WO2012098149A2

WO2012098149A2 - Process for producing a composite material

Info

Publication number: WO2012098149A2
Application number: PCT/EP2012/050690
Authority: WO
Inventors: Arno Lange; Gerhard Cox; Rainer Dyllick-Brenzinger; Oliver Gronwald; Theo SMIT
Original assignee: Basf Se
Priority date: 2011-01-19
Filing date: 2012-01-18
Publication date: 2012-07-26
Also published as: WO2012098149A3; EP2665764A2; CN103476837A; KR20130092624A; JP2014506608A

Abstract

The present invention relates to a process for producing composite materials which consist essentially of a) at least one oxidic phase and b) at least one organic polymer phase, by copolymerizing - at least one compound A selected from aryloxy metallates, aryloxy semimetallates and aryloxy esters of non-metals which form oxo acids and are different from carbon and nitrogen, with - at least one compound B selected from formaldehyde and formaldehyde equivalents, in a reaction medium which is essentially anhydrous, the compound B being used in an amount such that the molar ratio of formaldehyde to the aryloxy groups in the compound A is at least 0.9:1.

Description

Process for producing a composite material

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

a) at least one oxidic phase; and

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

2010/1 12581 and WO2010 / 128144). In the twin polymerization, compounds having several arylmethyl groups attached to one or two heteroatom (s), preferably one or two oxygen atoms, are polymerized to a metal or semimetal atom.

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 phase arrangement 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 silica on the other hand. As a result, the phase constituents form more or less synchronously and there is already a phase separation into the inorganic phase and the organic phase during the polymerization of the twin monomers. Preferred twin monomers are spiro-cyclic compounds as described in WO

2009/083083 be described. In these spirocyclic compounds, two 1-oxy-2- (oxymethyl) aryl groups are linked via their oxygen atoms to a metal or semimetal atom to form a spirocyclic structure. An example of such a spiro-cyclic compound is 2,2'-spiro [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. However, the production of starting materials, namely the 1-hydroxy-2-hydroxymethylaromaten, comparatively expensive. Although 1-hydroxy-2-hydroxymethylaromatics are formally monoaddition products of formaldehyde to hydroxyaromatics. However, 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 Rec.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-hydromethylphenylborate formed thereby to Saligenin (see FR 2626575) .These methods have in common that they are in the laboratory by cleaning operations to good and Incomplete reaction or byproducts lead to product loss Therefore, the 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 semimetallic 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 semimetal compounds be implemented. 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 A, th and aryloxymetalates, Aryloxyhalbmetalla- and aryloxy esters of oxo acids-forming non-metals, which are different from carbon and nitrogen, is selected, with

at least one compound B selected from formaldehyde and formaldehyde equivalents,

in a reaction medium substantially anhydrous, using compound B in an amount such that the molar ratio of formaldehyde to aryloxy groups in compound A is at least 0.9: 1, making composite materials similar to an arrangement of the phase domains those nanocomposite materials obtainable by twin polymerization as described in the prior art. 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 breaking 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 include aryloxymetalates, aryloxy-half-metalates and aryloxy-esters of nonmetals.

The present invention thus relates to a process for the production of composite materials, which consists essentially of

a) at least one oxidic phase; and

b) at least one organic polymer phase,

the process being the copolymerization of

at least one compound A which is selected from aryloxymetalates, aryloxy-half-metalates and aryloxy esters of non-metallic oxo-acids other than carbon and nitrogen

in a reaction medium which is substantially anhydrous, wherein the compound B is used in an amount such that the molar ratio of formaldehyde or formaldehyde equivalents in compound B to the aryloxy groups in the compound A is at least 0.9: 1, in particular at least 1 : 1, especially at least 1, 01: 1 and especially at least 1.05: 1.

The process according to the invention has a number of advantages. On the one hand, the process according to the invention provides composite materials which are also obtained in the twin polymerization, i. 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 are however, no poorly accessible starting materials such as the spiro compounds mentioned at the outset or labile arylmethyl (semimetals) such as tetrakis (furylmethyloxy) silane are necessary in order to obtain the desired composite materials. Rather, with the Aryloxymetallaten, Aryloxyhalbmetallaten and Ary- loxyestern of non-metals easily accessible and relatively stable starting materials can be used, which allows a production of the composite materials on a larger scale.

Furthermore, by selecting suitable compounds A or mixtures of compounds A, 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 A with one another, 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 various compounds A 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 different compounds A with one another which differ both in the type of metal, semimetal or nonmetal and in the aryl group.

As already mentioned, the method according to the invention provides composite materials which consist of at least one oxidic 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 100 nm or less than 50 nm, and more preferably less than 10 nm. Under adjacent phase domains of identical phases is meant two phase domains of two identical phases passing through one 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.

Aryloxymetalates, Aryloxyhalbmetallaten or aryloxy esters are understood as meaning compounds based on monohydroxyaromatics which formally contain one or more, in particular 1, 2, 3, 4, 5 or 6, monohydroxyaromatics by deprotonation of the aromatic hydrocarbons. having derived from the hydroxylic hydroxyl functional aryloxy groups or anions, wherein the or derived from the monohydroxy aromatic (s) aryloxy group (s) or anion (s) via the deprotonated oxygen atom of the hydroxy group of the monohydroxyaromatic bonded to a metal, semimetal or non-metal is or are. The metal, semimetal or non-metal atoms which form oxo acids and which are different from C and N are also referred to below as the central atoms. The compounds A can have one or more central atoms and, in the case of several central atoms, linear, branched, monocyclic or polycyclic structures. Suitable monohydroxyaromatics are, in particular, phenol, α-naphthol or β-naphthol which are unsubstituted or have one or more, for example 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.

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 from 3 to 20, often from 3 to 10 and especially 5 or 6 carbon atoms. The possible number of carbon atoms of a radical is typically given by the prefix C _n -C _m , where n is the minimum and m is the maximum number of carbon atoms. Here, alkyl is a saturated, linear or branched hydrocarbon radical which typically has 1 to 20, often 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, often 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-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 represents 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, 2-1-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 typically has 3 to 20, often 3 to 10 and especially 5 or 6 carbon atoms and which, for example, cyclopropyl, cyclobutyl, cyclopentyl, 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 is a mono-, bi- or tricyclic, saturated cycloaliphatic radical bonded via an oxygen atom, which typically has 3 to 20, often 3 to 10 and in particular 5 or 6 carbon atoms and which is, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, 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 addition to the aryloxy radical (s), further groups may be bound to the central atom (s), for example 1, 2 or 3 organic radicals which are selected, for example, from alkyl, alkenyl, cycloalkyl or aryl or 1 or 2 oxygen atoms. The total number of bound groups is typically given by the valence of the central atom, i. of the metal, semi-metal or nonmetal to which these groups are attached.

