EP2427466A1 - Verfahren zur herstellung eines partikelförmigen nanokompositmaterials - Google Patents

Verfahren zur herstellung eines partikelförmigen nanokompositmaterials

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Publication number
EP2427466A1
EP2427466A1 EP10717172A EP10717172A EP2427466A1 EP 2427466 A1 EP2427466 A1 EP 2427466A1 EP 10717172 A EP10717172 A EP 10717172A EP 10717172 A EP10717172 A EP 10717172A EP 2427466 A1 EP2427466 A1 EP 2427466A1
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EP
European Patent Office
Prior art keywords
polymerization
phase
metal
nanocomposite material
monomers
Prior art date
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Application number
EP10717172A
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German (de)
English (en)
French (fr)
Inventor
Samira Nozari
Rainer Dyllick-Brenzinger
Arno Lange
Stefan Spange
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BASF SE
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BASF SE
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Priority to EP10717172A priority Critical patent/EP2427466A1/de
Publication of EP2427466A1 publication Critical patent/EP2427466A1/de
Withdrawn legal-status Critical Current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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a method for producing a particulate nanocomposite material, wherein the particles of the nanocomposite material a) at least one inorganic or (semi) organometallic phase containing at least one (half) metal M; and b) at least one organic polymer phase.
  • the invention also relates to the nanocomposite materials obtainable by this process.
  • Nanocomposite materials i. Polymer-based composites containing in the organic polymer phase an inorganic phase, e.g. an inorganic (semi-) metal oxide phase with dimensions below 500 nm, in particular below 100 nm (hereinafter also nanoscale phase or in the case of a particulate phase nanoscale particles), contain, due to the large interface between the noskaligen Inorganic phase and the organic polymer phase high potential in terms of their chemical, physical and mechanical properties that can not be achieved by milli or microscale dispersions of conventional inorganic constituents in polymer phases (RP Singh, et al., J. Mater , 37, 781).
  • an inorganic phase e.g. an inorganic (semi-) metal oxide phase with dimensions below 500 nm, in particular below 100 nm (hereinafter also nanoscale phase or in the case of a particulate phase nanoscale particles
  • the hitherto known processes for the preparation of inorganic-organic nanocomposites are based on the direct mixing of nanoparticles or exfoliated phyllosilicates with a polymer in solution or melt, the in situ preparation of the organic phase by polymerization of organic monomers in the presence of inorganic nanoparticles or exfoliated phyllosilicates, Sol-gel Techniques and Combinations of These Measures (See eg, for incorporation of nanoparticles into a polymer melt: Garcia, M., et al., Polymers for Advanced Technologies 2004, 15, 164; for the polymerization of organic monomers in the presence of inorganic nanoparticles or exfoliated For phyllosilicates see: MC Kuo et al., Materials Chemistry and Physics 2005, 90 (1), 185; A.
  • a major disadvantage of nanocomposite production by in-situ production of the organic polymer phase in the presence of nanoparticles is the agglomerate formation of the nanoparticles that occurs, resulting in inhomogeneous products.
  • the advantage of the nanoparticles due to their large surface area to form extended interfaces with the polymer, can not be exploited.
  • the use of powdered nanofillers also poses a high health risk during compounding due to the formation of dust and the respirable nature of the nanoparticles.
  • the in-situ production of the inorganic phase by a sol-gel process in a polymer melt or solution usually leads to poorly reproducible results or requires complex measures to control the hydrolysis conditions.
  • phase domains in the composite material are in the range of a few nanometers.
  • the phase domains of the silica phase and the phase domains of the PFA phase have a co-continuous arrangement, i. Both the PFA phase and the SiO 2 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 averaging a maximum of 10 nm. A macroscopically visible separation into discontinuous domains of the respective phase does not occur.
  • twin polymerization is a novel polymerization principle.
