KR20150035750A - Process for producing a composite material - Google Patents

Process for producing a composite material Download PDF

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KR20150035750A
KR20150035750A KR20147036265A KR20147036265A KR20150035750A KR 20150035750 A KR20150035750 A KR 20150035750A KR 20147036265 A KR20147036265 A KR 20147036265A KR 20147036265 A KR20147036265 A KR 20147036265A KR 20150035750 A KR20150035750 A KR 20150035750A
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formula
compound
formaldehyde
alkyl
cycloalkyl
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KR20147036265A
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아르노 랑게
게르하르트 콕스
하네스 울프
실라르드 사이호니
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바스프 에스이
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
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    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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Abstract

The present invention relates to a process for producing a composite material having an arrangement of phase domains similar to that of a nanocomposite obtained by the double polymerization as described in the prior art, A process for the production of a composite material comprising a) at least one oxide phase, and b) an organic polymer phase, comprising the copolymerization of at least one compound selected from formaldehyde and formaldehyde equivalents, and a gas storage material, -K dielectrics and the use of such composites for the production of electrode materials for lithium-ion batteries,
[(ArO) m MO n R r H p] q (I)
Wherein m is 1, 2 or 3, n is 0 or 1, r is 0, 1 or 2, and m is 1, 2 or 3; p is 1, 2 or 3 and q is an integer of 1 or> 1, for example an integer of 2 to 20, in particular of 3 to 6, and m + 2n + r + p is 1, 2, 3, 4 or 5 and corresponds to the valence of M and Ar is phenyl or naphthyl wherein the phenyl ring or naphthyl ring is unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, alkyl or cycloalkyl-alkyl) 1 or more independently selected from, for example 1, may have a two or three substituents, R is alkyl, alkenyl, cycloalkyl or Wherein aryl is unsubstituted or is independently selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b , wherein R a and R b are each as defined above, And may have one or more substituents.

Description

PROCESS FOR PRODUCING A COMPOSITE MATERIAL [0001]

The present invention

a) at least one oxide phase, and

b) at least one organic polymer phase

To a method for producing a composite material.

Recently, there have been various descriptions for the production of a composite material called twin polymerization (Spange et al., Angew. Chem. Int. Ed., 46 (2007) 628-632) 2009/083083, WO 2009/133086, WO 2010/112581 and WO2010 / 128144). Pair-polymerization involves the polymerization of a compound having a plurality of arylmethyl groups bonded to a metal or semimetal via one or two heteroatom (s), preferably one or two oxygen atom (s).

In the case of bipolymerization, the phase domain has one or more oxide phases with a co-continuous arrangement and dimensions in the region of several nanometers (distance between adjacent identical phases) There is provided a composite material typically having an organic polymeric phase. It is believed that the particular phase arrangement and the short distance between the adjacent phases will primarily result in the dynamic coupling of the polymerization of the arylmethyl units of the bi-monomers and, secondly, the formation of silicon dioxide. As a result, the phase constituents are formed somewhat simultaneously and phase separation into the inorganic phase and the organic phase takes place early so that during the polymerization of the monomers.

Preferred paired monomers are spirocyclic compounds as described in WO 2009/083083. In these spirocyclic compounds, two 1-oxy-2- (oxymethyl) aryl groups are bonded to a metal or a half metal atom through their oxygen atom to provide a spirocyclic structure. An example of such a spirocyclic compound is the following 2,2'-spirobi [4H-1,3,2-benzodioxacillin]:

Figure pct00001

The spirocyclic compound is prepared by reacting a 1-hydroxy-2-hydroxymethylaromatic such as 1-hydroxy-2-hydroxymethylbenzene (saligenin) with a metal alkoxide or a semi- 2009/083083, but the preparation of the starting material, i.e. 1-hydroxy-2-hydroxymethylaromatic, is relatively complex. Although the 1-hydroxy-2-hydroxymethylaromatic is formally a monoaddition product of formaldehyde to the hydroxyaromatic, the addition of formaldehyde to the hydroxyaromatic, such as phenol, (See, for example, Rec. Trav. Chim. Pays-Bas 62, 57 (1943)). An o-hydroxyarylcarboxylic acid such as salicylic acid Can be reduced to the corresponding 1-hydroxy-2-hydroxymethylaromatic by using a suitable reducing agent [J. Chem. Soc. PT1, (1981) 1942-1952 and Bull. Chem. Soc. , 719-723, (1983)), or it can be hydrolyzed with o-hydroxymethylphenyl boric acid formed after the phenyl borate is reacted with formaldehyde to obtain end groups (see FR 2626575) . A common feature of all these processes is that they are subjected to refining operations The incomplete conversion or by-product results in a loss of product. Thus, the approach to spiro compounds described in WO 2009/083083 is complex and very difficult to achieve in the laboratory, , Which has hitherto been a barrier to the industrial use of bi-polymerization in the manufacture of nanocomposites.

DE 1816241 discloses a process for the preparation of naphthalene derivatives by reacting a specific metal or semimetal phenoxide with a sub-stoichiometric amount of formaldehyde, or by reacting a novolac, a phenol-formaldehyde condensate with a selected metal or semi- Discloses the preparation of metal-containing phenol-formaldehyde resins. The manufacture of a composite material having a phase structure in which the phase domain has dimensions in the nanometer range is not described.

Surprisingly, it has been found that by copolymerization of at least one compound selected from formaldehyde and formaldehyde equivalents with at least one compound represented by the following formula I in a substantially anhydrous reaction medium, It has now been found that composite materials with an arrangement of phase domains similar to nanocomposites can be produced:

[(ArO) m MO n R r H p] q (I)

In this formula,

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 an integer of 1 or > 1, such as an integer of 2 to 20, particularly an integer of 3 to 6,

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

Wherein Ar is phenyl or naphthyl wherein the phenyl ring or naphthyl ring is unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, Alkyl or cycloalkyl), which may have one or more substituents independently selected from, for example, 1, 2 or 3 substituents,

Wherein R is alkyl, alkenyl, cycloalkyl, or aryl wherein the aryl is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy, and NR a R b wherein R a and R b are each as defined above Lt; / RTI > and the like).