Typically, the central atoms of the compounds A are selected from the elements other than carbon and nitrogen of the following groups of the Periodic Table: IA, such as Li, Na or K, I IA, such as Mg, Ca, Sr or Ba, I NA, such as B, Al, Ga or In, IVA such as Si, Ge, Sn or Pb, VA such as P, As or Sb, VIA such as S, Se or Te, IVB such as Ti or Zr, VB such as V, VI B such as Cr, Mo or W and VI are the same as M n. The central atoms of the compounds A are preferably chosen from the elements of the groups INA, IVA, VA and IVB of the Periodic Table which are different from carbon and nitrogen, and these are in particular among the elements of the second, third and fourth Period. Most preferably, the central atoms are selected from B, Al, Si, Sn, Ti and P.

In a specific embodiment of the invention are used as compounds aryloxy- halbmetallate, i. Compounds of semimetals such as B or Si. In a specific embodiment of the invention, the compound A is selected from aryloxy-half-metals in which the semimetal comprises at least 90 mol%, based on the total amount of semimetal atoms, of silicon.

Compounds A which are suitable according to the invention can be described above all by the following general formula I: [(ArO) _m MO _n Rp] _q (I)

wherein

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

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

n is 0, 1 or 2,

p is 0, 1 or 2,

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

m + 2n + p is 1, 2, 3, 4, 5 or 6 and corresponds to the valency of M, Ar is phenyl or naphthyl, where the phenyl ring or the naphthyl ring are unsubstituted or may have one or more, for example 1, 2, or 3, substituents 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, eg 1, 2 or 3, substituents selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^{b have} the meanings given above.

Of course, when m in formula I is 2, 3, 4, 5 or 6, the radicals Ar may be the same or different and different Ar may differ in the nature of the aromatic cycle and / or in the nature of the substitution pattern. Of course, when p in formula I is 2, the radicals R may be the same or different.

Formula I is to be understood as so-called gross formula; it indicates the type and number of the structural units characteristic of the compounds A, namely the central atom M, and the groups bonded to the central atom, ie the aryloxy group ArO, oxygen atoms O and the carbon-bonded radicals R, and the number of these units. The units [(ArO) _m MO _n Rp] can form mono- or polycyclic structures or linear structures for q> 1.

In formula I, M is 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 elements other than nitrogen and carbon of the following groups of the periodic table: IA, such as Li, Na or K, I IA such as Mg, Ca, Sr or Ba, I NA, such as B, Al, Ga or In, IVA, such as Si, Ge, Sn or Pb, 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 VI IB like Mn. Preferably, M is an element which is selected from the elements of Groups I NA, IVA, VA and IVB of the Periodic Table other than carbon and nitrogen, in particular for a second, third and fourth period element. M is particularly preferably selected from B, Al, 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, p 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 A with formal dehyd or a formaldehyde equivalent copolymerized, wherein in at least one of the compounds of the formula I, the variable p = 0 and in at least one further compound of the formula I, the variable p = 0. Independently of this, the variables m, n, 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 2, 3 or 4;

n is 0 or 1;

p is 0, 1 or 2, in particular 0;

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 -cycloalkyl, alkoxy, in particular C 1 -C 4 -alkoxy, cycloalkoxy, in particular C 3 -C 4 -alkyl. C 1 -C 4 -cycloalkoxy and NR ^a R ^{b are} selected, in which R ^a and R ^b independently of one another represent 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 3 -C 5 -cycloalkyl or phenyl. In particular, the variables m, n, 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 is 1, 2, 3 or 4;

n is 0 or 1;

p 0;

Ar is 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 A are those compounds of the formula I in which q is the number 1. Such compounds can be regarded as ortho-esters of the central atom M underlying oxo-acid. In these compounds, the variables m, n, p, M, Ar and R have the abovementioned meanings and in particular, alone or in combination and especially in combination, one of the preferred or particularly preferred meanings.

A particularly preferred embodiment of compounds A are those compounds of formula I wherein M is selected from B, Si, Sn, Ti and P, m is 3 or 4, n is 0 or 1, p is 0 and q = 1 is. In it, Ar has the aforementioned and in particular the preferred meanings and is in particular 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 very particularly preferred embodiment of the compounds A are those compounds of the formula I in which M is selected from B, Si and Sn, m is 3 or 4, n is 0 and p is 0 and q = 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 -alkoxy , are selected.

A specific embodiment of the compounds A are those compounds of the formula I in which M is Si, m is 4, n is 0 and p is 0. 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 -alkoxy , are selected.

Examples of preferred compounds of the formula I according to the invention where q = 1 are tetraphenoxysilane, tetra (4-methylphenoxy) silane, triphenyl borate, triphenyl phosphate, tetraphenyl titanate, tetrakresyl titanate and tetraphenyl stannate. Further embodiments of compounds A are those compounds of the general formula I in which the radicals Ar are different from one another. This generally lowers the melting point of the compounds A, which may offer advantages in the polymerization. Examples of inventively preferred compounds of formula I with different Ar are triphenoxy (4-methylphenoxy) silane, diphenoxy-bis (4-methylphenoxy) silane, diphenyl (4-methylphenyl) borate, triphenyl (4-methylphenyl) titanate and diphenyl bis (4-methylphenyl) titanate and mixtures thereof. Another specific embodiment of the compounds A are those compounds of the formula I in which M is Si, m is 1, 2 or 3, n is 0 and p is 4-m. 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. 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 A of this embodiment are methyl (triphenoxy) silane, dimethyl (diphenoxy) silane, trimethyl (phenoxy) silane, phenyl (triphenoxy) silane and diphenyl (diphenoxy) silane.

Also suitable as compounds A are "condensation products" of compounds of the formula I where q = 1. These compounds usually have the empirical formula I where q is an integer> 1, e.g. an integer in the range of 2 to 20 and especially for 3, 4, 5 or 6 stands. Such connections are formally accepted

Condensation of compounds of formula I with q = 1, wherein formally in each case 2 units of ArO was removed to form a molecule Ar-O-Ar and a unit M (OAr) _m -2 (0) n + i R _P. Accordingly, they are essentially composed of the structural elements of the following formula Ia:

- [- OA -] - (la) where -A- is a group> M (ArO) _m -2 (0) n (R) _P , wherein M, Ar and R are the abovementioned, in particular those as preferred or having particularly preferred meanings mentioned,

m stands for 3 or 4,

n is 0 or 1 and in particular 0,

p is 0 or 1 and especially 0,

m + 2n + p is 3, 4, 5 or 6 and corresponds to the valency of M.

Preferably, M in the formula A is Si, Sn, B and P.

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:

where k is 1, 2 or 3 and -A- is a group> M (ArO) _m -2 (O) n (R) _P , where M, Ar and R are the meanings mentioned above for formula I and m, n and p have the meanings mentioned above in connection with structure Ia. In another preferred embodiment, condensation product is linear and saturated at the ends with an ArO unit. In other words, such compounds can be described by the following structure Ic: Ar - [- O-A-] _q -OAr (Ic) wherein q is an integer in the range of 2 to 20 and -A- represents a group > M (ArO) _m -2 (0) n () p, where M, Ar and R have the meanings given above for formula I and m, n and p have the meanings mentioned above in connection with structure Ia. This embodiment is particularly preferred if compounds have a distribution with respect to the number of repeat units, that is, with different q. For example, there may be mixtures in which at least 99%, 90%, 80% or 60% of the mass is present as an oligomer mixture with q = 2 to 6 or q = 4 to 9 or q = 6 to 15 or q = 12 to 20.