  • a monomer MM so-called twin monomer
  • a first, usually cationically polymerizable monomer unit A which contains a metal or metalloid M (in the TFOS the SiCU unit)
  • a second , usually cationically polymerizable organic monomer unit B in TFOS the furfuryl radicals
  • the polymerizable units A and B are chosen to polymerize under the same conditions.
  • a process for producing a nanocomposite material comprising: a) at least one inorganic or (half) organometallic phase containing at least one (semi-) metal M; and b) at least one organic polymer phase; which supplies the nanocomposite material in particle form.
  • the method should in particular be suitable for the production of particulate nanocomposite materials, wherein the particles of the nanocomposite material have dimensions below 5 .mu.m, in particular at most 2 .mu.m, in particular at most 1 .mu.m, especially at most 500 nm.
  • such a material can be prepared by a twin polymerization process by reacting a cationically polymerizable twin monomer in an aprotic solvent in which the nanocomposite material is insoluble but the monomer is at least partially soluble in the presence of at least one polymerization initiator and at least one further substance polymerized, which is selected from ⁇ ) at least one surface-active substance and ß) at least one particulate material.
  • such a material can be prepared by a twin polymerization process by carrying out a cationically polymerizable twin monomer in an aprotic solvent in which the nanocomposite material is insoluble but the monomer is at least partially soluble in the presence of at least one polymerization initiator the polymerization in the presence of at least one surfactant with a solution of a base in a protic solvent.
  • a twin polymerization process by carrying out a cationically polymerizable twin monomer in an aprotic solvent in which the nanocomposite material is insoluble but the monomer is at least partially soluble in the presence of at least one polymerization initiator the polymerization in the presence of at least one surfactant with a solution of a base in a protic solvent.
  • the present invention relates to a process for producing a particulate nanocomposite material, wherein the particles of the nanocomposite material a) comprises at least one inorganic or (semi) organometallic phase containing at least one (semi-) metal M; and b) at least one organic polymer phase; by polymerizing at least one monomer MM which has at least one first cationically polymerizable monomer unit A which comprises a metal or semimetal M and at least one second cationically polymerizable organic monomer unit B which has at least one, eg 1, 2, 3 or 4, covalent bond chemical bond is bonded to the polymerisable unit A under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerisable unit B polymerize to break the bond or bonds between A and B, wherein the polymerization in an aprotic solvent, in which the nanocomposite material is insoluble, in the presence of at least one polymerization initiator and at least
  • the present invention also relates to a process for producing a particulate nanocomposite material, preferably in the form of a dispersion in a protic solvent, wherein the particles of the nanocomposite material a) have at least one inorganic or (half) organometallic phase containing at least one (semi-) Contains metal M; and b) at least one organic polymer phase; by polymerizing at least one monomer MM which has at least one first cationically polymerizable monomer unit A which comprises a metal or semimetal M, and at least one second cationically polymerizable organic monomer unit B which has at least one, eg 1, 2, 3 or 4, covalent chemical bond is bonded to the polymerizable unit A, under cationic polymerization conditions, under which both the polymerizable monomer unit A and the polymerizable unit B polymerize B fractions or the bonds between A and B, wherein the polymerization in a aprotic solvent in which the nanocomposite
  • the polymer is in the form of discrete particles with dimensions in the micrometer or even nanometer range. Typically, average particle sizes (weight average) below 5 ⁇ m, frequently not more than 2 ⁇ m, in particular not more than 1000 nm, and especially not more than 500 nm, are produced.
  • the particles of the polymer obtained have both an inorganic or (semi) organometallic phase which contains at least one (semi-) metal M and results from the polymerization of the monomer unit A, as well as an organic see polymer phase, which from the polymerization of the monomer unit B results.
  • the different phases have a co-continuous arrangement, wherein the phase domains of identical phases have mean distances of up to 100 nm, often up to 40 nm, in particular up to 10 nm.
  • the preparation of the nanocomposite material comprises a polymerization of the monomers MM in an aprotic solvent in which the nanocomposite material formed is insoluble (solubility ⁇ 1 g / l at 25 ° C.).