This is surprising since the formation of nanocomposites has been supposed to be due to structural units present in the monomers with an aryl methylene group covalently bonded to the metal or semimetal through a heteroatom. To date, it has been assumed that these structural units result in the dynamic coupling of the polymerization of the organic molecular moiety of the bi-monomers and the formation of the "inorganic polymer ", i.e. the formation of the inorganic phase, Because of the destruction of the bond between the methylene carbon of the methylene group and the (half) metal-containing heteroatom. The resulting dynamic coupling was thought to be responsible for the formation of characteristic nanostructures in the bipolymerization. However, the compounds of formula I do not have characteristic structural units of the paired monomers.

Accordingly, the present invention relates to a process for the preparation of a compound of formula I, which comprises copolymerizing at least one compound selected from formaldehyde and formaldehyde equivalents with at least one compound of formula I in a substantially anhydrous reaction medium,

a) at least one oxide phase, and

b) at least one organic polymer phase

To a process for producing a composite material consisting essentially of: < RTI ID = 0.0 >

[(ArO) m MO n R r H p] q (I)

In this formula,

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 an integer of 1 or > 1, such as an integer of 2 to 20, particularly an integer of 3 to 6,

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

Wherein Ar is phenyl or naphthyl wherein the phenyl ring or naphthyl ring is unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, Alkyl or cycloalkyl), which may have one or more substituents independently selected from, for example, 1, 2 or 3 substituents,

Wherein R is alkyl, alkenyl, cycloalkyl, or aryl wherein the aryl is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy, and NR a R b wherein R a and R b are each as defined above Lt; / RTI > and the like).

The method according to the invention is also associated with a number of advantages. Firstly, the process according to the invention is also characterized in that the composite material obtained in the bi-

a) at least one oxide phase, and

b) at least one organic polymer phase

Wherein the oxide phase and the organic polymer phase substantially consist of a phase domain having a very short average distance between adjacent phase domains of the same phase. However, unlike the case of bipolymerization, unstable starting materials such as spiro compounds mentioned at the beginning or unstable arylmethyl (semi) metal salts such as tetrakis (furylmethyloxy) silane to reach certain composites are needed I do not. Instead, an easily obtainable and relatively stable starting material in the form of a compound of formula I, which enables the preparation of a composite material on a large scale, can be used.

In addition, the process according to the invention makes it possible, through the selection of a suitable compound of the formula I or a mixture of the compounds of the formula I, to control the material properties of the resulting composite material. For example, mixtures of different compounds of Formula I, different in type of metal, semimetal or nonmetal, may be copolymerized to alter the properties of the inorganic polymer. In a similar manner, a mixture of different compounds of formula I, for example different types of aryl groups, may be copolymerized to alter the properties of the organic polymer. Likewise, mixtures of different compounds of formula I may be copolymerized to alter the properties of the organic and inorganic polymers, for example by different types of metals, semi-metals or nonmetal M and aryloxy groups ArO.

As already mentioned, the process according to the invention provides a composite material comprising at least one oxide phase and at least one organic polymer phase, wherein the oxide phase and the organic polymer phase have a very short average distance between adjacent phase domains of the same phase Lt; / RTI > domain. The average distance between adjacent phase domains of the same phase is typically less than 200 nm, often less than 50 nm, in particular less than 10 nm. Adjacent phase domains of the same phase can be separated into two phase domains of two identical phases separated by one phase domain of the other phase, for example two phase domains on the oxide separated by one phase domain on the organic polymer, or one phase on the oxide Is understood to mean the two phase domains on the polymer separated by the domains.

Formula I must be understood as an empirical formula; This indicates the structural unit properties of the compound of formula I, namely the type and number of groups bonded to the atom M and the atom M, namely the aryloxy group ArO, the oxygen atom O, the carbon-bonded radical R and the hydrogen atom H. When q> 1, the unit of [(ArO) m MO n R r H p ] q may form a monocyclic or polycyclic structure or a linear structure.

The compounds of the formula I are in the form of an aryloxy group derived from a monohydroxyaromatic Ar-OH to a metal, semimetal or nonmetal atom M via a deprotonated oxygen atom of a hydroxyl group of a monohydroxy aromatic ) And the anion (s) Ar-O, with an anion derived from a monohydroxy aromatic by deprotonation of the aromatic hydroxyl functionality or a monohydroxy aromatic with 1, 2 or 3 aryloxy groups Ar-O As a main component. Thus, in formula I, the Ar-O radical corresponds to an aryloxy group and an aryloxy anion derived by deprotonation of the aromatic hydroxyl functionality of the hydroxyaromatic.

Suitable monohydroxyaromatic Ar-OH are, in particular, unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, alkyl or cycloalkyl Phenol,? -Naphthol or? -Naphthol having one or more, for example, 1, 2, 3 or 4 substituents independently selected from halogen atoms.

The compound of the formula I has at least one atom M and, in the case of a plurality of atoms M, may have a linear, branched, monocyclic or polycyclic structure.

The compound of formula I has one, two or three hydrogen atoms bonded to atom M in a formal sense.

In a further aspect of the compound of formula I, it may also have one or two substituents R on the atom M, wherein the substituent R is selected from alkyl, alkenyl, cycloalkyl and aryl, , Or one or more 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 cycloalkyl .

The compounds of formula I may also have one oxygen atom on atom M in formal terms.

The total number of groups bonded to the atom M is typically determined by the valency of the atom M bound to the above-mentioned group, and corresponds to the sum of m + 2n + r + p.

The term "alkyl", "alkenyl", "cycloalkyl", "alkoxy", "cycloalkoxy", and "aryl" are generic terms for monovalent organic radicals having the general definition, wherein alkyl and alkoxy Typically have 1 to 20, often 1 to 10, especially 1 to 4 carbon atoms, and cycloalkyl and cycloalkoxy typically have 3 to 20, often 3 to 10, especially 5 or 6 carbon Atoms. The possible number of carbon atoms in the radical is typically specified by the prefix C x -C y where x is the minimum carbon number and y is the maximum carbon number.

Alkyl typically has 1 to 20, often 1 to 10, especially 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Propyl, isopropyl, n-butyl, n-pentyl, 2-methylbutyl, 1-methylbutyl, , 1-methylnonyl, n-decyl, 3-propylheptyl, and the like, which is a straight, branched or branched hydrocarbyl radical.