Examples of such condensation products are triphenylmetaborate, hexaphenoxycyclotrisiloxane or octaphenoxycyclotetrasiloxane.

The compounds A are known or can be prepared analogously to known methods for the preparation of phenates, see e.g. O.F. 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, 1222-130 (1965).

In a further embodiment of the invention, the compounds A comprise at least two mutually different compounds A1 and A2, the compound A1 being selected from compounds of the formula I in which M represents B, Si, Sn, Ti or P and in particular B, Si or Sn, m is 1, 2, 3 or 4, n is 0 or 1, in particular 0, p is 0 and q is 0, 1, 3 or 4 and the compound A2 is selected from compounds of Formula I, wherein M is selected from Si and Sn, m is 2, n is 0, q = 0 and p is 2. In this case, Ar in the compounds A1 and A2 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 5 -C 5 -cycloalkyl or phenyl.

In a further, specific embodiment of the invention, the compounds A comprise at least two mutually different compounds A1 and A2, wherein the Compound A1 is selected from compounds of the formula I in which M is Si, m is 2 or 4, n is 0, p is 0 and q is 1, 3 or 4, and compound A2 is selected from compounds of the formula Formula I, wherein M is Si, m is 2, n is 0 and p is 2. In this case Ar in the compounds A1 and A2 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 ₅ -C ₆ -cycloalkyl or phenyl.

In the process according to the invention, the compounds A and formaldehyde or the formaldehyde equivalent (compounds B) are used in an amount such that the molar ratio of formaldehyde in compound B, i. the amount of monomeric formaldehyde used or the amount of formaldehyde contained in the formaldehyde equivalent, if a formaldehyde equivalent is used, to the aryloxy groups ArO present in the compounds A, at least 0.9: 1, preferably at least 1: 1, in particular at least 1.01: 1, more 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 Aryloxy ArO present in the compounds A does not exceed a value of 10: 1, preferably 5: 1 and in particular 2: 1. 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 A is in the range from 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 5: 1 or 1, 1: 1 to 2: 1.

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) _X , where X indicates the degree of polymerization. These include, in particular, trioxane (3 formaldehyde units) and paraformaldehyde (higher oligomer (CH 2 O) _X ). Preferably, the polymerization is carried out using compounds B (hereinafter also formaldehyde source), which is selected from gaseous formaldehyde, trioxane and paraformaldehyde. In particular, it is trioxane. In a preferred embodiment of the process according to the invention, the polymerization of the compounds A with the formaldehyde source is carried out in the presence of catalytic amounts of an acid. Typically, the acid is used in an amount of from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, based on the compounds A. Preferred acids here are Bronsted acids, for example organic carboxylic acids such as trifluoroacetic acid, oxalic acid or lactic acid, and organic sulfonic acids, in particular C 1 -C 20 -alkanesulfonic acids such as methanesulfonic acid, octanesulfonic acid, decanesulfonic acid or dodecane sulfonates, haloalkanesulfonic acids such as trifluoromethanesulfonic acid, benzenesulfonic acid or C 20 -alkylbenzenesulfonic acids, toluenesulfonic acid, nonylbenzenesulfonic acid or dodecylbenzenesulfonic acid. Also suitable are inorganic Bronsted acids such as HCl, H2SO4 or HCIO4. As Lewis acid, for example, BF3, BCI3, SnCl ₄ , TiCl ₄ , or AICI3 can be used. The use of complexed or dissolved in ionic liquids Lewis acids is also possible. The polymerization 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, Kt.Butylat or Mg-ethylate.

The polymerization can also be initiated thermally, i. the polymerization takes place without the addition of an acid by heating a mixture of the compounds A and B. The temperatures required for the polymerization are typically in the range of 50 to 250 ° C, in particular in the range of 80 to 200 ° C. In the case of an acid- or base-catalyzed polymerization, the polymerization temperatures are typically in the range from 50 to 200 ° C. and in particular in the range from 80 to 150 ° C. In the case of thermally initiated polymerization, the polymerization temperatures are typically in the range from 120 to 250 ° C. and in particular in the range from 150 to 200 ° C.

The polymerization can in principle be carried out as a so-called batch or as an addition process. When carried out as a batch, the compounds A and B in the desired amount in the reaction vessel and brought to the conditions required for the polymerization. In the addition process, at least one of the two components, ie compound A and / or compound B, is at least partially fed in the course of the polymerization until the desired quantitative ratio of compound A to compound B has been reached. Optionally, the addition is followed by a post-reaction phase. Preferably, the implementation is as a batch.

It has proved to be advantageous if the polymerization is carried out in one stage (in one stage), ie. the polymerization is carried out as a batch with the total amount of the compounds A and B to be polymerized, or the addition process is carried out in which the addition of the compounds A and B takes place so that the polymerization conditions are not interrupted until the total amount of the compounds A and B have been placed in the reaction vessel. The polymerization of compounds A and B can be carried out in bulk or in an inert diluent. Suitable diluents are, for example, halogenated hydrocarbons such as dichloromethane, trichloromethane, dichloroethene or hydrocarbons, for example aromatic hydrocarbons such as mono- or polysubstituted by C 1 -C 4 -alkyl-substituted benzene or naphthalene, e.g. Toluene, xylene, cumene or mesitylene or mono- and C 1 -C 4 -alkylnaphthalenes, furthermore aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane, heptane, cycloheptane, octane and its isomers, nonane and its isomers, decane and its isomers and their mixtures. Preferably, the polymerization of compounds A and B is carried out with substantial absence of water, i. the concentration of water at the beginning of the polymerization is less than 0.1 wt .-%.

For the preparation of particulate composite materials, it has been found useful to carry out the reaction of the compound A with the compound B in an inert diluent. Preferred inert diluents are those which are at least 80% by volume, in particular at least 90% by volume and especially at least 99% by volume or 100% by volume, based on the total amount of diluent, of the abovementioned hydrocarbons consist, aromatic hydrocarbons such as mono- or polysubstituted by Ci-C-4-alkyl-substituted benzene or naphthalene, eg Toluene,

Xylene, cumene or mesitylene or mono- and C 1 -C 4 -alkylnaphthalenes, furthermore aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane, heptane, cycloheptane, octane and its isomers, nonane and its isomers, decane and its isomers and mixtures thereof , For the preparation of particulate composite materials, it has also been found useful to carry out the reaction of the compound A with the compound B in the presence of at least one surface-active substance, preferably in an inert diluent.