  • an aprotic solvent in which the nanocomposite formed in the polymerization is insoluble promotes particle formation in general. If the polymerization is carried out in the presence of the surface-active substance or the particulate inorganic material, presumably the formation of the particles is controlled by the presence of the surface-active substance or of the particulate inorganic material, thereby avoiding the formation of a coarse-particle material.
  • the particles of the nanocomposite material which are primarily formed due to the insolubility of the composite material in the polymerization medium.
  • this agglomeration is suppressed by treating the polymerization product in the presence of at least one surfactant with a solution of a base in a protic solvent to obtain a finely divided dispersion of the nanocomposite material in the protic solvent from which the particulate nanocomposite material is removed by removal of the protic solvent finely divided powder can be isolated.
  • the measures of polymerizing the monomers MM in the presence of the surfactant or of the particulate inorganic material may also be combined with the step of treating the polymerization product in the presence of at least one surfactant with a solution of a base in a protic solvent.
  • the aprotic solvent is chosen so that the monomer is at least partially soluble. This is understood to mean that the solubility of the monomer in the solvent under polymerization conditions is at least 50 g / l, in particular at least 100 g / l.
  • the organic solvent is chosen so that the solubility of the monomers at 20 0 C 50 g / l, in particular at least 100 g / l.
  • the solvent is chosen so that the monomers are largely or completely soluble in it, ie, the ratio of solvent to monomer MM is chosen so that under polymerization at least 80%, in particular at least 90% or the total amount of monomers MM are dissolved.
  • Aprotic means that the solvent used for the polymerization contains substantially no solvents which have one or more protons bound to a heteroatom such as O, S or N, and thus more or less acidic protons.
  • the proportion of protic solvents in the organic used for the polymerization Accordingly, solvents are less than 10% by volume, in particular less than 1% by volume and especially less than 0.1% by volume, based on the total amount of organic solvent.
  • the polymerization of the monomers MM is carried out in the substantial absence of water, ie the concentration of water at the beginning of the polymerization is less than 0.1 wt .-%, based on the amount of organic solvent.
  • the solvent may be inorganic or organic or a mixture of inorganic and organic solvents. It is preferably an organic solvent.
  • aprotic organic solvents are hydrocarbons which may be aliphatic, cycloaliphatic or aromatic, and mixtures thereof with halogenated hydrocarbons.
  • Preferred solvents are hydrocarbons, e.g. acyclic hydrocarbons having generally 2 to 8 and preferably 3 to 8 carbon atoms, in particular alkanes, such as ethane, iso- and n-propane, n-butane and its isomers, n-pentane and its isomers, n-hexane and its isomers, n-heptane and its isomers, and also n-octane and its isomers, cycloalkanes having 5 to 8 carbon atoms, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, acyclic alkenes having preferably 2 to 8 carbon atoms, such as eth
  • halogenated hydrocarbons such as halogenated aliphatic hydrocarbons, e.g. such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1, 2-dichloroethane and 1, 1, 1-trichloroethane and 1-chlorobutane, and halogenated aromatic hydrocarbons such as chlorobenzene, 1, 2-dichlorobenzene and fluorobenzene.
  • the proportion of hydrocarbons is preferably at least 50% by volume, in particular at least 80% by volume and especially at least 90% by volume, based on the total amount of organic solvent.
  • the organic solvent used for the polymerization comprises at least one aromatic hydrocarbon, in particular at least one alkylaromatic, such as toluene, xylene and xylene mixtures, 1, 2,4-trimethylbenzene, mesitylene, ethylbenzene, cumene, isocumene and tert-butylbenzene and mixtures of these solvents.
  • the organic solvent preferably comprises the aromatic hydrocarbon, in particular alkylaromatics, in an amount of at least 50% by volume, in particular at least 80% by volume and especially at least 90% by volume, based on the total amount of organic solvent.
  • the remaining amount of organic solvents is preferably selected from alkanes and cycloalkanes in this embodiment.
