EP2665764A2 - Procédé de production d'un matériau composite - Google Patents

Procédé de production d'un matériau composite

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Publication number
EP2665764A2
EP2665764A2 EP12701479.3A EP12701479A EP2665764A2 EP 2665764 A2 EP2665764 A2 EP 2665764A2 EP 12701479 A EP12701479 A EP 12701479A EP 2665764 A2 EP2665764 A2 EP 2665764A2
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EP
European Patent Office
Prior art keywords
compound
compounds
formaldehyde
phase
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12701479.3A
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German (de)
English (en)
Inventor
Arno Lange
Gerhard Cox
Rainer Dyllick-Brenzinger
Oliver Gronwald
Theo SMIT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Priority to EP12701479.3A priority Critical patent/EP2665764A2/fr
Publication of EP2665764A2 publication Critical patent/EP2665764A2/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C07F7/06—Esters of silicic acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • 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
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a method for producing a composite material
  • 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
  • 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.
  • 1-hydroxy-2-hydroxymethylaromatics such as 1-hydroxy-2-hydroxymethylbenzene (saligenin)
  • metal alkoxides or semimetal alkoxides according to the method described in WO 2009/083083.
  • 1-hydroxy-2-hydroxymethylaromatics are formally monoaddition products of formaldehyde to hydroxyaromatics.
  • 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.
  • the present invention thus relates to a process for the production of composite materials, which consists essentially 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
  • 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.
  • 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
  • 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.
  • 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.
  • Aryloxymetallaten, Aryloxyrudmetallaten 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.
  • the process according to the invention makes it possible to selectively modify the material properties of the composite material obtainable thereafter.
  • 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.
  • 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.
  • 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.
  • 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, Aryloxyrudmetallaten 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, ⁇ -naphthol or ⁇ -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.
  • 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.
  • 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,
  • 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-
  • 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.
  • 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.
  • 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.
  • aryloxy- rudmetallate i. Compounds of semimetals such as B or Si.
  • 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.
  • M is a metal, metalloid or oxoacid-forming non-metal other than carbon and nitrogen;
  • n 1, 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • p 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • M is B or Si and especially Si.
  • p in formula I is 0, ie the atom M carries no radicals R.
  • 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 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.
  • 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:
  • n 1, 2, 3 or 4;
  • n 0 or 1
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • n 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.
  • M in the formula A is Si, Sn, B and P.
  • 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.
  • condensation product is linear and saturated at the ends with an ArO unit.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the compounds A and formaldehyde or the formaldehyde equivalent 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.
  • 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.
  • 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.
  • X indicates the degree of polymerization.
  • these include, in particular, trioxane (3 formaldehyde units) and paraformaldehyde (higher oligomer (CH 2 O) X ).
  • 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.
  • the polymerization of the compounds A with the formaldehyde source is carried out in the presence of catalytic amounts of an acid.
  • 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.
  • organic carboxylic acids such as trifluoroacetic acid, oxalic acid or lactic acid
  • organic sulfonic acids in particular C 1 -C 20 -alkanesulfonic acids such as methane
  • Lewis acids such as HCl, H2SO4 or HCIO4.
  • 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.
  • the polymerization temperatures are typically in the range from 50 to 200 ° C. and in particular in the range from 80 to 150 ° C.
  • 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.
  • the compounds A and B in the desired amount in the reaction vessel and brought to the conditions required for the polymerization.
  • 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.
  • the addition is followed by a post-reaction phase.
  • the implementation is as a batch.
  • 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.
  • 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 .-%.
  • 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 ,
  • 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 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).
  • anionic emulsifiers can also be used in their acidic form and then act as initiators.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the calcination is carried out in an inert gas atmosphere, for example under nitrogen or argon.
  • the inert gas atmosphere will contain less than 1% by volume, in particular less than 0.1% by volume, of oxygen.
  • 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.
  • 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.
  • 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.
  • low-k dielectrics ie as dielectrics with low dielectric constants (k ⁇ 3.7)
  • the composite materials obtainable according to the invention 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 100 mg of trifluoroacetic acid was added to give a homogeneous, clear solution.
  • 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.
  • 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.
  • 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.
  • the average particle size (surface-averaged) of the powder determined by light scattering was determined to be 27 ⁇ . Elemental analysis (thermally stable oxides can lead to minor findings):
  • 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.
  • Monomer B tetraphenylsilicate
  • 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
  • tetraphenylsilicate 48.3 g
  • 1, 3,5-trioxane 21, 7 g
  • n-decane 400 g
  • 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.
  • Example 17 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.
  • 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.
  • Example 9 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.

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