Suitable surface-active substances are, in particular, anionic emulsifiers and nonionic emulsifiers. Anionic emulsifiers generally have, in addition to at least one hydrophobic group, e.g. at least one aliphatic group or araliphatic group having at least 6 C atoms, especially at least 10 C atoms or at least one oligo- or poly (alkylsiloxane) group and at least one anionic group, e.g. 1 or 2 anionic groups, for example, sulfonate groups and

Phosphonate groups are selected, wherein the sulfonate groups and phosphonate groups may also be present as sulfate groups or phosphate groups. Preferred inorganic anionic emulsifiers have 1 or 2 sulfonate or sulfate groups. The anionic emulsifiers include aliphatic, araliphatic and aromatic sulfonic acids having generally at least 6 C atoms and salts thereof, in particular their ammonium and alkali metal salts, sulfuric monoesters of ethoxylated alkanols and alkylphenols and salts thereof, in particular their ammonium and alkali metal salts, and Alkyl, aralkyl and aryl phosphates including phosphoric acid half esters of alkanols and alkylphenols and salts thereof, in particular their ammonium and alkali metal salts.

Preferred anionic emulsifiers are:

Alkali and ammonium salts of dialkyl esters of sulfosuccinic acid (alkyl radical:

Alkali and ammonium salts of alkyl sulfates (alkyl radical: Cs to Cis),

Alkali and ammonium salts of alkyl sulfonates (alkyl radical: Cs to Cis),

Alkali and ammonium salts of alkylarylsulfonic acids (alkyl radical: Cs to Cis), compounds of the general formula

wherein R ¹ and R ^{2 are} hydrogen or C ₄ - to cis-alkyl and are not simultaneously hydrogen, and X and Y may be alkali metal ions and / or ammonium ions. R ¹ , R ^{2 are} preferably linear or branched alkyl radicals having 6 to 14 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, where R ¹ and R ^{2 are} not both simultaneously hydrogen. X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous compounds are those in which X and Y are sodium, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} hydrogen or has one of the meanings given for R ¹ other than hydrogen. Industrial mixtures are used, which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax ^® 2A1 (trademark of Dow Chemical Company).

The anionic emulsifiers can also be used in their acidic form and then act as initiators.

Examples of suitable nonionic emulsifiers are typically ethoxylated alkanols having 8 to 36 carbon atoms in the alkyl radical, ethoxylated mono-, di- and tri-

Alkylphenols having typically 4 to 12 carbon atoms in the alkyl radicals, wherein the ethoxylated alkanols and alkylphenols typically have a degree of ethoxylation in the range of 2 to 100, in particular 3 to 50. Examples of suitable nonionic surface-active compounds are furthermore ethoxylated oligo- and poly (dialkylsiloxanes), in particular ethoxylated oligo- and poly (dimethylsiloxanes), these compounds having at least 2, e.g. 2 to 50 dialkylsiloxane units and a degree of ethoxylation in the range of 2 to 100, in particular 3 to 50 have.

The polymerization of compounds A and B may be followed by purification steps and optionally drying steps.

The polymerization of compounds A and B may be followed by calcination. Here, the organic polymeric material formed in the polymerization of the monomer unit (s) B is carbonized to the carbon phase. The polymerization of compounds A and B may be followed by oxidative removal of the organic polymer phase. In this case, the organic polymeric material formed during the polymerization of the organic constituents is oxidized and a nanoporous oxidic or nitridic material is obtained.

The composite material obtainable by the process of the present invention has at least one oxide phase containing the metal, metalloid or non-metal other than C and N, and at least one organic polymer phase resulting from polymerization of the aryloxy groups with the formaldehyde. The dimensions of the phase domains in the resulting composite material are usually in the range of a few nanometers, but it is possible to obtain materials with domain sizes up to 100-200 nm. In addition, the phase domains of the oxide phase and the phase domains of the organic phase usually have a co-continuous arrangement, ie both the organic phase and the inorganic or organometallic phase penetrate each other and form substantially no discontinuous areas. 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 100 nm, often at most 50 nm, in particular a maximum of 10 nm or a maximum of 5 nm and especially a maximum of 2 nm but it is possible to obtain materials with domain sizes up to 100-200 nm. A macroscopically visible separation into discontinuous domains of the respective phase does not occur. 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 respect to the term continuous phase domain, discontinuous phase domain, and co-continuous phase domain, also 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, especially p. 2003. Hereinafter, a co-continuous arrangement of a two-component mixture means 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 interconnected by a continuous path, without the path being a phase interface traverses / thwarted. 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, depending on the compounds A selected, an oxide of the (semi) metal or the non-metal or a mixed form results. 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, for example 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 .-%.

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 essentially co-continuous phase domains, with the mean distance between two adjacent domains of identical phases generally 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, for example under nitrogen or argon. Preferably, the inert gas atmosphere will contain less than 1% by volume, in particular less than 0.1% by volume, of oxygen. In a likewise preferred embodiment of the invention, the calcination is carried out under reducing conditions, for example in an atmosphere comprising hydrogen (h), 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. The composite materials obtainable according to the invention and the porous, in particular nanoporous, inorganic materials produced therefrom as well as the electroactive nanocomposite materials which, in addition to an inorganic phase of a (semi-) metal, which may be both oxidic and (semi-) metallic, have a carbon phase C. can be successfully used in many applications to solve known problems or to improve properties.

For example, the composite materials obtainable according to the invention are suitable for the production of porous carbon materials for the storage of gases, in particular for the h-storage, for example in analogy to the manner described in WO 2009/083082. The relevant disclosure in WO 2009/083082 is hereby incorporated by reference in its entirety. The composite materials obtainable according to the invention, in particular those containing silicon, are also suitable for the production of elastomer or rubber compounds, especially rubber compounds for the production of pneumatic tires, for example in analogy to the manner described in US Pat. No. 201,140,0197. The relevant disclosure in US 201 1 -0240197 is hereby incorporated by reference.

The composite materials obtainable according to the invention are furthermore suitable for the production of porous oxidic materials which are used as so-called low-k dielectrics, ie as dielectrics with low dielectric constants (k <3.7), for example in analogy to that described in WO 2009/133082 Wise. The relevant disclosure in WO 2009/133082 is hereby incorporated by reference in its entirety.

The composite materials obtainable according to the invention, in particular those containing silicon, are furthermore suitable for the production of electroactive materials which are suitable for lithium ion batteries, especially for anode materials, for example in analogy to the manner described in WO 2010/1 12580. The relevant disclosure in WO 2010/1 12580 is hereby incorporated by reference in its entirety. Furthermore, the composite materials according to the invention can be used in analogy to the manner described in WO 201 1/000858 for the production of separators for electrochemical cells, especially for lithium cells. The relevant disclosure in WO 201 1/000858 is hereby incorporated by reference in its entirety. Furthermore, the composite materials according to the invention can be used in analogy to the manner described in WO 201 1/039139 for the preparation of membranes for separation processes. The relevant disclosure in WO 201 1/039139 is hereby incorporated by reference in its entirety.

The following examples and figures serve to illustrate the invention.