  • inorganic aprotic solvents are, in particular, supercritical carbon dioxide, carbon dioxide sulfide, carbon disulfide, nitrogen dioxide, thionyl chloride, sulfuryl chloride and liquid sulfur dioxide, where the last three solvents can also act as polymerization initiators.
  • the polymerization of the monomers MM takes place in the presence of a polymerization initiator.
  • the polymerization initiator is selected to initiate or catalyze cationic polymerization of monomer units A and B. Accordingly, in the polymerization of the monomers MM, the monomer units A and B polymerize synchronously.
  • the term "synchronous" does not necessarily mean that the polymerization of the first and second monomer units proceeds at the same rate. Rather, "synchronous" means that the polymerization of the first and second monomer units are kinetically coupled and triggered by the cationic polymerization conditions.
  • polymerization initiators include protonic acids (Brönstedt acids) and aprotic Lewis acids.
  • Preferred protic catalysts are Bronsted acids, for example organic carboxylic acids such as trifluoroacetic acid or lactic acid, and in particular organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or toluenesulfonic acid.
  • inorganic Bronsted acids such as HCl, H 2 SO 4 or HCIO 4 .
  • the Lewis acid for example, BF3, BCb, SnCU, TiCU, or AICb can be used.
  • the use of complexed or dissolved in ionic liquids Lewis acids is also possible.
  • the polymerization initiator is usually used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5%, based on the monomer MM.
  • Suitable surface-active substances are in principle all substances which are suitable for reducing the surface energy of the particles of the nanocomposite material in the polymerization medium. These include, in principle, all organic and organometallic compounds which have at least one hydrophobic group and at least one hydrophilic group, and which are also referred to below as emulsifiers. be referred to.
  • the surface-active substances may also have a polymerizable group which is copolymerizable with the unit A and / or the unit B of the monomers MM. Such substances are also referred to below as polymerizable emulsifiers.
  • the surface-active substances also include polymeric substances which have hydrophobic repeating units and hydrophilic repeating units and / or amphiphilic repeating units having at least one hydrophobic group and at least one hydrophilic group and which are also referred to below as protective colloids.
  • Protective colloids have a number average molecular weight above 1500 daltons, unlike emulsifiers whose number average molecular weight typically does not exceed 1500 daltons.
  • Suitable hydrophobic groups are hydrocarbon radicals and fluorinated hydrocarbon radicals having at least 6, in particular at least 7 or at least 8 C atoms, for example 6 to 200, in particular 7 to 100 or 8 to 80 C atoms.
  • the optionally fluorinated hydrocarbon radical may be aliphatic, cycloaliphatic, aromatic or araliphatic.
  • the hydrophobic groups of the surface-active substances preferably comprise at least one aliphatic, aromatic or araliphatic hydrocarbon radical having at least 6, in particular at least 7 or at least 8 carbon atoms, for example 6 to 200, in particular 7 to 100 or 8 to 80 carbon atoms and / or or at least one aliphatic fluorinated hydrocarbon radical having at least 6, in particular at least 7 or at least 8 C atoms, for example 6 to 200, in particular 7 to 100 or 8 to 80 C atoms.
  • alkyl radicals having from 6 to 200, in particular 7 to 100 or 8 to 80, carbon atoms and also mono-, di- or trialkyl-substituted phenyl radicals, in particular monoalkylphenyl radicals, in which the alkyl radicals have a total of 6 to 200, in particular 7 to 100 or 8 to 80 carbon atoms.
  • the alkyl groups can be linear or branched and can be derived, for example, from fatty alcohols, oxo alcohols or from olefin oligomers, for example from ONgo or polyisobutene.
  • Suitable hydrophobic groups are furthermore oligo- and poly (dialkylsiloxane) groups, in particular oligo- and polydimethylsiloxane groups with generally at least 2, eg 2 to 50 dialkylsiloxane units.
