EP2864381A1

EP2864381A1 - Process for producing a composite material

Info

Publication number: EP2864381A1
Application number: EP13731744.2A
Authority: EP
Inventors: Arno Lange; Gerhard Cox; Hannes Wolf; Szilard Csihony
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-06-26
Filing date: 2013-06-25
Publication date: 2015-04-29
Also published as: SG11201408570TA; JP2015526544A; KR20150035750A; CN104603170A; WO2014001273A1

Abstract

The present invention relates to a process for producing a composite material composed of a) at least one oxidic phase and b) an organic polymer phase, comprising the copolymerization of at least one compound which is described by the following general formula I [(ArO)_mMO_nR_rH_p]_q(I) in which M is B, Al, Ga, In, Si, Ge, Sn, P, As or Sb, m is 1, 2 or 3, n is 0 or 1, r is 0, 1 or 2, p is 1, 2 or 3, q is 1 or an integer > 1, for example an integer from 2 to 20, especially an integer from 3 to 6, m + 2n + r + p is 1, 2, 3, 4 or 5 and corresponds to the valency of M, Ar is phenyl or naphthyl, where the phenyl ring or the naphthyl ring is unsubstituted or may have one or more, for example 1, 2 or 3, substituents selected from independently alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR^aR^b in which R^a and R^b are each independently hydrogen, alkyl or cycloalkyl, R is alkyl, alkenyl, cycloalkyl or aryl, where aryl is unsubstituted or may have one or more substituents selected independently from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR^aR^b in which R^a and R^b are each as defined above, with at least one compound selected from formaldehyde and formaldehyde equivalents, in a reaction medium which is essentially anhydrous, to obtain a composite material having an arrangement of phase domains similar to those nanocomposite materials obtainable by twin polymerization as described in the prior art, and to the use of the composite material for production of gas storage materials, rubber mixtures, low-K dielectrics and electrode materials for lithium ion batteries.

Description

Process for producing a composite material

Description: The present invention relates to a method for producing a composite material

a) at least one oxide phase and

b) at least one organic polymer phase. More recently, the production of composite materials by so-called twin polymerization has been variously described (see, for example, Spange et al., Angew Chem. Int. Ed., 46 (2007) 628-632, WO 2009/083083, WO 2009/133086 .

WO 2010/1 12581 and WO 2010/128144). In the twin polymerization, compounds having several arylmethyl groups attached to a metal or semimetal atom via one or two heteroatom (s), preferably one or two oxygen atoms, are polymerized.

The twin polymerization provides composite materials typically having at least one oxide phase and at least one organic polymer phase wherein the phase domains have a co-continuous configuration and dimensions in the range of a few nanometers (spacing between adjacent identical phases). It is believed that the particular phasing and short spacing of adjacent phases is a consequence of the kinetic coupling of the polymerization of the arylmethyl units in the twin monomers on the one hand and the formation of the silicon dioxide on the other hand. As a result, the phase constituents form more or less synchronously, and phase separation into the inorganic phase and the organic phase takes place already during the polymerization of the twin monomers. Preferred twin monomers are spiro-cyclic compounds as described in U.S. Pat

WO 2009/083083 are described. In these spirocyclic compounds, two 1-oxy-2- (oxymethyl) aryl groups are linked together via their oxygen atoms with a metal or semimetal atom to form a spirocyclic structure. An example of such a spirocyclic compound is 2,2'-spirobi [4H-1,2,2-benzodioxasiline]:

Although the spirocyclic compounds can be prepared comparatively easily by reacting 1-hydroxy-2-hydroxymethylaromatics, such as 1-hydroxy-2-hydroxymethylbenzene (saligenin), with metal alkoxides or semimetal alkoxides according to the method described in WO 2009/083083, the preparation of Starting materials, namely the 1-hydroxy-2-hydroxymethylaromaten, comparatively expensive. Although 1-hydroxy-2-hydroxymethylaromatics are formally monoaddition products of formaldehyde to hydroxyaromatics, the addition of formaldehyde to hydroxyaromatics such as phenol generally does not lead to the desired monoadduct, but to the ο, ο-bishydroxymethyl compound (see Ree. Trav. Chim. Pays-Bas 62, 57 (1943)). It is also known to reduce o-hydroxyarylcarboxylic acids such as salicylic acid with suitable reducing agents to the corresponding 1-hydroxy-2-hydroxymethylaromatics (see J. Chem. Soc. PT1, (1981) 1942-1952 and Bull. Chem. Soc. Jap. 56, 719-723, (1983)) or phenylborate with formaldehyde to the monoadduct and then to hydrolyze the o-hydroxymethyl phenylborate formed thereby to Saligenin (see FR 2626575). All these methods have in common that they lead in the laboratory by cleaning operations to good and reproducible results, but overall are consuming to perform. Incomplete reaction or by-products lead to product loss. Therefore, access to the spiro compounds described in WO 2009/083083 is complex and remains severely limited, which hitherto precludes an industrial application of the twin polymerization for the production of nanocomposite materials.

DE 1816241 discloses the preparation of soluble metal- or semimetal-containing phenol-formaldehyde resins in which either certain metal or semimetal phenolates are reacted with substoichiometric amounts of formaldehyde or novolacs, ie phenol-formaldehyde condensates, with selected inorganic metal - or semi-metal compounds are reacted. The production of composite materials with a phase structure whose phase domains have dimensions in the nanometer range is not described.

It has now surprisingly been found that by copolymerization of at least one compound which is described by the following general formula I, [(ArO) _m MOnRrH _p ] _q (I)

wherein

M is B, Al, Ga, In, Si, Ge, Sn, P, As or Sb,

m is 1, 2 or 3,

n is 0 or 1, r is 0, 1 or 2,

p is 1, 2 or 3,

q for 1 or an integer> 1, z. B. is an integer from 2 to 20, in particular an integer from 3 to 6,

m + 2n + r + p is 1, 2, 3, 4 or 5 and corresponds to the valency of M,

Ar is phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring is unsubstituted or one or more, for. 1, 2 or 3, substituents independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^b are each independently hydrogen, alkyl or

Are cycloalkyl,

R is alkyl, alkenyl, cycloalkyl or aryl wherein aryl is unsubstituted or may have one or more substituents independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b wherein R ^a and R ^b are as previously defined having at least one compound selected from formaldehyde and formaldehyde equivalents in a reaction medium which is substantially anhydrous, can produce composite materials having an arrangement of the phase domains similar to those of nanocomposite materials prepared by twin polymerization as described in US Pat State of the art described are available.