Alkenyl typically has 2 to 20, often 2 to 10, especially 2 to 6 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl Methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl- Methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, Propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4- Hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, Pentene, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, Methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl- Methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl Dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, Butenyl, 2,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, Butenyl, 3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, Butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, Methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl- Radical.

Alkoxy has 1 to 20, often 1 to 10, especially 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2- Methylbutyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1-methylheptyloxy, 2-methyl Is an alkyl radical as defined hereinabove bonded through an oxygen atom such as heptyloxy, 2-ethylhexyloxy, n-nonyloxy, 1-methylnonyloxy, n-decyloxy, 3-propylheptyloxy and the like.

Cycloalkyl typically has 3 to 20, often 3 to 10, especially 5 or 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo [ 2.2.1] hept-7-yl, bicyclo [2.2.2] octan-1-yl, bicyclo [2.2.1] hept- Bicyclic or tricyclic, saturated alicyclic radical which is cyclopropyl, cyclo [2.2.2] octan-2-yl, 1-adamantyl or 2- adamantyl.

Cycloalkyloxy typically has 3 to 20, often 3 to 10, especially 5 or 6 carbon atoms, such as 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- 2.2.2] octane-1-yloxy, bicyclo [2.2.2] octane-2-yloxy, 1-adamantyloxy or 2- adamantyloxy, a monocyclic, bicyclic Or a tricyclic, saturated alicyclic radical.

Aryl is a monocyclic or polycyclic aromatic hydrocarbyl radical such as phenyl, 1-naphthyl or 2-naphthyl.

In a preferred compound of formula I, the atom M is selected from B, Si, Sn and P, in particular selected from Si and Sn. In certain embodiments of the present invention, M is Si, i.e. the compound of formula I is selected from compounds of formula I wherein atom M comprises at least 90 mole percent silicon based on the total amount of atom M.

In a preferred embodiment of the invention, r in formula I means that the atom M does not carry an R radical. In another preferred embodiment of the invention, two or more different compounds of formula I are copolymerized with formaldehyde or formaldehyde equivalents wherein at least one of the compounds of formula I has variable r 0 and one or more additional compounds of formula I The variable r is zero.

Regardless, in the formula I, the variables m, n, r, p, Ar and R, either individually or in combination with one of the preferred and particularly preferred definitions of M, Defined:

m is 1, 2 or 3;

n is 0 or 1;

r is 0, 1 or 2;

p is 1, 2 or 3;

Ar is an unsubstituted or alkyl, especially C 1 -C 4 - alkyl, cycloalkyl, in particular C 3 -C 10 - cycloalkyl, alkoxy, especially C 1 -C 4 - alkoxy, cyclo-alkoxy, in particular C 3 -C 10 -cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, alkyl, especially C 1 -C 4 -alkyl, or cycloalkyl, especially C 3 -C 10 -cycloalkyl, Phenyl which may have one, two or three substituents selected from < RTI ID = 0.0 >

When present, R is selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 10 -cycloalkyl or phenyl, especially C 1 -C 4 -alkyl, C 5 -C 6 -cycloalkyl or Phenyl.

More specifically, in the formula I, the variables m, n, r, p, Ar and R, either alone or in combination with one of the preferred and particularly preferred definitions of M, Defined as:

m is 1, 2 or 3;

n is 0 or 1;

r is 0 or 1;

p is 1 or 2;

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

When present, R is selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 10 -cycloalkyl or phenyl, especially C 1 -C 4 -alkyl, C 5 -C 6 -cycloalkyl or Phenyl.

When the compound of formula I has a plurality of ArO radicals, the individual Ar radicals may be the same or different. Similarly, in the case of plural R radicals, they may be the same or different.

A preferred embodiment of the compound of formula I is a compound wherein q is 1. Such a compound can be regarded as an orthoester of moxo acid of atom M. In these compounds, the variables m, n, r, p, M, Ar and R are each as defined above and in particular, alone or in combination, have one of the preferred or particularly preferred definitions.

Particularly preferred embodiments of the compounds of formula I are those 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 which Ar has the abovementioned definition, in particular the definition mentioned as being particularly preferred, and is especially unsubstituted or substituted by one, two or three substituents selected from alkyl, especially C 1 -C 4 -alkyl and alkoxy, especially C 1 -C 4 -alkoxy, Phenyl which may have 2 or 3 substituents.

Very particularly preferred embodiments of the compounds of formula I are those wherein 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 is 1 Lt; / RTI > In which Ar has the abovementioned definition, in particular the definition mentioned as being particularly preferred, and is especially unsubstituted or substituted by one, two or three substituents selected from alkyl, especially C 1 -C 4 -alkyl and alkoxy, especially C 1 -C 4 -alkoxy, Phenyl which may have 2 or 3 substituents.

Particular embodiments of the compounds of formula I are those wherein 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 to be. In which Ar has the abovementioned definition, in particular the definition mentioned as being particularly preferred, and is especially unsubstituted or substituted by one, two or three substituents selected from alkyl, especially C 1 -C 4 -alkyl and alkoxy, especially C 1 -C 4 -alkoxy, Phenyl which may have 2 or 3 substituents.

Examples of compounds of formula I which are preferred according to the invention and q is 1 are diphenoxymethylsilane, triphenoxysilane and diphenoxysilane.

M is 1, 2 or 3, n is 0, r is 0 or 1, p is 1, 2 or 3, and q is 1 Lt; / RTI > In which Ar has the abovementioned definition, in particular the definition mentioned as being particularly preferred, and is especially unsubstituted or substituted by one, two or three substituents selected from alkyl, especially C 1 -C 4 -alkyl and alkoxy, especially C 1 -C 4 -alkoxy, Phenyl which may have 2 or 3 substituents. In these compounds, R is as defined for formula I; More specifically, R is methyl, ethyl, phenyl, vinyl or allyl. Examples of preferred compounds of formula I in this embodiment are diphenoxymethylsilane, triphenoxysilane and diphenoxysilane.