I. Analysis: The samples obtained in the copolymerization were examined by means of TEM: The TEM investigations were carried out as HAADF-STEM using a Tecnai F20 transmission electron microscope (FEI, Eindhoven, NL) at a working voltage of 200 kV in ultrathin layer technique (embedding of the samples in synthetic resin as a matrix). The results are shown in the following Figures 1 a, 1 b, 2 a, 2 b, 3 and 4. Arrows in the figures indicate particularly characteristic areas of the sample, indicating that the domain distances are in the range of a few nm (<10 nm).

II. Illustrations:

Figure 1 a: HAADF-STEM examination of the sample from Example 1 with a magnification of 2x10 ⁵ .

Figure 1 b: HAADF-STEM examination of the sample from Example 1 with an enlargement of 10 ⁶ .

Figure 2a: HAADF-STEM examination of the sample from Example 2 with a magnification of 2x10 ⁴ . Uniform black areas are due to the embedding agent.

Figure 2b: HAADF-STEM examination of the sample from Example 2 with a magnification of 10 ⁶ .

Figure 3: HAADF-STEM examination of the sample from Example 3 with an enlargement of 10 ⁶ .

Figure 4: HAADF-STEM examination of the sample from Example 4 with a magnification of 10 ⁶ . Figure 5: HAADF-STEM examination of the sample from Example 9 with a magnification of 10 ⁶ .

Figure 6: HAADF-STEM examination of the sample from Example 20 with an enlargement of 10 ⁶ .

III. Used compounds A:

Tetraphenylsilicate (compound of the formula I where M = Si, m = 4, n = p = 0, q = 1, Ar = phenyl)

In a 2-L four-necked flask equipped with glass stirrer and sleeve, condenser with bubble counter and washing tower, 498 g of phenol were placed and melted at 70 ° C. 270 g of SiCl ₄ were added dropwise so that the scrubbing tower could bind the resulting amounts of HCl. With decreasing HCI evolution, the internal temperature was slowly increased (about 6 h) to 250 ° C. 550 g of a pale, clear oil were obtained, which crystallized at room temperature.

¹ H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ): 7.25 ppm (2H, triplet), 7.05 ppm (1H, triplet), 7.03 ppm (2H, doublet) hexaphenoxycyclotrisiloxane (Compound of the formula I where M = Si, m = 2, n = 1, p = 0, q = 3 or Ib with M = Si, m = 4, n = 0, p = 0, k = 1, Ar = Phenyl)

a) In a 1-L four-necked flask equipped with glass stirrer and sleeve, condenser with bubble counter and wash tower, 188 g of phenol were introduced and melted at 50 ° C. 170 g of SiCU were added dropwise so that the wash tower could bind the resulting HCl amounts. As the evolution of HCl decreased, the internal temperature was slowly increased (about 6 h) to 250 ° C. 310 g of a light, clear oil were obtained.

¹ H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ): 2 signal groups 7.4 - 7.2 ppm (2X2H), 6.95-7.15 ppm (2X3H) b) In a 0.5- L four-necked flask equipped with glass stirrer and sleeve, bubble counter and washing tower condenser was charged with 57 g of the adduct of a) in 200 ml of toluene. 3.2 g of water in 50 ml of dry THF were added dropwise at 25 ° C and stirred for 1 h. The solution was aspirated with exclusion of water and evaporated on a rotary evaporator at 80 ° C / 10 mbar. One received 38 g of a bright, clear oil, which crystallized.

¹ H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ): 7.25 ppm (triplet, 3X2H); 7.04 ppm (triplet, 3X1 H); 7.03 ppm (doublet, 3X2H) Triphenylmetaborate (compound of the formula I where M = B, m = 1, n = 1, p = 0, q = 3 and Ar = phenyl or Ib where M = B, m = 3, n = 0, p = 0, k = 1 and Ar = phenyl)

In a 2-L four-necked flask equipped with glass stirrer, thermometer and condenser, 156 g of boric acid and 400 mL of xylene were submitted. The batch was heated to reflux. After 2 hours, the condenser was removed and a Wasserauskreiser put on. Within 3 h, a total of 41 mL of water were removed from the system at an internal temperature of 122-138 ° C. Subsequently, the reaction mixture was heated to reflux and was added within 1 h, a solution of 226 g of phenol in 300 mL of xylene. Thereafter, the mixture was stirred for a further 5 h under reflux and circled a total of another 22 mL of water. The resulting reaction mixture was concentrated at 100 ° C and 5 mbar to dryness. 230 g of the title compound were obtained as a solid.

¹ H-NM R (500 MHz, 16 scans, CD ₂ CI ₂ ): 7.29 ppm (2H, triplet), 7.12 ppm (1H, triplet), 7.05 ppm (2H, doublet) p- Tolyl-diphenylmetaborat (mixture of compounds of formula I with M = B, m = 1, n = 1, p = 0, q = 3 and Ar = phenyl and p-toly or mixture of compounds of

In a 2-L four-necked flask equipped with glass stirrer, thermometer and condenser, 185 g of boric acid and 500 mL of xylene were submitted. The batch was heated to reflux. After 2 hours, the condenser was removed and a Wasserauskreiser put on. Within 3 h, 52 mL of water were removed at an internal temperature of 122-137 ° C. Subsequently, the reaction mixture was heated to reflux and this was within 1 h, a solution of 198 g of phenol and 108 g of p-cresol in 300 mL of xylene. Thereafter, the mixture was stirred for a further 5 h under reflux and circled a total of 46 mL of water. The resulting reaction mixture was concentrated at 100 ° C and 5 mbar to dryness. This gave 340 g of a mixture of tri-p-tolyl-metaborate (1), di-p-tolylphenyl-metaborate (2), p-tolyl-diphenyl-metaborate (3) and triphenyl-metaborate (4) as a solid. ¹ H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ):

7.4 - 6.6 ppm (14 H, various superimposed aromatic signals)

2.31 ppm (3H, singlet) tetraphenyltitanate (compound of the formula I where M = Ti, m = 4, n = p = 0, q = 1, Ar = phenyl)

The preparation was carried out according to the method described in DE 1816241.

Tetrakresyl titanate (compound of formula I where M = Ti, m = 4, n = p = 0, q = 1, Ar = 4-methylphenyl) - Commercial product

Triphenyl phosphate (compound of the formula I where M = P, m = 3, n = 1, p = 0, q = 1, Ar = phenyl) - commercial product aluminum phenolate: (compound of the formula I where M = Al, m = 3, n = p = 0, q = 1, Ar = phenyl)

In a 0.5 L 4-necked flask equipped with stirrer, condenser with bubble counter and washing tower, 188 g of phenol were introduced and melted at 50 ° C. 30 g of AlC were added at 50 ° -70 ° C in 3 portions, in which case the temperature was increased in each case to about 180 ° C and maintained until the completion of HCI development. Excess phenol was then removed at 180 ° C bath temperature, at the end of water jet vacuum was applied. In this way, 95 g of the title compound were obtained as an oil, which solidifies at about 130 ° C crystalline. The title compound is insoluble in dichloromethane, acetone, chloroform or toluene and soluble in DMSO.