  • Suitable hydrophilic groups are anionic, cationic or nonionic hydrophilic groups. Examples of anionic hydrophilic groups are sulfonate groups, carboxylate groups and phosphonate groups, where the sulfonate groups and phosphonate groups can be bonded directly, ie with the sulfur atom or the phosphorus atom, or via oxygen (sulfate groups or phosphate groups).
  • Examples of cationic groups are trimethylammonium and triethylammonium groups, N-pyridinium groups and N-methyl-N-imidazolinium groups.
  • Examples of hydrophilic nonionic groups are oligo- and poly-C 2 -C 3 -alkylene oxide groups such as oligo- and polyethylene oxide groups and oligo- and poly (ethylene oxide-co-propylene oxide) groups with generally at least 2, for example 2 to 100 C 2 -C 3 Alkylene oxide units and mono- or oligosaccharide groups or polyhydroxy-functionalized groups, wherein oligo- and poly-C2-C3-alkylene oxide groups are preferred.
  • Suitable hydrophobic repeat units in protective colloids are those derived from monomers which have a low water solubility, eg a water solubility of less than 20 g / l at 20 ° C. and which generally have none of the abovementioned hydrophilic groups.
  • Suitable hydrophilic repeat units in protective colloids are those derived from hydrophilic monomers which have high water solubility, eg a water solubility of at least 50 g / l at 20 ° C. and which as a rule comprise at least one hydrophilic group, in particular at least one anionic group or a nonionic hydrophilic group as defined above.
  • Amphiphilic repeating units are those derived from monomers having both a hydrophobic hydrocarbon group having at least 6 C atoms, eg, an alkyl group having at least 6 C atoms or a phenyl group, and at least one hydrophilic group as defined above.
  • Suitable polymerizable groups are, in particular, those groups which have a metal atom M, in particular one of the preferred metal atoms M, and a polymerizable group B.
  • Examples of such groups are those of the formulas X and Xa:
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the periodic system, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or
  • Bi more preferably B, Si, Ti, Zr or Sn, especially Si;
  • A is an aromatic or heteroaromatic ring fused to the double bond;
  • m is 0, 1 or 2, in particular 0;
  • G is O, S or NH, in particular O or NH and especially O;
  • Q is O, S or NH, in particular O;
  • Radicals R are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and are in particular methyl or methoxy;
  • R a , R b are independently selected from hydrogen and methyl or R a and R b together represent an oxygen atom, and in particular both are hydrogen;
  • R d is C 1 -C 4 -alkyl, in particular methyl.
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the Periodic Table, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, especially Si; m is 0, 1 or 2, in particular 0;
  • G is O, S or NH, in particular O or NH and especially O;
  • Radicals R are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and are in particular methyl or methoxy;
  • R a , R b are independently selected from hydrogen and methyl or R a and R b together represent an oxygen atom, and in particular both are hydrogen;
  • R d is C 1 -C 4 -alkyl, in particular methyl.
  • the surface-active substance comprises at least one anionic surface-active compound, which are also referred to below as anionic emulsifiers, and optionally one or more nonionic surface-active substances, hereinafter also referred to as nonionic emulsifiers.
  • Anionic emulsifiers generally have in addition to at least one hydrophobic group, for example at least one aliphatic group or araliphatic group having at least 6 C atoms, as defined above, or at least one oligo- or poly (alkylsiloxane) group, as defined above, at least an anionic group, for example 1 or 2 anionic groups, which are selected for example from sulfonate groups, carboxylate groups and phosphonate groups, wherein the sulfonate groups and phosphonate groups can 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 carboxylic acids having generally at least 10 carbon atoms and salts thereof, in particular their ammonium and alkali metal salts, aliphatic, araliphatic and aromatic sulfonic acids having generally at least 6 carbon atoms and salts thereof, in particular their ammonium and alkali metal salts, sulfuric acid semi-esters of ethoxylated alkanols and alkylphenols and salts thereof, in particular their ammonium and alkali metal salts, and alkyl, aralkyl and aryl phosphates including phosphoric monoesters 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:
  • alkyl sulfates alkyl radical: Cs to Cs 6
  • alkali metal and ammonium salts of sulfuric acid monoesters of ethoxylated alkanols degree of ethoxylation: from 4 to 30, alkyl radical: Cs to Cis
  • Alkali metal and ammonium salts of sulfuric acid monoesters with ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 - to C 6),
  • alkyl radical: C12 to Cis Alkali and ammonium salts of alkylsulfonic acids
  • alkyl radical: Cg to Cis alkali metal and ammonium salts of alkylarylsulfonic acids
  • 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. Often technical mixtures are used which account for 50 to 90% by weight.