This is surprising, since it has hitherto been assumed that the formation of the nanocomposite materials is due to the structural units present in twin monomers, which arylmethylene groups which are covalently bonded via a heteroatom to a metal or semimetal have. It has previously been assumed that these structural units cause a kinetic coupling of the polymerization of the organic moiety of the twin monomers and the formation of the "inorganic polymer", namely the inorganic phase, since polymerization and formation of the inorganic phase have a common reaction step, namely the bond break between the methylene carbon of the arylmethylene group and the (semi-) metal-bearing heteroatom. The resulting kinetic coupling was seen in twin polymerization as the cause of the formation of the characteristic nanostructures. However, the characteristic structural units of the twin monomers do not have the compounds of the formula I.

The present invention thus relates to a process for the production of composite materials, which consists essentially of a) at least one oxide phase and

b) at least one organic polymer phase,

comprising the copolymerization of at least one compound which is described by the following general formula I,

[(ArO) _m MOnRrH _p ] _q (I)

wherein

M is B, Al, Ga, In, Si, Ge, Sn, P, As or Sb,

m is 1, 2 or 3,

n is 0 or 1,

r is 0, 1 or 2,

p is 1, 2 or 3,

m + 2n + r + p is 1, 2, 3, 4 or 5 and corresponds to the valency of M,

Are cycloalkyl,

R is alkyl, alkenyl, cycloalkyl or aryl wherein aryl is unsubstituted or may have one or more substituents independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b wherein R ^a and R ^b are as previously defined having at least one compound selected from formaldehyde and formaldehyde equivalents in a reaction medium which is substantially anhydrous.

The process according to the invention has a number of advantages. On the one hand, the process according to the invention provides composite materials as are also obtained in the twin polymerization, ie. H. Composite materials consisting of a) at least one oxide phase and

b) at least one organic polymer phase,

wherein the oxide phase and the organic polymer phase consist essentially of phase domains in which the mean spacing of adjacent phase domains of identical phases is very small. Unlike the twin polymerization, however, are not difficult to access starting materials such as those mentioned above Spiro compounds or labile arylmethyl (semimetals) such as tetrakis (furylmethyl-oxy) silane necessary to get to the desired composite materials. Rather, easily accessible and comparatively stable starting materials can be used with the compounds of the formula I, which makes it possible to produce the composite materials on a larger scale.

On the other hand, by selecting suitable compounds of the formula I or mixtures of compounds of the formula I, the process according to the invention makes it possible to selectively modify the material properties of the composite material obtainable thereafter. Thus, for example, the properties of the inorganic polymer phase can be modified by copolymerizing mixtures of different compounds of the formula I which differ in the nature of the metal, semimetal or nonmetal. In an analogous manner, for example, the properties of the organic polymer phase can be modified by copolymerizing mixtures of different compounds of the formula I which differ in the nature of the aryl group. Likewise, it is possible, for example, to modify the organic and inorganic polymer phases in their properties by copolymerizing mixtures of various compounds of the formula I which differ both in the nature of the metal, semimetal or nonmetal M and in the aryloxy group ArO.

As already mentioned, the method according to the invention provides composite materials which consist of at least one oxide phase and at least one organic polymer phase, the oxidic phase and the organic polymer phase consisting essentially of phase domains in which the mean spacing of adjacent phase domains of identical phases is very small is. The average spacing of adjacent phase domains of identical phases is typically less than 200 nm, often less than 50 nm, more preferably less than 10 nm. Under adjacent phase domains of identical phases is meant two phase domains of two identical phases separated by a phase domain of the other phase, for example two phase domains of the oxide phase separated by a phase domain of the organic polymer phase, or two phase domains of the polymer phase separated by a phase domain of the oxide phase. Formula I is to be understood as a so-called gross formula, it indicates the type and number of the structural units characteristic of the compounds of formula I, namely the atom M and the groups bonded to the atom M, ie the aryloxy group ArO, the oxygen atom O, the carbon -bonded radicals R and the hydrogen atoms H. The units [(ArO) _m MO _n RrHp] q can form mono- or polycyclic structures or linear structures for q> 1.

Compounds of the formula I can be regarded as compounds based on monohydroxyaromatics which formally have 1, 2 or 3 aryloxy groups Ar-O or anions derived from monohydroxyaromatics by deprotonation of the aromatic hydroxy function, where the monohydroxyaromatic or aromatic OH) aryloxy group (s) or anion (s) Ar-O is bonded via the deprotonated oxygen atom of the hydroxy group of the monohydroxyaromatic to a metal, metalloid or non-metal atom M. Accordingly, the radical Ar-0 in formula I corresponds to an aryloxy group or an aryloxy anion derived by deprotonation of the aromatic hydroxy function of a hydroxyaromatic.

Suitable monohydroxyaromatic Ar-OH are especially phenol, α-naphthol or ß-naphthol, which are unsubstituted or one or more, for. As 1, 2, 3 or 4, substituents which are typically selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^{b are} independently hydrogen, alkyl or cycloalkyl. The compounds of the formula I have one or more atoms M and, in the case of several atoms M, can have linear, branched, monocyclic or polycyclic structures.

The compounds of the formula I have formally 1, 2 or 3 hydrogen atoms bound to the atom M.

The compounds of the formula I can also formally have 1 or 2 substituents R on the atom M, where the substituents R are selected from alkyl, alkenyl, cycloalkyl or aryl, where aryl is unsubstituted or can have one or more substituents which are independent of one another are selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^{b are} independently hydrogen, alkyl or cycloalkyl.

The compounds of the formula I can also formally have an oxygen atom on the atom M.

The total number of groups bound to the atom M is typically determined by the valence of the atom M to which the above-mentioned groups are bound, and corresponds to the sum m + 2n + r + p. Here and below, the terms alkyl, alkenyl, cycloalkyl, alkoxy, cycloalkoxy and aryl are collective terms for monovalent organic radicals having the usual meaning for them, wherein alkyl and alkoxy typically 1 to 20, often 1 to 10 and especially 1 to 4 carbon atoms and cycloalkyl and cycloalkoxy typically have 3 to 20, often 3 to 10 and in particular 5 or 6 carbon atoms. The possible number of carbon atoms of a radical is typically given by the prefix C _x -C _y , where x is the minimum and y is the maximum carbon number.