¹ H-NMR (500 MHz, 16 scans, DMSO-D ₆ ): 9.36 ppm (1H, singlet), 7.16 ppm (2H, triplet), 6.76 ppm (1H, triplet), 6 , 75 ppm (2H, doublet), besides about 5% free phenol and water at 3.34 ppm and DMSO-D5

Tetra (4-methylphenyl) silicate (compound of the formula I where M = Si, m = 4, n = p = 0, q = 1, Ar = 4-methylphenyl)

In a 1 L 4-necked flask equipped with glass stirrer, condenser with bubble counter and washing tower, 229 g of p-cresol were placed and melted at 50 ° C. 107 g of SiCU were added dropwise so that the scrubbing tower was able to bind the resulting amounts of HCl. As HCI evolution slowed, the indoor temperature slowly (about 6h) to 250 ° C. 210 g of a pale, clear oil were obtained, which crystallized at room temperature.

¹ H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ): 7.04 ppm (2H, doublet), 6.89 ppm (2H, doublet),

Diphenoxy-dimethylsilane (compound of the formula I where M = Si, m = 2, n = 0, p = 2, q = 1, Ar = phenyl, R = methyl)

In a 1 L 4-necked flask equipped with glass stirrer, condenser with bubble counter and washing tower, 344 g of phenol were placed and melted at 50 ° C. Here- was added dropwise to 227 g (CH3) ₂ SiCl ₂ to such that the washing tower the HCI formed was able to bind amounts. With decreasing HCI evolution, the internal temperature was slowly increased (about 6 hours) to 250 ° C. This gave 440 g of a light, clear oil.

¹ H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ): 7.24 ppm (2x2H, triplet), 6.98 ppm (2x1H, triplet), 6.94 ppm (2x2H, doublet), 0, 36 ppm (2x3H, singlet)

IV. Examples according to the invention:

Example 1: Polymerization of tetraphenylsilicate in substance

3 g of trioxane and 10 g of tetraphenylsilicate were melted in a 100 mL round bottom flask on a rotary evaporator at 65 ° C to give a homogeneous, clear solution. To this was added 100 mg of trifluoroacetic acid and homogenized. A quantity of 5 g was filled into a penicillin jar, provided with a crimp cap and heated to 90-100 ° C in a drying oven. After 15 h, a clear, transparent resin body of 4.4 g was obtained.

A sample of the obtained resin body was examined by HAADF-STEM. The phase structure is shown in Figures 1 a and 1 b and demonstrates the presence of domain sizes in the range of a few nanometers (<10 nm).

Example 2: Precipitation polymerization of tetraphenylsilicate in solution

In a 250 mL four-necked flask, 20.0 g of tetraphenylsilicate were melted with 6.6 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 became mushy and 60 g of xylene were added and boiled for a further 30 min at reflux. The approach was up Cooled room temperature, filtered with suction through a D4 frit, washed with xylene and dried in a vacuum oven. This gave 22.5 g of a finely divided pink powder with an average particle size of 14 μιτι, which consist of spherical primary particles with about 1 μιτι diameter (see Figure 2a). The primary particles showed typical twin-structure domain structures with dimensions in the 2-5 nm range (see Figure 2b).

Example 3: Polymerization of Triphenyl Phosphate in Substance 33 g of trioxane and 109 g of triphenyl phosphate were melted in a round bottom flask on a rotary evaporator at 50 ° C., giving a homogeneous, clear solution.

Experiment a)

5 g of this solution were filled into a 50 mL ampoule and 51 mg trifluoroacetic acid and homogenized. The ampoule was provided with a crimp cap and heated to 90-140 ° C in a drying oven. After 5 days, a dark brown resin body of 4.2 g was obtained.

Trial b)

5 g of this solution was poured into a 50 mL ampoule and 55 mg of lactic acid and homogenized. The ampoule was provided with a crimp cap and heated to 90-140 ° C in a drying oven. After 5 days, a dark green resin body of 4.1 g was obtained.

A sample of the obtained resin body was examined by HAADF-STEM. The phase structure is shown in Figure 3 and demonstrates the presence of domain sizes in the range of a few nanometers (<10 nm).

Example 4: Polymerization of Tetrakresyltitanat in substance 27.8 g of trioxane and 100 g Tetrakresyltitanant were melted in a round bottom flask on a rotary evaporator at 50 ° C to give a homogeneous, clear solution. 5 g of this solution were poured into a 50 ml ampoule and 61 mg of trifluoroacetic acid were homogenized. The ampoule was provided with a crimp cap and heated to 120-140 ° C in a drying oven. After 6 days, a brittle, red-brown resin body of 4 g was obtained.

A sample of the obtained resin body was examined by HAADF-STEM. The phase structure is shown in Figure 3 and demonstrates the presence of domain sizes in the range of a few nanometers (<10 nm). Example 5: Polymerization of Triphenylmetaborate in Substance

4 g of boron ester were melted at 90-100 ° C in a 20 ml_ ampoule. To this was added 1, 1 g of trioxane. The sample was stored for 1 d in a drying oven at 100 ° C. A polymer was obtained in an amount of 5 g.

EXAMPLE 6 Precipitation Polymerization of Triphenyl Metaborate in Solution In a 250 ml four-necked flask, 20.0 g of triphenylborate were melted with 5.5 g of trioxane under nitrogen at 50-55 ° C. and diluted with 80 g of xylene. To this was added 0.2 g of methanesulfonic acid at 55 ° C and homogenized. Subsequently, the mixture was stirred at 80 ° C. for 30 minutes at a stirrer speed of 600 rpm, at 100 ° C. for 30 minutes and at 120 ° C. for 30 minutes. The approach was cloudy and there was a sandy coating on the piston wall. The batch was cooled to room temperature, filtered off with suction through a D4 frit, washed with xylene and dried in a vacuum oven. 20.5 g of a pink powder were obtained.

Example 7: Precipitation polymerization of p-tolyl-diphenyl metaborate in solution

In a 500 mL HWS vessel with Ultra-Turrax stirrer and reflux condenser, 60.0 g of p-tolyl-diphenyl metaborate (see above for substance mixture) were mixed with 40 g of xylene and with 19.5 g of trioxane under nitrogen at 50-55 ° C melted and the melt was diluted with 200 g of xylene. To this was added 0.8 g of methanesulfonic acid at 55 ° C and homogenized. Subsequently, the mixture was stirred at 80 ° C. for 30 minutes at a stirrer speed of 8000 rpm, at 100 ° C. for 30 minutes and at 120 ° C. for 30 minutes. The approach became cloudy and there was a sandy precipitate. The reaction mixture was cooled to room temperature, filtered with suction through a D4 frit, the residue washed with xylene and dried in a vacuum oven. 58.5 g of a red-colored powder were obtained.

