane according to the formula RSi (OR ') ₃ . In this way one obtains functionalized polyhedral oligomeric silsesquioxanes with the substituents of the type X, R and A '. The The inventive method is thus suitable for the preparation of functionalized polyhedral oligomeric silsesquioxanes with one or more different types of substituents of type X in addition to the substituent of type A ^f .

XSi (OR ') 3 + ASi (OR') 3 + RSi (OR ') ₃ -> [(R _a X _b A' _r Si0i, ₅ ) m (R _c X _d A ' _s Si0) _n ]

In a further embodiment, in particular halosilanes, preferably trichlorosilanes, are used together with alkoxysilanes in the process according to the invention.

The process according to the invention is preferably carried out at a pH of from 3 to 11, preferably at a pH of from 4 to 9, particularly preferably from 5.5 to 8.5. In a particular embodiment of the process according to the invention, this is carried out at a pH of 7 + 0.3.

In the first process substep of the invention

Procedure, the aminosilane used is modified with an acid, these may be mono- or poly-protic acids. As acid here can be used both inorganic acids and their derivatives, selected from hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid or carbonic acid, as well as mono- or polyprotic organic acids. In particular, saturated and unsaturated alkyl, aryl and alkylaryl acid and their derivatives can be used as acids in the process according to the invention. However, preference is given in the process according to the invention to formic acid, acetic acid, acrylic acid, methacrylic acid, palmitic acid, stearic acid, oleic acid, maleic acid, adipic acid, lauric acid, dodecanedioic acid, benzoic acid, Salicylic acid or its derivatives used. In a particular embodiment of the method according to the invention are acids which have a stabilizing effect for plastics, such as 3, 5-di-tert. Butyl-4-hydroxybenzoic acid or 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid used.

The inventive method for the conversion of aminosilanes and silanes to functionalized polyhedral oligomeric silsesquioxanes is preferably carried out in solution. As solvents both a polar and a nonpolar solvent can be used. The solvents used are preferably halogen-free solvents selected from the group of alcohols, ketones, aldehydes, ethers, acids, esters, anhydrides, alkanes, aromatics and / or nitriles or else a mixture of these solvents. Alcohols, ethers, acetone, acetonitrile, benzene or toluene are particularly preferably used as solvent. Very particular preference is given to using acetone, methanol or ethanol or a mixture of two or more of these compounds as solvent.

In a particular embodiment of the process according to the invention, the reaction of the silanes is carried out in the presence of water. In this case, water is added to the reaction mixture or the educt composition.

In the first process step, the aminosilane used is modified with an acid. The molar ratio of the aminosilanes to the acid is preferably to be selected such that per one primary, secondary or tertiary amino group of 0.5 to 1.5 molar equivalents of a monoprotic acid are available, but preferably 1 molar equivalent of a monoprotic acid is added. When using polyaminosilanes or mehrprotonigen Acids or organic acids with multiple acid functions, the molar ratio should be chosen so that the amino groups of aminosilane are completely neutralized.

If the process according to the invention is carried out in solution, the initial concentration of all silanes according to the formulas (R _a X _b ) m SiY _n and A _1n SiY _n in the solution is preferably from 0.01 mol / 1 to 10 mol / l, preferably from 0 , 1 mol / 1 to 6 mol / 1, more preferably from 0.3 mol / 1 to 4 mol / 1.

The reaction of the silanes and modified aminosilanes in the present process is preferably conducted at a temperature from 0 to 200 ⁰ C, preferably at a temperature of 10 to 150 ⁰ C, particularly preferably at a temperature of 20 to 100 ⁰ C. Most preferably, this reaction of the silanes is carried out at a temperature of 40 to 80 oC. In a particular embodiment of the method according to the invention, the temperature over the entire reaction time is not kept constant, it is for example advantageous to lower the reaction temperature towards the end of the reaction time in order to be able to completely isolate the functionalized polyhedral oligomeric silsesquioxanes as possible.