Alkyl is a saturated, linear or branched hydrocarbon radical which typically has 1 to 20, frequently 1 to 10 and in particular 1 to 4 carbon atoms and which is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, Isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 1-methylbutyl, 3-pentyl, n -hexyl, n-heptyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 2-ethylhexyl, n-nonyl , 1-methylnonyl, n-decyl, 3-propylheptyl and the like.

Alkenyl is an olefinically unsaturated, linear or branched hydrocarbon radical which typically has 2 to 20, frequently 2 to 10 and in particular 2 to 6 carbon atoms and which is, for example, vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1 -Methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,

1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,

2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,

2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl,

1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl,

1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,

1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3 Methyl 2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4 pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,

1: 1 - dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl,

1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl,

1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,

2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,

3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 - butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,

1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl. Alkoxy stands for an alkyl radical bonded via an oxygen atom, as defined above, which typically has 1 to 20, frequently 1 to 10 and in particular 1 to 4 carbon atoms and which is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , 2-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-methylbutyloxy, 1-methylbutyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1-methylheptyloxy, 2-methylheptyloxy, 2-ethylhexyloxy, n- Nonyloxy, 1-methylnonyloxy, n-decyloxy, 3-propylheptyloxy and the like. Cycloalkyl is a mono-, bi- or tricyclic, saturated cycloaliphatic radical which has typically 3 to 20, often 3 to 10 and in particular 5 or 6 carbon atoms and which, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] octan-1-yl, bicyclo [2.2 .2] octan-2-yl, 1-adamantyl or 2-adamantyl.

Cycloalkyloxy represents a mono-, bi- or tricyclic, saturated cycloaliphatic radical bonded via an oxygen atom, which has typically 3 to 20, often 3 to 10 and in particular 5 or 6 carbon atoms and which is, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy , Cyclooctyloxy, bicyclo [2.2.1] hept-1-yloxy, bicyclo [2.2.1] hept-2-yloxy, bicyclo [2.2.1] hept-7-yloxy, bicyclo [2.2.2] octane-1 -yloxy, bicyclo [2.2.2] octan-2-yloxy, 1-adamantyloxy or 2-adamantyloxy. Aryl is a mononuclear or polynuclear aromatic hydrocarbon radical such as phenyl, 1-naphthyl or 2-naphthyl.

In the preferred compounds of the formula I, the atoms M are selected from B, Si, Sn and P, in particular from Si and Sn. In a specific embodiment of the invention, M is Si, d. h., the compound of the formula I is selected from compounds of the formula I in which the atom M comprises at least 90 mol%, based on the total amount of atoms M, of silicon.

In a preferred embodiment of the invention, r in formula I is 0, ie, the atom M carries no radicals R. In another preferred embodiment of the invention, at least two mutually different compounds of formula I are copolymerized with formaldehyde or a formaldehyde equivalent, wherein in at least one of the compounds of the formula I is the variable r is 0 and in at least one further compound of the formula I the variable r is 0. Independently of this, the variables m, n, r, p, Ar and R in formula I, taken alone or in combination, and in particular in combination with one of the preferred and particularly preferred meanings of M, preferably have the following meanings: m 1, 2 or 3;

n is O or l;

r is 0, 1 or 2;

p is 1, 2 or 3;

Ar is phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, cycloalkyl, in particular C 3 -C 10 -alkyl,

Cycloalkyl, alkoxy, in particular C 1 -C 4 -alkoxy, cycloalkoxy, in particular C 3 -C 10 -cycloalkoxy, and NR ^a R ^{b are} selected, wherein R ^a and R ^b independently of one another represent hydrogen, alkyl, in particular C 1 -C 4 -alkyl, or cycloalkyl , in particular C3-Cio-cycloalkyl;

R if present, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 10 -cycloalkyl or phenyl, in particular C 1 -C 4 -alkyl, C 6 -C 12 -cycloalkyl or phenyl.

In particular, the variables m, n, r, p, Ar and R in formula I, by themselves or in combination and in particular in combination with one of the preferred and particularly preferred meanings of M, preferably have the following meanings: m 1, 2 or 3 ;

n is O or l;

r is 0 or 1;

p 1 or 2;

Ar is phenyl which is unsubstituted or may have 1, 2 or 3 substituents selected from alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkoxy;

If the compound of the formula I has several radicals ArO, the individual radicals Ar can be identical or different. Likewise, if there are several radicals R, they may be the same or different.

A preferred embodiment of the compounds of the formula I are those compounds in which q is 1. Such compounds can be considered as ortho-esters of the atom M underlying oxo acid. In these compounds, the variables m, n, r, p, M, Ar and R have the meanings given above and in particular, individually or in combination, one of the preferred or particularly preferred meanings.

A particularly preferred embodiment of the compounds of formula I are those compounds wherein M is selected from B, Si, Sn and P, m is 2 or 3, n is 0 or 1, r is 0, p is 1 or 2 and q is 1. In this Ar has the meanings mentioned above and in particular the preferred meanings and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkyl. Alkoxy, are selected.

A very particularly preferred embodiment of the compounds of the formula I are those compounds in which M is selected from B, Si and Sn, m is 2 or 3, n is 0, r is 0, p is 1 or 2 and q stands for 1 In this Ar has the meanings mentioned above and in particular the preferred meanings and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkyl. Alkoxy, are selected. A specific embodiment of the compounds of the formula I are those compounds in which M is Si, m is 1, 2 or 3, n is 0, r is 0 or 1, p is 1, 2 or 3 and q is 1 stands. In this formula, Ar has the meanings mentioned above and in particular the preferred meanings, and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkyl. C4 alkoxy are selected.