The average particle size (surface-averaged) of the powder determined by light scattering (Mastersizer 2000) was determined to be 27 μιτι. Elemental analysis (thermally stable oxides can lead to minor findings):

C19H17B306 C H O B Total

Theory 61, 1 4,6 25,7 8,7 100,0

Found 54.9 5.4 26.0 6.8 93.1 Examples 8-1 to 8-12:

The compounds of the formula I and trioxane indicated in Table 1 were mixed in the amounts indicated in Table 1 and melted in a 20 ml penicillin glass at 60 to 70 ° C. 0.05 g of trifluoroacetic acid was then added to the melt, the penicillin glass sealed with a metal Teflon cap and heated to 1 10 ° C for 48 h. The mixtures of Examples 1 to 7 gave red to brown, clear transparent composite materials, examples 8 to 12 red to brown opaque composite materials.

Table 1 (Examples 8-1 to 8-12)

Monomer A: tetra (4-methylphenyl) silicate

Monomer B: tetraphenylsilicate

Monomer C: diphenoxydimethylsilane

Example 9: 1, 00 Tetraphenyltitanat and 0.32 g of trioxane were placed in a penicillin and brought into solution by the addition of 1, 3 g of toluene. The penicillin was closed and heated to 90 ° C. After 1 h, the polymerization was complete. A powder was obtained. Examples 10 to 16: Production of Particulate Nanocomposite Materials The particle size distribution of the powders prepared in Examples 10 to 16 was determined by Fraunhoferbeugung on a Malvern Master Sizer S, (module: cuvette MS7, analytical model: polydisperses) at 23 ° C.

Elemental analysis: the Si determination was carried out after reaction of the samples with concentrated sulfuric acid and subsequent digestion with soda / borax using optical emission spectrometry (ICP-OES, Varian, model: Varian Vista Pro). The carbon analysis was carried out according to the classical method of elemental analysis (Dumas) (F. Ehrenberger "Quantitative Organic Elemental Analysis" ISBN 3-527-28056-1). Device: company Elementar, device type: elemental analyzer, model: Vario EL Cube or Vario Micro Cube

Example 10:

In a 2 l glass flask equipped with a stirrer, reflux condenser and metering devices, tetraphenylsilicate (100 g), 1, 3,5-trioxane (45 g) and xylene (isomer mixture, 850 g) were added at room temperature and under a nitrogen atmosphere. initially charged and heated to 80 ° C at atmospheric pressure with stirring (100 rpm). When the temperature was reached, the stirrer speed was set to 400 rpm and stirred until a clear solution had formed (about 5 minutes). A solution of 4-dodecylbenzenesulphonic acid (5.2 g) in xylene (isomer mixture, 40 g) was added over 10 minutes. Thereafter, the temperature was raised to 135 ° C (bath temperature) and it was polymerized under the predetermined conditions for 3 hours. After cooling, a sample of the suspension was taken to determine the particle size distribution (weight average (D50) = 1 15 μιτι). The composite material was isolated by filtration and subsequently dried (yield 142 g).

Example 1 1:

In a 250 ml glass flask equipped with a magnetic stirrer and reflux condenser, at room temperature and under a nitrogen atmosphere, tetraphenylsilicate (18.4 g), 1, 3,5-trioxane (8.3 g) and xylene (isomer mixture, 123 g) were and heated at 70 ° C under atmospheric pressure with stirring (325 rpm). Upon reaching the temperature, 0.34 g of methanesulfonic acid was added. Thereafter, the temperature was raised to 135 ° C and polymerized under the predetermined conditions for 3 hours. After cooling, the solid composite material was separated by filtration from the liquid reaction phase and subsequently dried (yield 14.0 g). Element analysis: C 69.7%, Si 5.9%

Example 12:

In a 250 ml glass flask equipped with a magnetic stirrer and reflux condenser at room temperature and under nitrogen atmosphere tetrakis (4- methylphenyl) silicate (10.8 g), 1, 3,5-trioxane (4.2 g) and xylene (mixture of isomers, 85.0 g) and heated to 70 ° C at atmospheric pressure with stirring (325 rpm) , Upon reaching the temperature, 0.23 g of methanesulfonic acid was added. Thereafter, the temperature was raised to 135 ° C and polymerized under the predetermined conditions for 3 hours. After cooling, the composite material was separated by filtration from the liquid reaction phase and subsequently dried (yield 3.60 g). Elemental analysis: C 48.6%, Si 15.3%

Example 13:

In a 2 l glass flask equipped with a homogenizer (Polytron® PT 6100), baffles, reflux condenser and dosing devices, tetraphenylsilicate (48.3 g), 1, 3,5-trioxane (21, 7 g) was incubated at room temperature and under a nitrogen atmosphere. and n-decane (400 g) and heated to 80 ° C at atmospheric pressure with stirring (1000 rpm). When the temperature was reached, the stirrer speed was set to 7000 rpm and a solution of 4-dodecylbenzenesulfonic acid (7.0 g) in n-decane (40 g) was metered in within 10 minutes. Thereafter, the temperature was raised to 135 ° C (bath temperature) and it was polymerized under the predetermined conditions for 3 hours. After cooling, a sample of the suspension was taken to determine the particle size distribution (weight average (D50) = 11 cm). The composite material was separated by filtration from the liquid reaction phase and subsequently dried (yield 58.2 g).

Example 14:

In a 2 l glass flask equipped with a homogenizer (Polytron® PT 6100), baffles, reflux condenser and dosing devices, tetraphenylsilicate (48.3 g), 1, 3,5-trioxane (21, 7 g) was incubated at room temperature and under a nitrogen atmosphere. and n-decane (400 g) and heated to 80 ° C at atmospheric pressure with stirring (1000 rpm). When the temperature was reached, the stirrer speed was set at 7000 rpm and sodium dodecylbenzenesulfonate (7.0 g) was added. Thereafter, within 10 minutes, a solution of methanesulfonic acid (1, 1 g) in n-

Decane (40 g) added. The temperature was raised to 135 ° C. Under the given conditions was polymerized for 3 hours. After cooling, a sample of the suspension was taken to determine the particle size distribution (weight average (D50) = 11 cm). The composite material was separated by filtration from the liquid reaction phase and subsequently dried (yield 57.5 g).

Example 15:

In a 2 l glass flask equipped with a homogenizer (Polytron® PT 6100), baffles, reflux condenser and dosing devices were placed at room temperature and under nitrogen atmosphere tetraphenylsilicate (48.3 g), 1, 3,5-trioxane (21, 7 g) and n-decane (400 g) and heated at atmospheric pressure with stirring (1000 rpm) to 80 ° C. When the temperature was reached, the stirrer speed was set to 7000 rpm. To this was added sodium dodecylbenzenesulfonate (7.0 g) and a solution of tin tetrachloride (2.5 g) in n-decane (40 g) added in 10 minutes. Thereafter, the temperature was raised to 135 ° C and it was polymerized under the predetermined conditions for 3 hours. After cooling, a sample of the suspension was taken to determine the particle size distribution (weight average (D50) = 18 μιτι). The composite material was separated by filtration from the liquid reaction phase and subsequently dried (yield 28.8 g).