The process according to the invention can be carried out continuously or batchwise, the reaction of the silanes to give functionalized polyhedral oligomeric silsesquioxanes in a one-step reaction.

The reaction of the silanes into functionalized polyhedral oligomeric silsesquioxanes is preferably carried out in the process according to the invention by adding the aminosilane A _1n SiY _n or else several aminosilanes

Solvents. This is followed by the addition of the acid. Only in the next process step, the addition of the further silanes according to the formula (R ₃ X _b ) mSiY _n to the reaction mixture. After adding the components though even before that, care should be taken to ensure that the components in the reaction mixture are thoroughly mixed. This can be done in a manner known to those skilled in the art, for example by stirring or by generating turbulent flows.

After the end of the reaction of the silanes to the functionalized polyhedral oligomeric silsesquioxanes in the process according to the invention, the target product can be separated from the reaction mixture in a manner known to the person skilled in the art. Preferably, by a thermal separation process such as distillation, the solvent or solvent mixture can be separated from the desired composition of functionalized polyhedral oligomeric silsesquioxanes.

The inventive method is particularly suitable for the preparation of a composition of functionalized polyhedral oligomeric silsesquioxanes, which understood in the context of this invention under silsesquioxanes both fully condensed and incompletely condensed silsesquioxanes.

Silsesquioxanes are oligomeric or polymeric substances whose fully condensed representatives have the general formula (SiC> 3 _/ 2R) n, where n> 4 and the radical R can be a hydrogen atom, but mostly an organic

Rest represents. The smallest structure of a silsesquioxane is the tetrahedron. Voronkov and Lavrent'yev (Top. Curr. Chem. 102 (1982), 199-236) describe the synthesis of fully condensed and incompletely condensed oligomeric silsesquioxanes by hydrolytic

Condensation of trifunctional RSiY ₃ ~ precursors, wherein R is a hydrocarbon radical and Y represents a hydrolyzable group, such as chloride, alkoxide or siloxide. Lichtenhan et al. describe the base-catalyzed preparation of oligomers Silsesquioxanes (WO 01/10871). Silasesquioxanes of the formula R ₈ Si ₈ Oi ₂ (with identical or different hydrocarbon radicals R) can base catalysis to form functionalized, incompletely condensed silsesquioxanes, such as R ₇ Si ₇ Og (OH) ₃ or also

R ₈ Si ₈ On (OH) ₂ and R ₈ Si ₈ Oi ₀ (OH) _{4 are} reacted (Chem. Commun. (1999), 2309-10; Polym. Mater. Sei. Eng. 82 (2000), 301- 2, WO 01/10871) and thus serve as a parent compound for a large number of different incompletely condensed and functionalized silsesquioxanes. In particular, the silsesquioxanes (trisilanols) of the formula R ₇ Si ₇ Og (OH) ₃ can be converted into correspondingly modified oligomeric silsesquioxanes by reaction with functionalized monomeric silanes (corner capping).

The composition according to the invention comprises at least one functionalized polyhedral oligomeric silsesquioxane according to the following formula:

[(R _a X _b A ' _r Si0i, ₅ ) m (R ₀ XdA' _s Si0) _n ]

With :

a, b, c, r = 0-1; d, s = 0-2;

m + n = 4-14; a + b + r = 1; c + d + s = 2; r + s> 1

X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl blocked isocyanate, Acrylate, methacrylate, mercapto, nitrile, phosphine or at least one such type X substituent of type R,

A ^f = amino, ammonium or at least one amino or ammonium group-containing substituents of type R,

wherein both the substituents of type R and type A ^f and of type X are identical or different, and having at least one substituent of type A ^f .