A suitable compound of formula I is also a "condensation product" of a compound of formula I wherein q is 1. These compounds generally have empirical formulas of the formula I wherein q is an integer greater than 1, for example an integer in the range of 2 to 20, in particular 3, 4, 5 or 6. These compounds are formally characterized by formal condensation of two ArO units for the formation of Ar-O-Ar molecules and by condensation with removal of M (ArO) m- 2O n + 1 R r H p units Lt; RTI ID = 0.0 > I. ≪ / RTI > They are thus formed substantially from the structural elements of the formula Ia:

- [- O - A -] - (Ia)

Wherein, -A- is> M (ArO) 2-m O n R r H p group (wherein, M, Ar and R are defined above, respectively, in particular, define preferred or mentioned that particularly preferred the , ≪ / RTI &

m is 3,

n is 0,

r is 0,

p is 1,

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

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

Figure pct00002

Wherein M is 1, 2 or 3, and -A- is> M (ArO) m-2 O n R r H p wherein M, Ar and R are each as defined above for formula I, And m, n, r and p have the above-mentioned definition with respect to structure Ia above.

In a further preferred embodiment, the condensation product is linear and saturated with ArO units at each end. That is, such a compound can be represented by the following structure Ic:

Ar - [- OA -] s - OAr (Ic)

Wherein s is an integer ranging from 2 to 20 and -A- is> M (ArO) m-2 O n R r H p group wherein M, Ar and R are each as defined above for formula I, With m, n, r and p having the above-mentioned definition in connection with structure Ia above. This embodiment is preferred when the compound has a distribution about the number of repeating units, i. E. Having a different s. For example, a mixture wherein at least 99%, 90%, 80%, or 60% of the mass is present as an oligomer mixture wherein s is from 2 to 6, s is from 4 to 9, or s is from 6 to 15, or s is from 12 to 20, Can exist.

An example of such a condensation product is triphenoxycyclotrisiloxane or tetraphenoxycyclotetrasiloxane.

May be prepared analogously to the known method of preparing a compound of formula I, or analogously to the preparation of known phenoxides; See, e.g., O. F. Senn, WADC Technical Report 54-339, SRI (1955), DE 1816241, Z. Anorg. Allg. Chem. 551, 61-66 (1987), Houben-Weyl, volume VI-2 35-41, Z. Chem. 5, 122-130 (1965).

In a further embodiment of the invention, the compound of formula I comprises two or more different compounds V1 and V2. The compounds V1 and V2 preferably differ on the basis of at least one of the following characteristics (1) to (4): (1) the phase of Ar, (2) the phase of M, (3) (4) p, that is, the number of hydrogen atoms bonded to M. For example, the compound V1 may be a compound V1 wherein M is B, Si, Sn or P, in particular B, Si or Sn, m is 1,2 or 3, n is 0 or 1, in particular 0, r is 0 and p is 1 Or 2. ≪ / RTI > For example, M is selected from B, Si, Sn and P, M is in particular Si or Sn, m is 1, 2 or 3, n is 0 or 1, in particular 0, r is 1 or 2 , p is 1, 2 or 3. Ar in compounds V1 and V2 may be the same or different and wherein Ar has the abovementioned definition, especially the definition mentioned as being particularly preferred, and is especially unsubstituted or substituted by alkyl, especially C 1 -C 4 -alkyl and alkoxy, Especially phenyl which may have one, two or three substituents selected from C 1 -C 4 -alkoxy. R is then preferably C 1 -C 6 -alkyl, C 3 -C 10 -cycloalkyl or phenyl, especially C 1 -C 4 -alkyl, C 5 -C 6 -cycloalkyl or phenyl.

In this embodiment, the molar ratio of compound V1 to compound V2 can vary over a wide range and is typically in the range of 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 a further more specific embodiment of the invention, the compound of formula I is characterized in that compound V1 is selected from the group consisting of B, Al, Ga, In, Ge, Sn, P, As or Sb, 1, 2 or 3, n is 0 or 1, r is 0, 1 or 2 and p is 1, 2 or 3, compound V2 is M is Si and m is 1 , 2 or 3, n is 0, r is 0, 1 or 2, and p is 1, 2 or 3. Ar in compounds V1 and V2 may be the same or different and wherein Ar has the abovementioned definition, especially the definition mentioned as being particularly preferred, and is especially unsubstituted or substituted by alkyl, especially C 1 -C 4 -alkyl and alkoxy, Especially phenyl which may have one, two or three substituents selected from C 1 -C 4 -alkoxy. R is then preferably C 1 -C 6 -alkyl, C 3 -C 10 -cycloalkyl or phenyl, especially C 1 -C 4 -alkyl, C 5 -C 6 -cycloalkyl or phenyl.

In this embodiment, the molar ratio of compound V1 to compound V2 can vary over a wide range and is typically in the range of 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 .

Compounds of formula I may also be used in combination with one or more compounds of formula II:

[(Ar'O) a M'O c R 'b] d (II)

In this formula,

M ' is one of the definitions given for M in carbon and nitrogen, preferably M in formula I, particularly the definition provided there, forming a metal, semimetal, or oxo acid;

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

b is 0, 1 or 2,

c is 0, 1 or 2,

d is an integer of 1 or > 1, such as an integer of 2 to 20, particularly an integer of 3 to 6,

a + b + 2c is 1, 2, 3, 4, 5 or 6, and corresponds to the valence of M '

Ar ' is one of the definitions given in formula I for Ar, especially one of the definitions given there for preferred;

R < 1 > is one of the definitions given in formula I for R, especially one of the definitions given here as preferred.

When the compound of formula II has multiple Ar'O radicals, the individual Ar 'radicals may be the same or different. Likewise, for multiple R 'radicals, they may be the same or different.

In the formula II, M 'is a metal or a semimetal, or a nonmetal which forms an oxoacid and is different from carbon and nitrogen, and the metal, semimetal and nonmetal are generally selected from the following elements of the periodic table other than nitrogen and carbon Such as Li, Na or K, IIA such as Mg, Ca, Sr or Ba, IIIA such as B, Al, Ga or In, IVA such as Si, Ge or Sn, VA such as P, As or Sb VIA such as S, Se or Te, IVB such as Ti or Zr, VB such as V, VIB such as Cr, Mo or W, and VIIB such as Mn. M 'is preferably selected from elements other than carbon and nitrogen from group IIIA, IVA, VA and IVB of the periodic table, among which elements of the second, third and third period are particularly preferred. M 'is more preferably selected from B, Si, Sn, Ti and P. In a particularly preferred embodiment of the present invention, M 'is B or Si, especially Si.