Examples of compounds of the formula I which are preferred according to the invention in which q is 1 are diphenoxymethylsilane, triphenoxysilane and diphenoxysilane. Another specific embodiment of the compounds of the formula I are those compounds in which M is Si, m is 1, 2 or 3, n is 0, r is 0 or 1, p is 1, 2 or 3 and q stands for 1 In this formula, Ar has the meanings mentioned above and in particular the preferred meanings and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are unsubstituted by alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C4 alkoxy are selected. In these compounds, R has the meanings described for formula I; in particular, R is methyl, ethyl, phenyl, vinyl or allyl. Examples of preferred compounds of formula I of this embodiment are diphenoxymethylsilane, triphenoxysilane and diphenoxysilane. Also suitable as compounds of the formula I are "condensation products" of compounds of the formula I where q is 1. These compounds generally have the empirical formula of formula I, wherein q is an integer greater than 1, z. B. an integer in the range of 2 to 20 and in particular for 3, 4, 5 or 6 stands. Such compounds are derived formally by condensation of compounds of the formula I with q equal to 1, wherein formally two units each ArO condense to form a molecule Ar-O-Ar and a unit M (ArO) m-20 _n + iRrH _{p was} removed , Accordingly, they are essentially made up of the structural elements of the following formula Ia,

- [- OA -] - (la) where -A- is a group> M (ArO) m-20 _n RrH _p , where M, Ar and R are those mentioned above, in particular those mentioned as preferred or particularly preferred , Meanings,

m stands for 3,

n is 0,

r stands for 0,

p stands for 1

m + 2n + r + p is 3, 4 or 5 and corresponds to the valency of M.

In a preferred embodiment, the condensation product is cyclic and q is 3, 4 or 5. Such compounds can be described in particular by the following structure Ib,

where k is 1, 2 or 3 and -A- is a group> M (ArO) m-20 _n RrH _p , where M, Ar and R are the meanings given above for formula I and m, n, r and p have the meanings mentioned above in connection with structure Ia.

In a further preferred embodiment, the condensation product is linear and saturated at the ends with one ArO unit each. In other words, such compounds can be described by the following structure Ic

Ar - [- O-A-] _s -OAr (Ic) where s is an integer in the range from 2 to 20 and -A- is a group> M (ArO) m-20 _n RrHp, where M, Ar and R are the meanings mentioned above for formula I and m, n, r and p have the meanings previously mentioned in connection with structure 1a. This embodiment is particularly preferred if compounds have a distribution with respect to the number of repeat units, that is, with different s. For example, mixtures may be present in which at least 99%, 90%, 80% or 60% of the mass is present as an oligomer mixture with s equal to 2 to 6 or s equal to 4 to 9 or s equal to 6 to 15 or s equal to 12 to 20 ,

Examples of such condensation products are triphenoxycyclotrisiloxane or tet raphenoxycyclotetrasiloxane. The compounds of formula I are known or can be prepared in analogy to known methods for the preparation of phenolates, see, for. Senn, WADC Technical Report 54-339, SRI (1955), DE 1816241, Z. Anorg. Gen. Chem. 551, 61-66 (1987), Houben-Weyl, Vol. VI-2 35-41, Z. Chem. 5,122-130 (1965). In a further embodiment of the invention, the compounds of the formula I comprise at least two mutually different compounds V1 and V2. The compounds V1 and V2 preferably differ in at least one of the following features (1) to (4): (1) difference in Ar, (2) difference in M, (3) difference in r, d. h., number of radicals R, (4) difference in p, d. h., number of hydrogen atoms bound to M. For example, compound V1 is selected from compounds of the formula I in which M is B, Si, Sn or P and in particular B, Si or Sn, m is 1, 2 or 3, n is 0 or 1, in particular 0 , r is 0, p is

1 or 2 stands. The compound V2 is selected, for example, from compounds of the formula I in which M is selected from B, Si, Sn or P and M is in particular Si or Sn, m is 1, 2 or 3, n is 0 or 1, in particular 0 stands, r for 1 or

2, p is 1, 2 or 3. In this case Ar in the compounds V1 and V2 may be identical or different, Ar having the abovementioned meanings and in particular the preferred meanings and in particular being phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl , in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkoxy. R then preferably represents C 1 -C 6 -alkyl, C 3 -C 10 -cycloalkyl or phenyl, in particular C 1 -C 4 -alkyl, C 6 -C 12 -cycloalkyl or phenyl. The molar ratio of compound V1 to compound V2 of this embodiment can be varied over wide ranges and typically ranges from 1: 1000 to 1000: 1, often in the range of 100: 1 to 1: 100 or in the range of 50: 1 to 1: 50 lie.

In a further, more specific embodiment of the invention, the compounds of the formula I comprise at least two mutually different compounds V1 and V2, the compound V1 being selected from compounds of the formula I in which M is B, Al, Ga, In, Ge, Sn, P, As or Sb and in particular B, Sn or P, m is 1, 2 or 3, n is 0 or 1, r is 0, 1 or 2, p is 1, 2 or 3 and the Compound V2 is selected from compounds of the formula I in which M is Si, m is 1, 2 or 3, n is 0, r is 0, 1 or 2, p is 1, 2 or 3. In this case, Ar in the compounds V1 and V2 may be identical or different, Ar having the abovementioned and in particular the preferred meanings and in particular being phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular Ci-C4-alkyl, and alkoxy, in particular Ci-C4-alkoxy, are selected. R then preferably represents C 1 -C 6 -alkyl, C 3 -C 10 -cycloalkyl or phenyl, in particular C 1 -C 4 -alkyl, C 6 -C 12 -cycloalkyl or phenyl. The molar ratio of compound V1 to compound V2 of this embodiment can be varied over wide ranges and typically ranges from 1: 1000 to 1000: 1, often in the range of 100: 1 to 1: 100 or in the range of 50: 1 to 1: 50 lie. The compounds of the formula I can also be used together with one or more compounds of the formula II:

[(Ar'0) aM'OcR'b] d (II)

wherein

M 'is a metal, metalloid or oxoacid-forming non-metal other than carbon and nitrogen, preferably one of the meanings given in formula I for M, in particular one of the meanings mentioned therein as being preferred;

a is 1, 2, 3, 4, 5 or 6,

b is 0, 1 or 2,

c is 0, 1 or 2,

d is 1 or an integer> 1, e.g. an integer from 2 to 20, in particular an integer from 3 to 6,

a + b + 2c is 1, 2, 3, 4, 5 or 6 and corresponds to the valence of M ', Ar 'has one of the meanings given in formula I for Ar, in particular one of the meanings mentioned there as preferred;

R 'has one of the meanings given in formula I for R, in particular one of the meanings mentioned there as preferred.