  • anionic emulsifiers the following are particularly preferred:
  • Alkali and ammonium salts of dialkyl esters of sulfosuccinic acid alkyl radical:
  • Alkali and ammonium salts of alkyl sulfates (alkyl: Cs to de), and mixtures thereof
  • suitable nonionic emulsifiers are typically ethoxylated alkanols having 8 to 36 C atoms in the alkyl radical, ethoxylated mono-, di- and tri-alkylphenols having typically 4 to 12 C atoms in the alkyl radicals, 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 surfactant comprises at least one compound having a cationic polymerizable group which is copolymerizable with the monomer unit A and / or B, for example one of the groups X or Xa.
  • a cationic polymerizable group which is copolymerizable with the monomer unit A and / or B, for example one of the groups X or Xa.
  • Such compounds are also referred to below as polymerizable emulsifiers.
  • the polymerizable emulsifier has at least one hydrophobic radical, preferably an alkyl group having at least 6 C atoms, for example 6 to 200 C atoms, in particular 10 to 100 C atoms.
  • polymerizable emulsifiers are those of the formula X-Hb in which X is a radical of the formula X, in particular of the formula Xa, and Hb is a hydrazine rophoben radical, in particular an alkyl group having at least 6 C atoms, for example 6 to 200 carbon atoms, in particular 10 to 100 carbon atoms.
  • polymerizable emulsifiers may also be used in combination with other surface-active substances, e.g. in combination with one or more anionic and / or nonionic emulsifiers.
  • the surface-active substance comprises at least one anionic or nonionic surface-active polymer, which are also referred to below as anionic or nonionic protective colloids, and optionally one or more anionic or nonionic emulsifiers.
  • anionic protective colloids are alginates, such as sodium alginate, copolymers of ethylenically unsaturated carboxylic acids, sulfonic acids or phosphonic acids with hydrophobic monomers, for example copolymers of acrylic acid or of methacrylic acid with hydrophobic monomers, copolymers of sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, (sulfoethyl) maleimide which comprises 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acid and / or vinylsulfonic acid with at least one hydrophobic monomer and copolymers of vinylphosphonic acid, 2-acryloxyethyl phosphate, 2-methacryloxyethyl phosphate, 2-acryloxypropyl phosphate, 2-methacryloxypropyl phosphate, 2
  • hydrophobic comonomers are Ci-Cio-alkyl esters and Cs-do-cycloalkyl esters of ethylenically unsaturated monocarboxylic acids such. the esters of acrylic acid and methacrylic acid, vinylaromatic monomers such as styrene, ⁇ -methylstyrene, vinyltoluene and the like, and C 2 -C 20 -olefins.
  • anionic protective colloids are also phenolsulfonic acid and naphthalenesulfonic acid-formaldehyde condensates and phenolsulfonic acid and naphthalenesulfonic acid-formaldehyde-urea condensates.
  • nonionic protective colloids examples include cellulose derivatives such as hydroxyethyl cellulose, methylhydroxyethylcellulose, methylcellulose and methylhydroxypropylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone with the abovementioned hydrophobic monomers, gelatin, gum arabic, xanthan, casein, poly (ethylene oxide-co-propylene oxide) block polymers, polyvinyl alcohol and partially hydrolyzed polyvinyl acetates.