In a preferred embodiment of the present invention, b in formula II is 0, meaning that the atom M 'does not bear the R' radical.

Regardless, in the formula II, the variables a, b, c, Ar 'and R', alone or in combination with one of the preferred and particularly preferred definitions of M ' It has the same definition:

a is 2, 3 or 4;

c is 0 or 1;

b is 0, 1 or 2;

Ar 'is unsubstituted or alkyl, especially C 1 -C 4 - alkyl, cycloalkyl, in particular C 3 -C 10 - cycloalkyl, alkoxy, especially C 1 -C 4 - alkoxy, cyclo-alkoxy, in particular C 3 - C 10 -cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, alkyl, especially C 1 -C 4 -alkyl, or cycloalkyl, especially C 3 -C 10 -cycloalkyl 2, or 3 substituents selected from the group consisting of:

R 'is selected from the group consisting of 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 5 -C 6 -cyclo Alkyl or phenyl.

More specifically, in the formula II, the variables a, b, c, Ar 'and R', alone or in combination with one of the preferred and particularly preferred definitions of M ' Has the same definition as:

a is 1, 2, 3 or 4;

c is 0 or 1;

b is 0;

Ar 'is phenyl which may be unsubstituted or may have one, two or three substituents selected from alkyl, especially C 1 -C 4 -alkyl and alkoxy, especially C 1 -C 4 -alkoxy.

A preferred embodiment of the compound of formula II is a compound of formula II wherein d is the number 1. Such a compound can be regarded as an orthoester of the oxo acid of the central atom M '. In these compounds, the variables a, b, c, M ', Ar' and R 'are each as defined above, and in particular in combination, have one of the preferred or particularly preferred definitions.

Particularly preferred embodiments of the compounds of formula II are those wherein M 'is selected from B, Si, Sn, Ti and P, a is 3 or 4, c is 0 or 1, b is 0 and d = Lt; / RTI > Where Ar 'has the definition stated that the definitions referred to above, particularly preferred, especially unsubstituted or alkyl, especially C 1 -C 4 - alkyl and alkoxy, in particular C 1 -C 4 - 1 is selected from alkoxy dog , Phenyl which may have 2 or 3 substituents.

A very particularly preferred embodiment of the compound of formula II is a compound of formula II wherein M 'is selected from B, Si and Sn, a is 3 or 4, c is 0, b is 0 and d = 1 . Where Ar 'has the definition stated that the definitions referred to above, particularly preferred, especially unsubstituted or alkyl, especially C 1 -C 4 - alkyl and alkoxy, in particular C 1 -C 4 - 1 is selected from alkoxy dog , Phenyl which may have 2 or 3 substituents.

Particular embodiments of the compounds of formula II are those of formula II wherein M 'is Si, a is 4, c is 0, and b is 0. Where Ar 'has the definition stated that the definitions referred to above, particularly preferred, especially unsubstituted or alkyl, especially C 1 -C 4 - alkyl and alkoxy, in particular C 1 -C 4 - 1 is selected from alkoxy dog , Phenyl which may have 2 or 3 substituents.

Examples of compounds of formula II wherein d = 1, which is preferred according to the invention, are tetraphenoxysilane, tetra (4-methylphenoxy) silane, triphenylborate, triphenylphosphate, tetraphenyltitanate, tetracresyl titanate and Tetraphenyl stannate.

A further specific embodiment of the compound of formula II is a compound of formula II, wherein M 'is Si, a is 1, 2 or 3, c is 0, and b is 4-a. Where Ar 'has the definition stated that the definitions referred to above, particularly preferred, especially unsubstituted or alkyl, especially C 1 -C 4 - alkyl and alkoxy, in particular C 1 -C 4 - 1 is selected from alkoxy dog , Phenyl which may have 2 or 3 substituents. In these compounds, R 'is as defined for formula II; More specifically, R 'is methyl, ethyl, phenyl, vinyl or allyl. Examples of preferred compounds of formula II in this embodiment are methyl (triphenoxy) silane, dimethyl (diphenoxy) silane, trimethyl (phenoxy) silane, phenyl (triphenoxy) silane and diphenyl Silane.

A suitable compound of formula II is also a "condensation product" of a compound of formula II wherein d = 1. These compounds generally have empirical formula II in which d is an integer> 1, such as an integer in the range of 2 to 20, especially 3, 4, 5 or 6. These compounds are in each case in the form Ar-Ar'O aspect, removal of the two Ar'O unit for forming the molecule and M '(OAr') a- 2 (O) in the form of cotton, c + It is derived from 1 R b condensed compound of d = 1 in formula II by involving the removal of the unit. They are therefore formed substantially from the constituents of formula IIa:

- [- O - A '-] - (IIa)

Wherein R, -A'- is> M '(Ar'O) a- 2 (O) c (R') b group (wherein, M ', Ar' and R 'each is defined above, in particular, Preferred or < RTI ID = 0.0 > and / or < / RTI &

a is 3 or 4,

c is 0 or 1, especially 0,

b is 0 or 1, especially 0,

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

In the formula A ', M' is preferably Si, Sn, B and P.

In a preferred embodiment, the condensation product is cyclic and d is 3, 4 or 5. Such compounds may in particular be represented by the following structure IIb:

Figure pct00003

Wherein, k is 1, 2 or 3, -A'- is> M '(Ar'O) a- 2 (O) c (R') b group (wherein, M ', Ar', and R ' Have the abovementioned definition for formula II, and a, c and b have the above-mentioned definition in connection with structure IIa.

In a further preferred embodiment, the condensation product is linear and saturated at the end with Ar'O units. That is, these compounds may be represented by the following structure IIc:

Ar '- [-O-A'-] d- OAr' (IIc)

Wherein, d is an integer from 2 to 20 range, -A'- is> M '(Ar'O) a- 2 (O) c (R') b group (wherein, M ', Ar' and R Have the abovementioned definition for formula II, a, b and c have the above-mentioned definition in connection with structure IIa. This embodiment is particularly preferred when the compound has a distribution about the number of repeating units, i. E. Having a different d. For example, a mixture wherein at least 99%, 90%, 80% or 60% of the mass is present as an oligomer mixture wherein d = 2 to 6, d = 4 to 9, or d = 6 to 15 or d = Can exist.