If the compound of the formula II has several radicals Ar'O, the individual radicals Ar 'may be identical or different. Likewise, if there are several radicals R ', they may be the same or different. In formula II, M 'represents a metal or semimetal or a non-metal other than carbon or nitrogen which forms oxo acids, the metals, semi-metals and non-metals being selected, as a rule, from the non-nitrogen and carbon elements of the following groups of the periodic table IA, such as Li, Na or K, IIA, such as Mg, Ca, Sr or Ba, INA, such as B, Al, Ga or In, IVA, such as Si, Ge or Sn, VA, such as P, As or Sb, VIA, like S, Se or Te, IVB, like Ti or Zr, VB, like V, VIB like Cr, Mo or W and VIIB, like Mn. Preferably, M 'is an element selected from the group consisting of elements of INA, IVA, VA and IVB other than carbon and nitrogen of the periodic table, in particular a second, third and fourth period element. More preferably, M 'is selected from B, Si, Sn, Ti and P. In a particularly preferred embodiment of the invention, M' is B or Si and especially Si.

In a preferred embodiment of the invention, b in formula II is 0, d. that is, the atom M 'carries no residues R'.

Independently of this, the variables a, b, c, Ar 'and R' in formula II, either alone or in combination and in particular in combination with one of the preferred and particularly preferred meanings of M ', preferably have the following meanings: a 2, 3 or 4 ;

c O or I;

b is 0, 1 or 2;

Ar 'phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, cycloalkyl, in particular C 3 -C 10 -cycloalkyl, alkoxy, in particular C 1 -C 4 -alkoxy, cycloalkoxy, in particular C 3 - Cio-cycloalkoxy and NR ^a R ^{b are} selected, wherein R ^a and R ^b independently of one another are hydrogen, alkyl, in particular C 1 -C 4 -alkyl, or cycloalkyl, in particular C 3 -C 10 -cycloalkyl;

R ', if present, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 10 -cycloalkyl or phenyl, in particular C 1 -C 4 -alkyl, C 1 -C 6 -cycloalkyl or phenyl. In particular, the variables a, b, c, Ar 'and R' in formula II, taken alone or in combination, and in particular in combination with one of the preferred and particularly preferred meanings of M ', preferably have the following meanings:

a is 1, 2, 3 or 4;

c O or I;

b 0;

Ar 'phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are selected from alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkoxy.

A preferred embodiment of the compounds of the formula II are those compounds of the formula II in which d is the number 1. Such compounds can be considered as ortho-esters of the central atom M 'underlying oxo-acid. In these compounds, the variables a, b, c, M ', Ar' and R 'have the abovementioned meanings and especially in combination one of the preferred or particularly preferred meanings.

A particularly preferred embodiment of the compounds of the formula II are those compounds of the formula II in which M 'is selected from B, Si, Sn, Ti and P, a is 3 or 4, c is 0 or 1 and b is 0 and d = 1. In it, Ar 'has the meanings mentioned above and in particular the preferred meanings and is in particular phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 - Alkoxy, are selected.

A very particularly preferred embodiment of the compounds of the formula II are those compounds of the formula II in which M 'is selected from B, Si and Sn, a is 3 or 4, c is 0 and b is 0 and d = 1 , In it, Ar 'has the meanings mentioned above and in particular the preferred meanings and is in particular phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 - Alkoxy, are selected. A specific embodiment of the compounds of the formula II are those compounds of the formula II in which M 'is Si, a is 4, c is 0 and b is 0. In this formula, Ar 'has the meanings mentioned above and in particular the preferred meanings, and in particular represents phenyl which is unsubstituted or is 1, 2 or 3 subunits. having substituents which are selected from alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkoxy.

Examples of preferred compounds of the formula II where d = 1 are tetraphenoxysilane, tetra (4-methylphenoxy) silane, triphenyl borate, triphenyl phosphate, tetraphenyl titanate, tetrakresyl titanate and tetraphenyl stannate.

Another specific embodiment of the compounds of the formula II are those compounds of the formula II in which M 'is Si, a is 1, 2 or 3, c is 0 and b is 4-a. In it, Ar 'has the meanings mentioned above and in particular the preferred meanings and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 Alkoxy, are selected. In these compounds R 'has the meanings described for formula II; in particular, R 'is methyl, ethyl, phenyl, vinyl or allyl. Examples of preferred compounds of formula II of this embodiment are methyl (triphenoxy) silane, dimethyl (diphenoxy) silane, trimethyl (phenoxy) silane, phenyl (triphenoxy) silane and diphenyl (diphenoxy) silane.

Suitable compounds of the formula II are also "condensation products" of compounds of the formula II where d = 1. These compounds usually have the empirical formula II, wherein d is an integer> 1, z. B. an integer in the range of 2 to 20 and in particular for 3, 4, 5 or 6 stands. Such compounds are derived formally by condensation of compounds of the formula II where d = 1, formally in each case 2 units Ar'O to form a molecule Ar'-O-Ar 'and a unit M' (OAr ') _a -2 ( 0) c + iRb were removed. Accordingly, they are essentially composed of the structural elements of the following formula IIa:

- [- O-A '-] - (lla) wherein -A'- is a group>M' (ArO) a-2 (0) _c (R ') b, where M', Ar 'and R' have the abovementioned meanings, in particular those mentioned as preferred or particularly preferred,

a stands for 3 or 4,

c is 0 or 1 and in particular 0,

b is 0 or 1 and especially 0,

a + b + 2c is 3, 4, 5 or 6 and corresponds to the valence of M '.

Preferably, M 'in the formula A' is Si, Sn, B and P. In a preferred embodiment, the condensation product is cyclic and d is 3, 4 or 5. Such compounds can be described in particular by the following structure IIb:

wherein k is 1, 2 or 3 and -A'- is a group> M '(ArO) a-2 (0) _c (R') b, wherein M ', Ar' and R 'are as above for formula II and a, c and b have the meanings mentioned above in connection with structure IIa.

In a further preferred embodiment, the condensation product is linear and saturated at the ends with an Ar'O unit. In other words, such compounds can be described by the following structure IIc, Ar '- [- O-A'-] _d -OAr' (IIc) where d is an integer in the range of 2 to 20, and -A ' - is a group> M '(Ar'0) a-2 (0) c (R') b, wherein M ', Ar' and R 'are the meanings given above for formula II and a, b and c are the above in the context of structure IIa. This embodiment is particularly preferred if compounds have a distribution with respect to the number of repeat units, that is to say they are present with different d. For example, there may be mixtures in which at least 99%, 90%, 80% or 60% of the mass exist as oligomer mixture with d = 2 to 6 or d = 4 to 9 or d = 6 to 15 or d = 12 to 20.