  • the at least one surface-active substance is generally used in an amount of 0.5 to 50% by weight, in particular in an amount of 1 to 30% by weight, based on the total amounts of the monomers MM.
  • the polymerization of the monomers MM is carried out in the presence of at least one particulate material.
  • the type of particulate material is usually of minor importance and may be inorganic or organic or a composite material.
  • the particulate material preferably has particle sizes below 2 .mu.m, in particular of at most 1 .mu.m.
  • the particle size means the size of the primary particles (primary particle size) which form the agglomerate.
  • the particulate inorganic material preferably has an average particle size (weight average particle diameter), in the case of agglomerates, a primary particle size (weight average primary particle diameter) in the range of 1 to 2000 nm, often in the range of 2 to 1000 nm, preferably in the range of 2 to 500 nm and in particular in the range of 2 to 200 nm.
  • the mean particle diameters specified here relate to the weight average or weight average determined in a conventional manner by means of light scattering or ultracentrifuging.
  • the particulate material is an inorganic material.
  • inorganic materials which contain metals or semimetals of the type defined above, in particular oxides, nitrides or oxynitrides of the abovementioned metals or semimetals M, in particular of silicon, aluminum, tin or boron.
  • oxides, and in particular the oxides of titanium, silicon, tin, aluminum or boron and especially silicon dioxide are preferred.
  • examples of preferred inorganic particulate materials are titanium dioxide powders, in particular pyrogenic titanium dioxide, aluminum oxide, in particular pyrogenic aluminum oxide, and silicic acid, in particular highly disperse silicas such as pyrogenic silicic acid or precipitated silica, wherein the particles preferably have particle size or primary particle sizes in the abovementioned ranges exhibit.
  • Such materials are commercially available, for example, under the trade names Aerosil® and Aeroxide® (Evonik), Cab-O-Sil® and Spectral® (Cabot) or Syloid® (Grace) commercially available, in a particularly preferred embodiment of In the invention, the inorganic particulate material is a finely divided silica, in particular a fumed silica.
  • the particulate material is an organic material.
  • organic particulate materials are polymer particles as obtainable, for example, by suspension polymerization or dispersion polymerization in nonaqueous organic solvents (see, for example, K.E.J. Barret (ed.), "Dispersion Polymerization in Organic Media”, Wiley 1974).
  • suitable polymers are, in particular, those which comprise at least one of the abovementioned hydrophobic monomers, optionally one or more hydrophilic monomers, in particular at least one ionic monomer which has a sulfonic acid group, a phosphonic acid or a carboxyl group (for example acrylic acid, methacrylic acid, Sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, (sulfopropyl) maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, 2-acryloxyethyl phosphate, 2-methacryloxyethyl phosphate, 2-acryloxypropyl phosphate, 2-methacryloxypropyl phosphate, 2 -Acrylamido-2-methylpropyl phosphate and
  • the particulate material is an organic / inorganic composite material, for example a nanocomposite material according to the invention.
  • the particulate material contains at least a portion of the polymerization initiator.
  • This can be achieved, for example, by treating the particulate material with the polymerization initiator, e.g. by mixing the particulate material in a solution of the polymerization initiator, e.g. in a solution in the organic solvent used for the polymerization.
  • This can be achieved, for example, by using a particulate material which incorporates a suitable initiator in sufficient quantity, e.g. Monomers having a carboxyl, sulfonic acid or phosphonic acid group contains.
  • the polymerization is carried out in the presence of a particulate material, this is generally employed in an amount of 0.01 to 100 parts by weight, in particular in an amount of 0.05 to 50 parts by weight, based on 1 part by weight of the monomers MM (or in an amount of 1 to 10000% by weight, in particular in particular in an amount of 5 to 5000% by weight, based on the total amount of the monomers MM or in a quantitative ratio of particulate material to the total amount of the monomers MM in the range from 100: 1 to 1: 100, in particular 50: 1 to 1: 20).