Examples of such condensation products are triphenylmethane borate, hexaphenoxycyclotrisiloxane or octaphenoxycyclotetrasiloxane.

Compounds of formula II are known or can be prepared analogously to the preparation of known phenoxides; See, e.g., O. F. Senn, WADC Technical Report 54-339, SRI (1955), DE 1816241, Z. Anorg. Allg. Chem. 551, 61-66 (1987), Houben-Weyl, volume VI-2 35-41, Z. Chem. 5, 122-130 (1965).

When a mixture of one or more compounds of formula I and one or more compounds of formula II is copolymerized with a formaldehyde or formaldehyde equivalent, the molar ratio of the compound of formula I to the compound of formula II may vary over a wide range, : 1000 to 1000: 1, often in the range of 100: 1 to 1: 100 or 50: 1 to 1:50.

In the process according to the invention, on the one hand, the compound of the formula I or a mixture of the compound of the formula I and the compound of the formula II and, on the other hand, formaldehyde or formaldehyde equivalents, in a molar ratio of formaldehyde or formaldehyde equivalents The molar ratio of the aryloxy groups ArO or Ar'O present in the existing formaldehyde to the compounds of the formula I and optionally in the compounds of the formula II is preferably at least 0.9: 1, in particular at least 1: 1, in particular at least 1.01: Preferably at least 1.05: 1, in particular at least 1.1: 1. Since a large excess of formaldehyde is generally, but not necessarily, unnecessary, the formaldehyde or formaldehyde equivalents can be converted to formaldehyde in a molar ratio of formaldehyde, usually in formaldehyde equivalents, to formaldehyde to compounds of formula I and optionally to compounds of formula II Is used in an amount such that the molar ratio of the aryloxy group ArO or Ar'O present in the compound does not exceed a value of 10: 1, preferably 5: 1, in particular 2: 1. The molar ratio of formaldehyde or formaldehyde equivalents, preferably formaldehyde, or the aryloxy groups ArO or Ar'O present in the formaldehyde to compounds of Formula I and optionally in Formula II, present in the formaldehyde equivalent, Is used in an amount ranging from 1: 1 to 10: 1, particularly 1.01: 1 to 5: 1, especially 1.05: 1 to 1: 5 or 1.1: 1 to 2: 1.

It should be understood that the formaldehyde equivalent means a compound that releases formaldehyde under polymerization conditions. Formaldehyde equivalent is preferably an oligomeric or polymeric material of formaldehyde, i.e. experience expression (CH 2 O) z (In the formula, z is also specified the polymerization degree). These include in particular trioxane (three formaldehyde units) and paraformaldehyde (advanced oligomer (CH 2 O) z ).

The copolymerization is preferably 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 compound of formula I and optionally the compound of formula II is copolymerized with a compound selected from formaldehyde and formaldehyde equivalents in the presence of a catalytic amount of acid. Typically, the acid is used in an amount of from 0.1 to 10% by weight, especially from 0.2 to 5% by weight, based on the compound of formula I and, optionally, the compound of formula II. The preferred acids herein are Bronsted acids such as organic carboxylic acids such as trifluoroacetic acid, oxalic acid or lactic acid, and organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or p-toluenesulfonic acid. Inorganic Bronsted acids such as HCl, H 2 SO 4 or HClO 4 are also suitable. The Lewis acid used may be, for example, BF 3 , BCl 3 , SnCl 4 , TiCl 4 or AlCl 3 . Lewis acid in the form of a complex bond or dissolved in an ionic liquid may also be used.

The copolymer can also be catalyzed using a base. Examples are amines, such as triethylamine or dimethylaniline, an alkali metal, hydroxides and basic salts of alkaline earth metals, such as LiOH, NaOH, KOH, Ca ( OH) 2, Ba (OH) 2 or Na 3 PO 4, and also alkali Alkoxides of metals and alkaline earth metals, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide or magnesium ethoxide.

Copolymerization can also be initiated by heat, which means that, without the addition of an acid, a compound selected from formaldehyde and formaldehyde equivalents and a mixture of compounds of formula I and optionally a compound of formula II is subjected to copolymerization.

The temperature required for copolymerization is usually in the range of 50 to 250 占 폚, particularly 80 to 200 占 폚. In catalysis catalysed by acids or bases, the polymerization temperature is usually in the range of 50 to 200 ° C, in particular in the range of 80 to 150 ° C. In heat-initiated copolymerization, the polymerization temperature is usually in the range of 120 to 250 占 폚, particularly 150 to 200 占 폚.

The copolymerization can be carried out in principle as a batch or addition process. For as-batch performance, the compound of formula I or a mixture of at least one compound of formula I with at least one compound of formula II and a compound selected from formaldehyde and formaldehyde equivalents are first charged to the reaction vessel in a predetermined amount, . In the case of an addition process, the compound selected from two components, namely the compound (s) of formula I and optionally one or more of the compounds of formula II and / or formaldehyde and formaldehyde equivalents, is reacted with a compound of formula I and optionally a compound of formula II Until at least a predetermined ratio of the compound selected from formaldehyde, formaldehyde and formaldehyde equivalents is achieved. The reaction phase is optionally continued after addition. Performing as ash is desirable.

When carrying out the copolymerization in one step, i.e. carrying out the polymerization as a batch with the total amount of the compound of the formula I to be polymerized and optionally the compound of the formula II and the formaldehyde and formaldehyde equivalents, The compound of formula I and optionally the compound of formula II and the formaldehyde and formaldehyde equivalents in such a way that the amount of the compound selected from formaldehyde and formaldehyde equivalents does not interfere with the polymerization conditions until the total amount of the compound selected from formaldehyde and formaldehyde equivalents is added to the reaction vessel. It has been found advantageous to employ an addition process in which the compound to be selected is added.