Example 16:

In a 2 l glass flask equipped with a homogenizer (Polytron® PT 6100), baffles, reflux condenser and dosing devices, tetraphenoxytitanium (50.7 g), 1, 3,5-trioxane (21, 7 g) were incubated at room temperature and under a nitrogen atmosphere. and n-decane (400 g) and heated to 80 ° C at atmospheric pressure with stirring (1000 rpm). When the temperature was reached, the stirrer speed was set at 7000 rpm and sodium dodecylbenzenesulfonate (7.0 g) was added. Thereafter, the temperature was raised to 135 ° C and it was polymerized under the given conditions for 3 hours. After cooling, a sample of the suspension was taken to determine the particle size distribution (weight average (D50) = 14 μιτι). The composite material was separated by filtration from the liquid reaction phase and subsequently dried (yield 50.7 g). applications

Example 17: Preparation of a B2O3 / C hybrid material

8.9 g of the powder from example 7 were calcined in a tube furnace under a stream of argon, the following temperature / time profile being chosen:

Heat at 3 - 4 ° C / min to 800 ° C

Residence time 120 min at 800 ° C

Cool overnight to room temperature.

This gave 4.9 g of a caked black solid, which could easily be rubbed into powder.

Elemental analysis:

C H O B Total

Found 59.1 1, 1 27.5 1 1, 1 98.8 Example 18: Producing a highly porous carbon

4 g of the powder from Example 17 were stirred with 70 ml of water at 70 ° C for 2 h. It was then allowed to cool to 23 ° C and filtered the approach through a 4D glass frit. The residue was washed with a little water and dried at 60 ° C. in a vacuum oven. In this way, 2.6 g of a black fine powder consisting essentially of elemental carbon was obtained.

Elemental analysis:

In a BET experiment, the surface properties of the carbon powder were determined:

Surface (Langmuir - evaluation): 715 m ² / g

Surface (multipoint evaluation): 517 m ² / g

Total pore volume: 0.442 ml / g

Average pore radius: 16.2 Ä

Example 19: Recovery of Boric Acid The water phase (filtrate) from example 18 was rotary evaporated to 100 ° C./15 mbar on a rotary evaporator. In this way, 2.2 g of a white powder, which proved after elemental analysis as boric acid B (OH) 3.

Elemental analysis:

Example 20: Preparation of a Nanoporous Titanium Dioxide

In a tube furnace, the powder from Example 9 was heated in an air stream to 500 ° C and held at this temperature for 4 h. This gave a fine white powder which was identified as titanium dioxide by elemental analysis. An X-ray powder diffractogram showed that it was titania in the Antas modification. A TEM study is shown in Figure 6.

Claims

claims:

1 . Process for the preparation of a composite material

a) at least one oxidic phase; and

b) an organic polymer phase;

by copolymerization of

at least one compound A which is selected from aryloxymetalates, aryloxy-half-metalates and aryloxy esters of non-metals forming oxo acids other than carbon and nitrogen, with at least one compound B which comprises formaldehyde and formaldehyde

Equivalents is selected

in a reaction medium which is substantially anhydrous, wherein the compound B is used in an amount such that the molar ratio of formaldehyde to the aryloxy groups in compound A is at least 0.9: 1.

A process according to claim 1, wherein the metal, metalloid or non-metal of the compounds A is selected from among elements other than carbon and nitrogen of groups IA, IIA, INA, IVA, VA, VIA, IVB, VB, VIB and VIIB of the periodic table.

3. The method of claim 1 or 2, wherein the metal, semimetal or non-metal of the compounds A is selected from Li, Na, K, Mg, Ca, Sr, Ba, B, Al, Ga, In, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Ti, Zr, V, Cr, Mn and W. 4. The method of claim 3, wherein the metal, metalloid or nonmetal of the compounds A is selected from B, Si, Sn, Ti and P.

5. The method according to any one of the preceding claims, wherein compound A is selected from Aryloxyhalbmetallaten wherein the semimetal comprises at least 90 mol%, based on the total amount of semimetal atoms, silicon.

6. The method according to any one of the preceding claims, wherein the compound B is used in an amount such that the molar ratio of formaldehyde in compound B to the aryloxy groups in compound A in the range of 1: 1 to 10: 1 and in particular in the range of 1, 05: 1 to 2: 1 is.

7. The method according to any one of the preceding claims, wherein the compounds A are described by the general formula I:

[(ArO) _m MO _n Rp] _q (I) wherein

M for a metal, metalloid or for an oxo acids, from

Carbon and nitrogen are different non-metals;

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

n is 0, 1 or 2,

p is 0, 1 or 2,

q for an integer, e.g. 1, 2, 3, 4, 5 or 6,

m + 2n + p is 1, 2, 3, 4, 5 or 6 and the valency of M, Ar is phenyl or naphthyl, wherein the phenyl ring or the

Naphthyl ring are unsubstituted or may have one or more substituents 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 selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR ^a R ^b , wherein R ^a and R ^b are as above have mentioned meanings. 8. The method of claim 7, wherein M is selected from B, Si, Sn, Ti and P, m is 1, 2, 3 or 4, n is 0 or 1 and p is 0.

9. The method according to claim 7 or 8, wherein the compound A comprises at least two mutually different compounds A1 and A2, wherein compound A1 is selected from compounds of the molecular formula I, wherein M is selected from B, Si, Sn, Ti and P, m is 1, 2, 3 or 4, n is 0 or 1 and p is 0 and the compound A2 is selected from compounds of the molecular formula I, wherein M is selected from Si and Sn, m is 2, n is 0 and p stands for 2.

10. The method of claim 6, 7 or 8, wherein the compounds A are selected from tetraphenoxysilane, hexaphenoxycyclotrisiloxane, octaphenoxycyclo tetrasiloxane, tetra (4-methylphenoxy) silane, methyl (triphenoxy) silane, dimethyl (diphenoxy) silane, trimethyl ( phenoxy) silane, phenyl (triphenoxy) silane, diphenyl (diphenoxy) silane, triphenyl borate, triphenyl metaborate, triphenyl orthophosphate,

Tetraphenyltitanat, Tetrakresyltitanat and tetraphenylstannate.

1 1. Method according to one of the preceding claims, wherein compound B

is selected from paraformaldehyde, trioxane and gaseous formaldehyde.

12. The method according to any one of the preceding claims, wherein the polymerization is carried out in the presence of an acid. 13. The method of claim 12, wherein the acid is used in an amount of 0.1 to 10 wt .-%, based on compound A.

14. The method according to any one of the preceding claims, wherein the polymerization is carried out in one stage.

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

16. The method according to any one of the preceding claims, wherein the polymerization is carried out in bulk.

17. Use of a composite material, obtainable by a method according to one of claims 1 to 16 for the production of gas storage materials. 18. Use of a composite material obtainable by a process according to any one of claims 1 to 16 for the preparation of rubber mixtures.

19. Use of a composite material, obtainable by a process according to one of claims 1 to 16 for the production of low-K dielectrics.

20. Use of a composite material obtainable by a method according to one of claims 1 to 16 for the production of electrode materials for lithium-ion batteries.