Examples of such condensation products are triphenyl metaborate, hexaphenoxyacotrisiloxane or octaphenoxycyclotetrasiloxane.

The compounds of formula II are known or can be prepared in analogy to known methods for the preparation of phenates, see, for. Senn, WADC Technical Report 54-339, SRI (1955), DE 1816241, Z. Anorg. Gen. Chem. 551, 61-66 (1987), Houben-Weyl, Vol. VI-2 35-41, Z. Chem. 5,122-130 (1965).

If a mixture of at least one compound of the formula I and at least one compound of the formula II is co-polymerized with the formaldehyde or formaldehyde equivalent, the molar ratio of the compound of the formula I to the compound of the formula II can be varied over a wide range typically in the ranging from 1: 1000 to 1000: 1, often in the range of 100: 1 to 1: 100 or in the range of 50: 1 to 1:50.

In the process according to the invention, the compounds of the formula I or the mixture of the compound of the formula I with the compound of the formula II on the one hand and formaldehyde or the formaldehyde equivalent on the other hand used in an amount such that the molar ratio of formaldehyde, or the molar ratio from the formaldehyde contained in the formaldehyde equivalent to the aryloxy groups ArO or Ar'O present in the compounds of the formula I and, if appropriate, the formula II, preferably at least 0.9: 1, in particular at least 1: 1, especially at least 1, 01: 1, very particularly preferably at least 1, 05: 1 and especially at least 1, 1: 1. Greater excesses of formaldehyde are generally not critical, but not necessary, so that one typically uses formaldehyde or the formaldehyde equivalent in an amount such that the molar ratio of formaldehyde, or the molar ratio of formaldehyde contained in the formaldehyde equivalent, to the in the compounds of formula I and optionally of the formula II aryloxy ArO or Ar'O present a value of 10: 1, preferably 5: 1 and in particular 2: 1 does not exceed. It is preferable to use formaldehyde or the formaldehyde equivalent in an amount such that the molar ratio of formaldehyde or the molar ratio of the formaldehyde contained in the formaldehyde equivalent to the aryloxy groups ArO present in the compounds of the formula I and optionally of the formula II or Ar'O in the range of 1: 1 to 10: 1, in particular in the range of 1, 01: 1 to 5: 1 and especially in the range of 1, 05: 1 to 1: 5 or 1, 1: 1 to 2: 1 lies. By a formaldehyde equivalent is meant a compound which releases formaldehyde under polymerization conditions. The formaldehyde equivalent is preferably an oligomer or polymer of formaldehyde, ie a substance having the empirical formula (CH 2 O) _Z , where z denotes the degree of polymerization. These include, in particular, trioxane (3 formaldehyde units) and paraformaldehyde (higher oligomer (CH ₂ O) _z ).

Preferably, the copolymerization is carried out using formaldehyde and formaldehyde equivalents selected from gaseous formaldehyde, trioxane and paraformaldehyde.

In a preferred embodiment of the process according to the invention, the copolymerization of the compounds of the formula I and optionally of the formula II with the compounds selected from formaldehyde and formaldehyde equivalents takes place in the presence of catalytic amounts of an acid. Typically, the acid is added an amount of from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, based on the compounds of the formula I and, if appropriate, of the formula II. Preferred acids here are Bronsted acids, for example organic carboxylic acids such. B. trifluoroacetic acid, oxalic acid or lactic acid and organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or p-toluenesulfonic acid. Also suitable are inorganic Bronsted acids such as HCl, H2SO4 or HCIO4. As the Lewis acid, for example, BF3, BC, SnCU, TiCU, or AICI3 can be used. The use of complexed or dissolved in ionic liquids Lewis acids is also possible.

The copolymerization can also be catalyzed with bases. Examples are amines such as triethylamine or dimethylaniline, hydroxides and basic salts of alkali metals and alkaline earth metals such as LiOH, NaOH, KOH, Ca (OH) ₂ , Ba (OH) ₂ or Na ₃ P0 ₄ and alkoxides of alkali metals and alkaline earth metals such as Na-methylate, Na-ethylate, K-tert-butylate or Mg-ethylate.

The copolymerization can also be thermally initiated, i. h., the copolymerization is carried out without the addition of an acid by heating a mixture of the compounds of formula I and optionally of formula II and the compounds selected from formaldehyde and formaldehyde equivalents.

The temperatures required for the copolymerization are typically in the range of 50 to 250 ° C, in particular in the range of 80 to 200 ° C. In an acid- or base-catalyzed copolymerization, the polymerization temperatures are typically in the range of 50 to 200 ° C and in particular in the range of 80 to 150 ° C. In the thermally initiated copolymerization, the polymerization temperatures are typically in the range of 120 to 250 ° C and in particular in the range of 150 to 200 ° C.

The copolymerization can in principle be carried out as a so-called batch or as an addition process. When carried out as a batch, the compounds of the formula I or the mixture of at least one compound of the formula I with at least one compound of the formula II and the compounds selected from formaldehyde and formaldehyde equivalents in the desired amount in the reaction vessel and those for the copolymerization required conditions. In the addition process, at least one of the two components, ie the compounds) of the formula I and optionally the formula II and / or the compound which is selected from formaldehyde and formaldehyde equivalents, at least partially fed in the course of the polymerization until the desired ratio from the compound of the formula I and, if appropriate, of the formula II to the compound which is maldehyde and formaldehyde equivalents is selected. Optionally, the addition is followed by a post-reaction phase. Preferably, the implementation is as a batch. It has proved to be advantageous if one carries out the copolymerization in one stage (in one step), ie, one carries out the polymerization as a batch with the total amount of the compounds of formula I to be polymerized and optionally of the formula II and the compounds under Formaldehyde and formaldehyde equivalents are selected, by or works by an addition method in which the addition of the compounds of formula I and optionally of formula II and the compounds described in US Pat

Formaldehyde and formaldehyde equivalents are selected, it is carried out so that the polymerization conditions are not interrupted until the total amount of the compounds of formula I and optionally of formula II and the compounds selected from formaldehyde and formaldehyde equivalents have been added to the reaction vessel ,

The copolymerization of the compounds of formula I or the mixture of at least one compound of formula I and at least one compound of formula II and the compounds selected from formaldehyde and formaldehyde equivalents may be carried out neat or in an inert diluent. Suitable diluents are, for example, halogenated hydrocarbons such as dichloromethane, trichloromethane, 1, 2-dichloroethene or hydrocarbons such as toluene, xylene or hexane and mixtures thereof. Preferably, the copolymerization of the compounds of formula I or of the mixture of at least one compound of formula I and at least one compound of formula II with the compounds selected from formaldehyde and formaldehyde equivalents is carried out with substantial absence of water, i. h., The concentration of water at the beginning of the polymerization is less than 0.1 wt .-%, based on the total amount of monomer to be polymerized.