The copolymerization of a compound of formula I or a mixture of compounds of formula I and one or more compounds of formula II with a compound selected from formaldehyde and formaldehyde equivalents can be carried out in bulk or in an inert diluent. Suitable diluents are, for example, halogenated hydrocarbons such as dichloromethane, trichloromethane, 1,2-dichloroethane, or hydrocarbons such as toluene, xylene or hexane, and mixtures thereof.

The copolymerization of a compound of formula I or a mixture of compounds of formula I and one or more compounds of formula II with a compound selected from formaldehyde and formaldehyde equivalents is carried out in the absence of substantial amounts of water, Less than 0.1% by weight based on the total amount of monomers).

After the copolymerization of the compound of formula I or one or more compounds of formula I and one or more compounds of formula II with a compound selected from formaldehyde and formaldehyde equivalents, the purification step and optionally the drying step may be followed.

After the copolymerization of the compound of formula I or one or more compounds of formula I and one or more compounds of formula II with a compound selected from formaldehyde and formaldehyde equivalents, calcination may be allowed. In this case, the organic polymer material formed from the copolymerization of the compound of formula I or one or more compounds of formula I and one or more compounds of formula II and a compound selected from formaldehyde and formaldehyde equivalents is carbonized to provide a carbon phase.

After copolymerization of a compound of formula I or a mixture of compounds of formula I and one or more compounds of formula II with a compound selected from formaldehyde and formaldehyde equivalents, the oxidation removal of the organic polymer may be followed. This entails oxidizing the organic polymer material formed in the copolymerization of the organic components to obtain a nanoporous oxide or nitride material.

The composite material obtainable by the process according to the present invention comprises at least one oxide phase comprising a metal, semimetal or nonmetal M or M ', and at least one oxide phase formed from the polymerization of an aryloxy group ArO or Ar'O and formaldehyde Organic polymer phase. The dimensions of the thus obtained composite inner-domain are generally within the range of a few nanometers, but materials with a domain size of 100-200 nm can be obtained. In addition, the phase domain of the oxide phase and the phase domain of the organic phase generally have a coherent arrangement. That is, both the organic phase and the inorganic or organic metal phase do not penetrate each other to form a substantially discontinuous region. The distance between the adjacent phase boundaries, or the distance between the domains on the adjacent same side, is considerably short and is on average 10 nm or less, preferably 5 nm or less, particularly 2 nm or less. Macroscopic visible separation into non-continuous domains of a particular phase does not occur.

The average distance between the domains on the contiguous same phase is calculated using the scattering vector q (small-angle X-ray scattering (SAXS)) by passing through a measurement at 20 ° C, monochromatic CuK α emission, 2D detector (image plate), slit collimation, . ≪ / RTI >

With respect to the terms "continuous phase domain "," non-continuous phase domain ", and "performance fast phase domain" J. Work et al. Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), Pure Appl. Chem., 76 (2004), p. 1985-2007, especially p. 2003]. According to this, the underframe arrangement of the two-component mixture can be divided into two phase-separated arrays in which a continuous path through any one phase domain can be drawn at all phase boundaries, without crossing any phase domain boundary in one domain of the specified phase As used herein.

The composite material obtainable according to the present invention can be converted into a nanoporous inorganic material in a manner known per se by oxidatively removing the organic component of the nanocomposite of the present invention. This preserves the nanostructure of the inorganic phase present in the nanocomposite of the present invention and the result is an oxide or mixed form of a (semi-) metal or non-metal depending on the compound of formula I selected. Oxidation is typically carried out by heating in an oxygen atmosphere as described in the article by Spange et al. In general, the heating is carried out by introducing oxygen at a temperature in the range of 400 to 1500 ° C, particularly in the range of 500 to 1000 ° C. Heating is typically carried out in an oxygen atmosphere, for example in an atmosphere of air or other oxygen / nitrogen mixture, wherein the volume ratio of oxygen varies over a wide range and ranges, for example, from 5 to 50% by volume, based on the total gas mixture.

The composite material obtainable according to the invention can also be converted into an electroactive nanocomposite material having a carbon phase C as well as an inorganic phase of a (semi-) metal which can be oxidative or (semi) metallic. Such a material can be obtained by substantially or completely eliminating oxygen and calcining the composite material obtainable according to the present invention. In the carbon nanocomposite material, the carbon phase C and the inorganic phase substantially form the performance fast phase domain, wherein the average distance between two adjacent domains of the same phase is generally 10 nm or less. In general, firing is carried out in the range of 400 to 2000 占 폚, particularly 500 to 1000 占 폚. The calcination is then carried out, usually with substantially no oxygen. That is, during firing, the partial oxygen pressure in the reaction zone in which the firing is performed is low, preferably not exceeding 20 mbar, especially 10 mbar. It is preferable to perform the firing under an inert gas atmosphere such as nitrogen or argon. The inert gas atmosphere preferably contains less than 1% by volume, especially less than 0.1% by volume of oxygen. In addition, preferred embodiments of the present invention, the firing in a reducing condition, such as hydrogen (H 2), hydrocarbon gases such as methane, ethane or propane, or optionally ammonia as a mixture with an inert gas such as nitrogen or argon (NH 3) Lt; / RTI > In order to remove volatile components, calcination may be carried out in a reducing gas, for example, a gas stream comprising hydrogen, a hydrocarbon gas or ammonia, or an inert gas stream.

The composite material obtainable according to the present invention is particularly useful for manufacturing gas storage materials, rubber mixtures, low-K dielectrics and electrode materials for lithium ion batteries according to the present invention.

The following examples serve to illustrate the invention.

The compounds of formula I used:

Compound of formula I wherein diphenoxysilane (M = Si, m = 2, n = 0, r = 0, p = 2, q = 1, Ar = phenyl). The preparation was carried out by the method described by G. Fester (Thesis, 2009, Bergakademie Freiberg / Sa, Example 20 f.).