The composition according to the invention is preferably prepared by the process according to the invention. Preferably, the composition according to the invention comprises various functionalized polyhedral oligomeric silsesquioxanes, which are characterized in that in addition to the substituents of the type R, they also have substituents of the type A ^f and, if appropriate, also of the type X. Thus, for example, a composition according to the invention may comprise the following functionalized polyhedral, oligomeric silsesquioxanes, as shown in structures 5a, 5b and 5c:

5a 5b 5c

The composition according to the invention may also contain further functionalized polyhedral oligomeric silsesquioxanes In addition to the polyhedral, oligomeric silsesquioxanes with a T ₈ cage, functionalized polyhedral, oligomeric silsesquioxanes with a T ₄ , Tβ- _r Ti ₀ or with a Ti ₂ cage may also be present. Furthermore, silsesquioxanes with a so-called ladder structure can also be present in the composition according to the invention. Under a T _z cage of this invention is understood, only the silicon-oxygen cluster in the sense, without further consideration of the substituents ^f or example, Type X, Type A Type R, wherein n represents the number of silicon atoms in the silicon-oxygen cluster is.

In a particular embodiment of the composition according to the invention, at least one of the functionalized polyhedral oligomeric silsesquioxanes has an ammonium group or an ammonium group-containing substituent of type R, the counter anion of the ammonium group being a base of the acid 3,5-di-tert. butyl-4-hydroxybenzoic acid or 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.

The functionalized polyhedral oligomeric silsesquioxanes according to the invention have a structure according to the formula

[(R _a X _b A ' _r Si0i, ₅ ) m (R ₀ XdA' _s SiO) _n ]

With :

a, b, c, r = 0-1; d, s = 0-2;

m + n + o + p = 4-14; a + b + r = 1; c + d + s = 2; r + s> 1

wherein both the substituents of the type R and type A ^f and the type X are the same or different, and having at least one substituent of the type A ^f , on.

Preferably, the functionalized polyhedral oligomeric silsesquioxanes of the invention have an ammonium group or an ammonium group-containing substituent of type R, wherein the counter anion of the ammonium group, the base of the acid 3, 5-di-tert. butyl-4-hydroxybenzoic acid or 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.

The functionalized polyhedral, oligomeric silsesquioxanes according to the invention are preferably prepared by means of the process according to the invention or isolated from the composition according to the invention.

Many of the functionalized polyhedral oligomeric silsesquioxanes according to the invention or the compositions according to the invention have water-soluble properties in the presence of an acid and are therefore preferably suitable for the preparation of solutions or dispersions in water. These solutions or dispersions are preferably suitable for the production of coatings based on water. The compositions of the invention can be used to synthesize and modify polymers in a wide range of applications. Since, on the one hand, the substituent of the type R itself, on the other hand via a functionalization - ie on the substituents of the type X and A ^f - the character and the property of the functionalized polyhedral oligomeric silsesquioxane can be varied widely, can in this way the inventive Composition can be added to all common polymers. This can be both chemical bonding and pure blending. By adding the composition according to the invention or the silsesquioxanes according to the invention to a polymer, the rheological properties of a large number of polymers can be favorably influenced, for example the adhesive and bonding properties as well as the barrier action to gases and liquids. In particular, organic polymers selected from polyolefins, amorphous polyalphaolefins, polyethers, polyamides, copolyamides, polyamide compounds, polyesters, copolyesters, polyurethanes, polyacrylates, polymethacrylates, polycarbonates, polyurethanes, phenolic resins, epoxy resins, polysiloxanes, polysilanes, rubbers, rubber compounds, polyvinyl chloride, vinyl chloride copolymers, polystyrene , Copolymers of styrene, ABS polymers and Olefinco- and - terpolymere. In particular, by blending polymer can be modified or formed by the addition of the composition of the invention or the silsesquioxanes according to the invention to the polymers composites having the desired properties. The polymers modified in this way can be used, for example, in the form of coatings, paints, injection-molded or extruded molded parts, calendered films, lubricants, adhesives, cosmetics, pharmaceuticals, fibers, glass fibers or packaging materials. Furthermore, the compositions according to the invention for ceramic compositions, as bioactive and fungicidal products, as polymer stabilizers, for electronic materials, in aerospace and for the manufacture of medical prostheses.