The copolymerization of the compounds of the formula I or the mixture of at least one compound of the formula I and at least one compound of the formula II with the compounds selected from formaldehyde and formaldehyde equivalents may be followed by purification steps and optionally drying steps.

The copolymerization of the compounds of the formula I or the mixture of at least one compound of the formula I and at least one compound of the formula II with the compounds selected from formaldehyde and formaldehyde equivalents can be followed by a calcination. In this case, the organic polymeric material formed in the copolymerization of the compounds of the formula I or of the mixture of at least one compound of the formula I and at least one compound of the formula II with the compound selected from formaldehyde and formaldehyde equivalents is carbonized to the carbon phase.

The copolymerization of the compounds of the formula I or the mixture of at least one compound of the formula I and at least one compound of the formula II with the compounds selected from formaldehyde and formaldehyde equivalents may be followed by oxidative removal of the organic polymer phase. In this case, the organic polymeric material formed during the copolymerization of the organic constituents is oxidized, and a nanoporous oxidic or nitridic material is obtained. The composite material obtainable by the process according to the invention has at least one oxide phase which contains the metal, semimetal or non-metal M or M 'and at least one organic polymer phase resulting from the polymerization of the aryloxy groups ArO or Ar'O with the formaldehyde , The dimensions of the phase domains in the composite material thus obtained are usually in the range of a few nanometers, but it is possible to obtain materials with domain sizes of up to 100-200 nm. In addition, the phase domains of the oxide phase and the phase domains of the organic phase typically have a co-continuous arrangement, i. that is, both the organic phase and the inorganic or organometallic phase penetrate each other and form essentially no discontinuous regions. The distances between adjacent phase boundaries, or the distances between the domains of adjacent identical phases, are extremely low and are on average at most 10 nm, preferably at most 5 nm and in particular at most 2 nm. A macroscopically visible separation into discontinuous domains of the respective phase occurs not up.

The mean distance between the domains of adjacent identical phases can be determined by means of combined X-ray small-angle scattering (SAXS) via the scattering vector q (measurement in transmission at 20 ° C., monochromatized CuK _a radiation, 2D detector ( Image plate), slit collimation).

With regard to the term continuous phase domain, discontinuous phase domain and co-continuous phase domain, it is also referred to WJ Work et al., Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), Pure Appl. Chem., 76 (2004), pp. 1985-2007, in particular p. 2003, referenced. Hereinafter, a co-continuous arrangement of a two-component mixture is understood to mean a phase-separated arrangement of the two phases, wherein within a domain of the respective phase each region of the phase interface of the domain can be connected to each other by a continuous path, without the path a phase interface passes through / intersects.

The composite materials obtainable according to the invention can be converted in a manner known per se into nanoporous inorganic materials by oxidatively removing the organic constituents of the nanocomposite material according to the invention. In this case, the nanostructure of the inorganic phase contained in the nanocomposite material according to the invention is maintained and results, depending on the selected compounds of the formula I, an oxide of the (semi-) metal or the non-metal or a mixed form. The oxidation is typically carried out by heating in an oxygen-containing atmosphere as in the above cited essay by Spange et al. described. As a rule, heating is carried out with access of oxygen at a temperature in the range from 400 to 1500 ° C., in particular in the range from 500 to 1000 ° C. The heating is typically carried out in an oxygen-containing atmosphere, e.g. As in air or other oxygen / nitrogen mixtures, wherein the volume fraction of oxygen can be varied over wide ranges and, for example, in the range of 5 to 50 vol .-%, based on the total gas mixture.

The composite materials obtainable according to the invention can also be converted into an electroactive nanocomposite material which, in addition to an inorganic phase of a (semi-) metal, which may be both oxidic and (semi-) metallic, has a carbon phase C. Such materials are obtainable by calcining the composite material obtainable according to the invention with substantial or complete exclusion of oxygen. In the carbonaceous nanocomposite material, the carbon phase C and the inorganic phase form substantially co-continuous phase domains, with the average spacing of two adjacent domains of identical phases typically being at most 10 nm. As a rule, the calcination is carried out at a temperature in the range from 400 to 2000.degree. C., in particular in the range from 500 to 1000.degree. The calcination is then usually carried out with substantial exclusion of oxygen. In other words, during the calcination, the oxygen partial pressure in the reaction zone in which the calcination is carried out is low and will preferably not exceed 20 mbar, in particular 10 mbar. Preferably, the calcination is carried out in an inert gas atmosphere, e.g. B. under nitrogen or argon. Preferably, the inert gas atmosphere less than 1 vol .-%, in particular less than 0.1 vol .-% oxygen contain. In a likewise preferred embodiment of the invention, the calcination is carried out under reducing conditions, for. Example, in an atmosphere containing hydrogen (Hb), hydrocarbon gases such as methane, ethane or propane, or ammonia (NH3), optionally as a mixture with an inert such as nitrogen or argon. For devolatilization, calcination may be carried out in an inert gas stream or in a gas stream containing reducing gases such as hydrogen, hydrocarbon gases or ammonia.

According to the invention, the composite materials obtainable in accordance with the invention are particularly advantageously used for the production of gas storage materials, rubber mixtures, low-K dielectrics and electrode materials for lithium-ion batteries.

The following example serves to explain the invention.

Compounds of the formula I used:

Diphenoxysilane (compound of the formula I where M = Si, m = 2, n = 0, r = 0, p = 2, q = 1, Ar = phenyl). The preparation was carried out according to the method described by G. Fester (Dissertation 2009, Bergakademie Freiberg / Sa, Example 20 f.).

Diphenoxymethylsilane (compound of the formula I where M = Si, m = 2, n = 0, r = 1, p = 1, q = 1, Ar = phenyl, R = CH ₃ ). The preparation was carried out according to the method described in DE 1 162365, Example 3.