(The compound of M = Si, m = 2, n = 0, r = 1, p = 1, q = 1, Ar = phenyl, R = CH 3 in formula I) diphenoxylate rust when methylsilane. The preparation was carried out by the method described in DE 1162365, 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 dissolved with 7.8 g of trioxane under nitrogen atmosphere at 40 to 50 DEG C and diluted with 80 g of xylene. To this was added 0.2 g of methanesulfonic acid at 50 DEG C and the mixture was homogenized. The mixture was then stirred at a stirrer speed of 500 to 600 rpm, at 80 DEG C for 30 minutes, at 100 DEG C for 30 minutes, and at 120 DEG C for 30 minutes. The mixture was cooled to room temperature, filtered through a D4 frit, washed with xylene and hexane and then dried in a vacuum drying cabinet. Thereby, 25 g of fine powder was obtained. The primary particles exhibited a typical domain structure for bipolymerization with dimensions ranging from 2 to 5 nm (determined by TEM).

Example 2:

Precipitation polymerization of diphenoxymethylsilane and tetraphenoxysilane in solution

In a 250 ml Erlenmeyer flask, 50 g of diphenoxymethylsilane and 14.3 g of trioxane were dissolved at 70 DEG C under a nitrogen atmosphere. To this was added a solution of 49.4 g of tin dichloride in 120 ml of THF and the solution was cooled to 22 [deg.] C with an ice bath and transferred to a dropping funnel. 250 ml of xylene and 2.5 g of methanesulfonic acid were charged into a 500 ml four-necked flask and heated to 126 DEG C in an oil bath. To this was added dropwise a solution of methyldiphenoxysilane, trioxane and tin dichloride in THF within 105 min, maintaining the temperature of the mixture at 120-125 < 0 > C. THF and water were distilled using a water separator. Stirring of the reaction mixture was continued at an internal temperature of 136 DEG C for an additional 60 minutes. The crude product was filtered off with suction filter, washed twice with 100 ml of toluene and twice with 100 ml of hexane. The crude product was dried at 80 < 0 > C and 5 mbar. This gave 47.7 g of crude product. The crude product was mixed with 5 g of sodium methoxide and 1 l of water and stirred at 22 ° C for 2 h, then the solid was filtered off and washed twice with 100 ml of methanol. The product was dried at 80 < 0 > C and 5 mbar. 12.6 g of composite material was obtained, which contained 4.3% of silicon according to elemental analysis.

The primary particles exhibited a typical domain structure for bipolymerization with dimensions ranging from 3 to 5 nm (determined by TEM).

Claims (18)

Which comprises copolymerizing at least one compound selected from formaldehyde and formaldehyde equivalents with at least one compound of formula I in a substantially anhydrous reaction medium,
a) at least one oxidic phase, and
b) an organic polymer phase
: ≪ / RTI >
[(ArO) m MO n R r H p] q (I)
In this formula,
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 an integer of 1 or > 1, such as an integer of 2 to 20, particularly an integer of 3 to 6,
m + 2n + r + p is 1, 2, 3, 4 or 5 and corresponds to the valence of M,
Wherein Ar is phenyl or naphthyl wherein the phenyl ring or naphthyl ring is unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b , wherein R a and R b are each independently hydrogen, Alkyl or cycloalkyl), which may have one or more substituents independently selected from, for example, 1, 2 or 3 substituents,
Wherein R is alkyl, alkenyl, cycloalkyl, or aryl wherein the aryl is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy, and NR a R b wherein R a and R b are each as defined above Lt; / RTI > and the like). The method of claim 1, wherein the compound selected from formaldehyde and formaldehyde equivalents is used in an amount such that the molar ratio of formaldehyde to aryloxy group ArO in the compound of formula I is at least 0.9: 1. 3. A compound according to claim 1 or 2, 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, 2. 4. The method according to any one of claims 1 to 3, wherein the variable M in the compound of formula I is Si. 5. The process according to any one of claims 1 to 4, wherein the compound of formula I is selected from diphenoxymethylsilane, triphenoxysilane and diphenoxysilane. 6. The method according to any one of claims 1 to 5, wherein the compound of formula I is used as a mixture with at least one compound of formula II:
[(Ar'O) a M'O c R 'b] d (II)
In this formula,
M 'is a non-metal other than carbon and nitrogen, forming a metal, semimetal, or oxo acid;
a is 1, 2, 3, 4, 5 or 6,
b is 0, 1 or 2,
c is 0, 1 or 2,
d is an integer of 1 or > 1, such as an integer of 2 to 20, particularly an integer of 3 to 6,
a + b + 2c is 1, 2, 3, 4, 5 or 6, and corresponds to the valence of M '
Ar 'is phenyl or naphthyl, wherein the phenyl or naphthyl ring is unsubstituted or substituted, or an alkyl, cycloalkyl, alkoxy, cycloalkoxy, and NR a R b (wherein, R a and R b are each independently hydrogen, , Alkyl, or cycloalkyl), such as, for example, 1, 2, or 3 substituents;
Wherein R 'is alkyl, alkenyl, cycloalkyl or aryl wherein the aryl is unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR a R b wherein R a and R b are as defined above Lt; / RTI > and the like). 7. A compound according to any one of claims 1 to 6, wherein the compound selected from formaldehyde and formaldehyde equivalents is selected from the group consisting of formaldehyde, a compound of formula I and optionally an aryloxy group ArO or Ar & 1 to 10: 1, especially 1.05: 1 to 2: 1. 8. A process according to any one of claims 1 to 7, wherein the compound selected from formaldehyde and formaldehyde equivalents is selected from paraformaldehyde, trioxane and gaseous formaldehyde. 9. The process according to any one of claims 1 to 8, wherein the copolymerization is carried out in the presence of an acid. The method of claim 9, wherein the acid is used in an amount of from 0.1 to 10% by weight, based on the compound of formula I or the mixture of compounds of formulas I and II. 11. The method according to any one of claims 1 to 10, wherein the copolymerization is carried out in one step. 12. The method according to any one of claims 1 to 11, wherein copolymerization is carried out in an inert solvent. 13. The method according to any one of claims 1 to 12, wherein copolymerization is carried out in bulk. 14. The method according to any one of claims 1 to 13, wherein the calcination is carried out after copolymerization. Use of a composite material obtainable by the process of any one of claims 1 to 14 for the production of a gas storage material. Use of a composite material obtainable by the process of any one of claims 1 to 14 for the preparation of rubber mixtures. The use of a composite material obtainable by the process of any one of claims 1 to 14 for the production of low-K dielectrics. Use of a composite material obtainable by the method of any one of claims 1 to 14 for the production of an electrode material for a lithium ion battery.
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