In addition to this type of modification, it is also possible to apply the composition according to the invention or silsesquioxanes according to the invention to a polymer surface. As polymer additives, the effect of the inventive composition or silsesquioxanes according to the invention is that in the resulting polymers they increase the glass, decomposition and thus the use temperature, increase the tensile strength, impact strength, scratch resistance and mechanical hardness, reduce the density, the thermal conductivity, lower the thermal expansion coefficient and the dielectric constant and viscosity, change the surface tension and adhesion, decrease the flammability, flammability and heat development, increase the O ₂ permeability, increase the oxidation and corrosion stability, simplify the processing, and restrain shrinkage processes.

The compositions according to the invention or silsesquioxanes according to the invention can furthermore serve as starting compounds for catalysts. By reaction with metal compounds homogeneous and heterogeneous catalysts can be formed, which in turn can be used for oxidation, metathesis, C-C coupling reactions, oligomerizations, polymerizations, additions, reductions, eliminations, rearrangements. Preference is given to the reaction with metal compounds of metals of the subgroups, the lanthanides, actinides and the 3rd and 4th main group.

Is used in the process according to the invention as acid, an acid which is characterized by a stabilizing effect in plastics, such as 3, 5-di-tert. Butyl-4-hydroxybenzoic acid and in particular 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, the inventive compositions prepared according to the invention or functionalized polyhedral oligomeric silsesquioxanes according to the invention can be used as stabilizers for plastics. Preference is given here to compositions according to the invention which have functionalized polyhedral oligomeric silsesquioxanes with vinyl groups as substituents of the R type. Because of the vinyl group, a covalent or ionic attachment of the functionalized polyhedral oligomeric silsesquioxane to a polymer and thus the production of high molecular weight stabilizers is made possible. This high molecular weight stabilizer has the advantage that it shows no migration tendency in a plastic.

The following examples are intended to illustrate the invention

Explain method and the composition of the invention in more detail, without the invention being limited to this embodiment.

Example 1:

Synthesis of a composition (propyl) _5, ₆ (aminopropyl) 2,4SisOi2 portions

In 860 ml ethanol are mixed with 14.41 g (0.24 mol) of concentrated acetic acid with stirring at room temperature 53.04 g (0.24 mol) of 3-aminopropyltriethoxysilane (DYNASYLAN ^® AMEO). Are then added 92.01 g (0.56 mol) of propyltrimethoxysilane (Dynasylan ^® PTMO) and then 64 g of water at room temperature. The temperature is then raised to 6O ⁰ C and allowed to stir for 3 days at this temperature. After distilling off the solvent in vacuo and drying the product in a vacuum oven at 4O ⁰ C to obtain 93.9 g (yield: 99.9%) of a white, water-soluble product (acetate salt), which is in the MS- MALDI-TOF analysis (Matrix Assisted Laser

Desorption / ionization time of flight) predominantly T ₈ -, Ti ₀ - and small amounts Ti2 ~ cages reveals. The HPLC analysis shows predominantly cages which have three substituents of type A ^f , in this example amino group or ammonium acetate, but also cages having two or four substituents of type A ^f .

Example 2: Synthesis of a composition with

(Propyl) 4, ₆ (methacrylic) (aminopropyl) 2,4SisOi2 moieties

In 860 ml ethanol are mixed with 14.41 g (0.24 mol) of concentrated acetic acid with stirring at room temperature 53.04 g (0.24 mol) of 3-aminopropyltriethoxysilane (DYNASYLAN ^® AMEO). Are then added at room temperature to 75.57 g (0.46 mol) of propyltrimethoxysilane (Dynasylan ^® PTMO) and 24.83 g (0.1 mol) of 3-methacryloxypropyltrimethoxysilane (DYNASYLAN ^® MEMO), and then 64 g of water. The temperature is then raised to 6O ⁰ C and allowed to stir for 3 days at this temperature. After distilling off the solvent in vacuo and drying the product in a vacuum oven at 4O ⁰ C to obtain 101.8 g (yield: 99.2%) of a white, water-soluble product (acetate salt), in the MS-MALDI-TOF analysis (Matrix Assisted Laser Desorption / Ionization Time of Flight) shows predominantly T ₈ , Ti ₀ and small amounts of Ti2 cages. The HPLC analysis shows predominantly cages which have three substituents of type A ^f , in this example methacrylic or aminopropyl or ammonium acetate group, but also cages having two or four substituents of type A ^f . Example 3:

Synthesis of a composition with (isobutyl) 4 (aminopropyl) 4SisOi2 moieties

In 860 ml of ethanol are added under stirring at room temperature 55.25 g (0.25 mol) of 3-aminopropyltriethoxysilane (DYNASYLAN ^® AMEO). These are quickly mixed with 18.26 g (0.125 mol) of adipic acid. Are then added at room temperature 44.6 g (0.25 mol) of isobutyltrimethoxysilane (DYNASYLAN ^® IBTMO) and then 40 g of water. The temperature is then raised to 6O ⁰ C and allowed to stir for 3 days at this temperature. After distilling off the solvent in vacuo and drying the product in a vacuum oven at 4O ⁰ C to obtain 73.1 g (yield: 100%) of a white, water-soluble product (adipate salt), which in the MS-MALDI-TOF analysis (matrix Assisted Laser Desorption / Ionization Time of Flight) shows predominantly T ₆ , T ₈ , Ti ₀ and small amounts of Ti ₂ cages. The HPLC analysis shows predominantly cages which have four substituents of type A ^f , in this example aminopropyl or ammonium adipate groups, but also cages having two or four substituents of type A ^f .

Example 4:

Synthesis of a composition with (aminopropyl) siso ^ moieties

In 860 ml of ethanol are added under stirring at room temperature 176.8 g (0.8 mol) of 3-aminopropyltriethoxysilane (DYNASYLAN ^® AMEO). These are rapidly mixed with 68.87 g (0.8 mol) of methacrylic acid. Then you give in

Room temperature 64 g of water. The temperature is then raised to 6O ⁰ C and allowed to stir for 3 days at this temperature. After distilling off the solvent in vacuo and drying the product in a vacuum oven at 4O ⁰ C to obtain 156.8 g (yield: 99.9%) of a white, water-soluble product (methacrylate salt), in the MS-MALDI-TOF analysis (Matrix Assisted Laser

Desorbtion / Ionization Time of Flight) predominantly T ₆ -, T ₈ -, Ti ₀ - and small amounts of Ti ₂ cages can be seen. The HPLC analysis shows fully substituted cages with ammonium methacrylate groups as substituents of type A ^f .

Claims

claims:

A process for preparing a composition comprising functionalized silsesquioxanes, characterized in that

II. One or more silanes according to the formula (R ₃ Xb) mSiY _n

with a, b = 0, 1; m, n = 1, 2 or 3; a + b = 1 and m + n = 4,

A = amino or at least one amino group-containing substituents of the R type,

Y = OH, ONa, OK, OR \ OCOR \ OSiR ^Λ ₃ , Cl, Br, I or NR ^Λ ₂ ,

wherein both the substituents of the type R, type R ^f and type A and the type X are the same or different and the rate constants of the modified aminosilanes and silanes used in the reaction to form functionalized polyhedral oligomeric silsesquioxanes in the same order are used.

2. The method according to claim 1, characterized in that the aminosilane is modified with from 0.5 to 1.5 molar equivalents of acid.

3. The method according to claim 1 or 2, characterized in that the aminosilane with a

Substance equivalent to acid is modified.

4. The method according to at least one of claims 1 to 3, characterized in that the acid is an organic acid selected from formic acid, acetic acid, acrylic acid, methacrylic acid, palmitic acid, stearic acid, oleic acid, maleic acid, adipic acid, lauric acid, dodecanedioic acid, benzoic acid, salicylic acid and Derivatives of these acids, is used.

5. The method according to at least one of claims 1 to 4, characterized in that the reaction of the silanes and aminosilanes is carried out at a pH of the reaction solution from 3 to 11.

6. The method according to at least one of claims 1 to 5, characterized in that silanes are used according to the formula (R ₃ X _b ) mSiYn having the substituents of the type Y selected from OH, OR \ OCOR ^Λ or Cl.