Example 1 :

Precipitation Polymerization of Diphenoxymethylsilane and Tetraphenoxysilane in Solution In a 250 mL four-necked flask, 15 g of diphenoxymethylsilane and 5 g of tetraphenoxysilane were melted with 7.8 g of trioxane under nitrogen at 40-50 ° C. and diluted with 80 g of xylene. To this was added 0.2 g of methanesulfonic acid at 50 ° C and homogenized. Subsequently, the mixture was stirred at 80 ° C. for 30 minutes at a stirrer speed of 500-600 rpm, at 100 ° C. for 30 minutes and at 120 ° C. for 30 minutes. The mixture was cooled to room temperature, filtered with suction through a D4 frit, washed with xylene and hexane and dried in a vacuum oven. 25 g of a finely divided powder were obtained. The primary particles showed the typical twin structure domain structures with dimensions in the range of 2-5 nm (determined by TEM). Example 2:

Precipitation polymerization of diphenoxymethylsilane and tetraphenoxysilane in solution

50 g of diphenoxymethylsilane and 14.3 g of trioxane were melted under nitrogen at 70 ° C. in a 250 mL Erlenmeyer flask. To this was added a solution of 49.4 g of tin dichloride in 120 ml of THF and cooled with an ice bath to 22 ° C and transferred the solution in a dropping funnel. 250 ml of xylene and 2.5 g of methanesulfonic acid were placed in a 500mL four-necked flask and heated to 126 ° C with an oil bath. For this purpose, the solution of methyldiphenoxysilane, trioxane and tin dichloride in THF was added dropwise over the course of 105 minutes while the temperature of the mixture was kept at 120-125 ° C. THF and water were distilled off via a water separator. The reaction mixture was stirred for a further 60 minutes at an internal temperature of 136 ° C. The crude product was filtered off through suction filters and washed twice with 100 ml of toluene and twice with 100 ml of hexane. The crude product was dried at 80 ° C and 5mbar. 47.7 g of crude product were obtained. The crude product was treated with 5 g of sodium methylate and 1 L of water and stirred for 2 h at 22 ° C, then filtered off and washed twice with 100mL of methanol. The product was dried at 80 ° C and 5mbar. There were obtained 12.6 g of composite material containing 4.3% of silicon by elemental analysis

The primary particles showed the typical twin structure domain structures with dimensions in the range of 3-5 nm (determined by TEM).

Claims

claims:

Process for the preparation of a composite material

a) at least one oxide phase and

b) an organic polymer phase

[(ArO) _m MOnRrH _p ] _q (I) represents B, Al, Ga, In, Si, Ge, Sn, P, As or Sb,

is 1, 2 or 3,

stands for 0 or 1,

stands for 0, 1 or 2,

is 1, 2 or 3,

for 1 or an integer> 1, z. B. is an integer from 2 to 20, in particular an integer from 3 to 6, stands for 1, 2, 3, 4 or 5 and the valency of M corresponds to phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring is unsubstituted or one or more, e.g. 1, 2 or 3, substituents independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b wherein R ^a and R ^{b are} independently hydrogen, alkyl or cycloalkyl, alkyl, Alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents which are independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^{b have} the meanings given above with at least one compound selected from formaldehyde and formaldehyde equivalents in a reaction medium which is substantially anhydrous. 2. The method of claim 1, wherein the compound selected from formaldehyde and formaldehyde equivalents used in an amount such that the molar ratio of formaldehyde to the aryloxy ArO in the compound of formula I is at least 0.9: 1. A process according to any one of the preceding claims, wherein M is selected from B, Si, Sn and P, m is 1, 2 or 3, n is 0 or 1, r is 0 or 1 and p is 1 or 2.

Method according to one of the preceding claims, wherein in the compounds of formula I, the variable M is Si.

Method according to one of the preceding claims, wherein the compound of formula I is selected from diphenoxymethylsilane, triphenoxysilane and diphenoxysilane.

Method according to one of the preceding claims, wherein the compound of formula I is used in admixture with at least one of the compounds of formula II:

[(Ar'0) aM'OcR'b] d (II)

wherein

M 'is a metal, metalloid or oxoacid-forming non-metal other than carbon and nitrogen;

a is 1, 2, 3, 4, 5 or 6,

b is 0, 1 or 2,

c is 0, 1 or 2,

d is 1 or an integer> 1, z. B. is an integer from 2 to 20, in particular an integer from 3 to 6, a + b + 2c is 1, 2, 3, 4, 5 or 6 and the valence of M 'corresponds, Ar' for Phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring is unsubstituted or one or more, for. 1, 2 or 3, substituents independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b wherein R ^a and R ^{b are} independently hydrogen, alkyl or cycloalkyl;

R 'is alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^{b are} the have previously mentioned meanings.

7. The method according to any one of the preceding claims, wherein the compound selected from formaldehyde and formaldehyde equivalents in a Amount sets that the molar ratio of formaldehyde to the aryloxy ArO or Ar'O in the compounds of formula I and optionally of the formula II in the range of 1: 1 to 10: 1 and in particular in the range of 1, 05: 1 to 2: 1 lies. 8. The method according to any one of the preceding claims, wherein the compound selected from formaldehyde and formaldehyde equivalents is selected from paraformaldehyde, trioxane and gaseous formaldehyde.

9. The method according to any one of the preceding claims, wherein the copolymerization is carried out in the presence of an acid.

10. The method according to claim 9, wherein the acid is used in an amount of 0.1 to 10 wt .-%, based on the compound of formula I or on the mixture of the compounds of formulas I and II.

1 1. Method according to one of the preceding claims, wherein the copolymerization is carried out in one stage.

12. The method according to any one of the preceding claims, wherein the copolymerization is carried out in an inert solvent.

13. The method according to any one of the preceding claims, wherein the copolymerization is carried out in bulk. 14. The method according to any one of the preceding claims, wherein a calcination is carried out after the copolymerization.

15. Use of a composite material, obtainable by a process according to one of claims 1 to 14, for the production of gas storage materials.

16. Use of a composite material, obtainable by a process according to any one of claims 1 to 14, for the preparation of rubber mixtures.

17. Use of a composite material, obtainable by a process according to one of claims 1 to 14, for the production of low-K dielectrics.

18. Use of a composite material, obtainable by a method according to one of claims 1 to 14, for the production of electrode materials for lithium-ion batteries.