7. The method according to claim 6, characterized in that silanes are used according to the formula (R ₃ Xb) mSi (OR ') n.

8. The method according to at least one of claims 1 to 7, characterized in that the reaction of the silanes and aminosilanes is carried out in solution.

9. The method according to claim 8, characterized in that the solvent is a halogen-free solvent selected from the group of alcohols, ketones, aldehydes, ethers, Acids, esters, anhydrides, alkanes, aromatics and nitriles or mixtures of these solvents, is used.

10. The method according to claim 9, characterized in that as the solvent acetone, methanol or ethanol or a

5 mixture of two or more of these solvents is used.

11. The method according to at least one of claims 1 to 10, characterized in that the reaction is carried out in the presence of water.

1012. The method according to claim 11, characterized in that the molar ratio of the sum of all silanes and aminosilanes to the water at the beginning of the reaction of 1: 100 to 100: 1.

13. The method according to at least one of claims 1 to 12, 15, characterized in that the reaction of the silanes is carried out at a temperature of ^{0 0} C to 200 ⁰ C.

14. The method according to at least one of claims 1 to 13, characterized in that the reaction in a

20 temperature below the boiling point of the solvent or solvent mixture is performed.

15. The method according to at least one of claims 1 to 14, characterized in that the sum of the concentrations of all silanes and aminosilanes in the

25 solution at the beginning of the reaction to the functionalized polyhedral oligomeric silsesquioxanes 0.01 mol / 1 to 10 mol / 1.

16. Composition, characterized in that the composition is functionalized polyhedral oligomeric

30 silsesquioxanes according to the formula

[(R _a X _b A ' _r Si0i, ₅ ) m (R ₀ XdA' _s SiO) _n ] With :

a, b, c, r = 0-1; d, s = 0-2;

m + n + o + p = 4-14; a + b + r = 1; c + d + s = 2; r + s> 1

X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl,

Alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, blocked isocyanate, acrylate, methacrylate, mercapto, nitrile, phosphine or at least one such type X substituent of type R,

A ^f = amino, ammonium or at least one

Amino- or ammonium-containing substituents of the R type,

wherein both the substituents of type R and type A and X are the same or different, and having at least one substituent of type A.

17. The composition according to claim 16, obtainable by a process according to at least one of claims 1 to 15.

18. The composition according to claim 16 or 17, that at least one of the functionalized polyhedral oligomeric silsesquioxane having an ammonium group or an ammonium group-containing substituents of type R, wherein the counter anion of the ammonium group, the base of the acid 3, 5-di-tert. butyl-4-hydroxybenzoic acid or 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.

19. Functionalized polyhedral oligomeric silsesquioxanes according to the formula

[(R _a X _b A ' _r Si0i, ₅ ) m (R ₀ XdA' _s SiO) _n ] with:

5 a, b, c, r = 0-1; d, s = 0-2;

m + n + o + p = 4-14; a + b + r = 1; c + d + s = 2; r + s> 1

R = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, each being substituted or unsubstituted,

X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl 15, blocked isocyanate, acrylate, methacrylate, mercapto, nitrile, phosphine group or at least one such type X substituent of type R,

A '= amino, ammonium or at least one amino- or ammonium-containing substituent 20 of the R type,

2520. Functionalized polyhedral oligomeric silsesquioxanes according to claim 18, characterized in that they have an ammonium group or an ammonium group-containing substituent of type R, wherein the counter anion of the ammonium group is the base of the acid

30 3, 5-di-tert. butyl-4-hydroxybenzoic acid or 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.

21. Use of a composition according to claim 16, 17 or 18 for the synthesis of catalysts and their starting compounds, for stabilizers and for the synthesis or modification of ceramic compositions and polymers.

22. Use of functionalized polyhedral oligomeric silsesquioxanes according to claim 19 or 20 for the synthesis of catalysts and their starting compounds, for stabilizers and for the synthesis or modification of ceramic compositions and polymers.