  • the particulate material is used in an amount of 0.01 to 1 parts by weight, in particular in an amount of 0.055 to 0.5 parts by weight, based on 1 part by weight of the monomers MM. In another preferred embodiment of the invention, the particulate material is used in an amount of 1 to 100 parts by weight, in particular in an amount of 1, 5 to 50 parts by weight, based on 1 part by weight of the monomers MM.
  • the particles obtainable in the polymerization have a core consisting of the particulate material used in the polymerization, and one on the Core arranged shell, which consists of the obtained by polymerization of the monomers MM nanocomposite material.
  • particulate material may also be used in combination with the aforementioned surface-active compounds, e.g. in combination with one or more anionic and / or nonionic emulsifiers.
  • the monomer (s) MM to be polymerized is brought into contact with the polymerization initiator in the organic solvent in the presence of the surface-active substance and / or in the presence of the particulate material.
  • the polymerization is carried out in the presence of the surface-active substance, it has generally proven useful if at least a subset of the surface-active substance is already in the polymerization vessel before the addition of the polymerization initiator, ie at least a partial amount or the total amount of the surface-active compound is present before the polymerization initiator added.
  • at least a subset of the surface-active substance is already in the polymerization vessel before the addition of the polymerization initiator, ie at least a partial amount or the total amount of the surface-active compound is present before the polymerization initiator added.
  • the addition of the polymerization initiator may be undiluted or diluted in the solvent used for the polymerization.
  • the non-submitted residual amount of the monomers MM and optionally remaining amounts of surfactant When carrying out the polymerization in the presence of a non-polymerizable substance, it is preferable to use at least 50% by weight, especially at least 80% by weight or the total amount of surface-active compound.
  • polymerizable emulsifiers it has proven useful to add at least a portion of the polymerizable emulsifiers, for example at least 50% by weight, based on the total amount of polymerizable emulsifier, in the course of the polymerization.
  • at least 80% or the total amount of the monomers MM to be polymerized are present.
  • the polymerization is carried out in the presence of the particulate material, it has generally proven useful to add the monomers MM under polymerization conditions to a suspension of the particles in the organic solvent.
  • "Under polymerization conditions" means that at least a portion of the polymerization initiator is already in the reaction vessel before adding the bulk of the monomers MM. For this purpose, preference is given to initially introducing a suspension of the particulate material in the organic solvent used for the polymerization, adding thereto at least a portion or the total amount of the polymerization initiator, and then adding the monomers to be polymerized.
  • the polymerization can also be carried out in the absence of a surface-active substance and simultaneous absence of the particulate substance.
  • the polymerization product is then treated, preferably in the form of the polymerization product suspended in the aprotic solvent, with a solution of a base, preferably an inorganic base, in a protic solvent or solvent mixture, preferably in an aqueous solvent, in the presence of at least one surface-active substance , preferably in the presence of at least one anionic surfactant.
  • the polymerization temperature is usually in the range from 0 to 150 0 C, in particular in the range of 10 to 100 0 C.
  • the polymerization is preferably carried out with thorough mixing of the polymerization batch.
  • the thorough mixing of the polymerization batch can be carried out in a conventional manner, for example by intensive stirring.
  • mechanical homogenizers for example by using mechanical homogenizers, by the use of ultrasound or by use of high-pressure homogenizers, jet nozzles or jet dispersers.
  • mechanical homogenizers are rotor-stator systems such as Ultra-Turrax® (IKA), Dispax® reactor (homogenizers), Sprocket dispersers and mills, eg ball mills, tooth colloid mills (eg those of FrymaKoruma GmbH).
  • Jet dispersants are known, for example, from EP 101007 and are commercially available from the company Lewa GmbH.
  • Ultrasonic homogenizers are also known to the person skilled in the art and are described, for example, by the companies Branson Ultrasonic Corp. NC, USA and dr. Hielscher GmbH, Berlin, offered.
  • the polymerization of the monomers MM can be followed by purification steps and optionally drying steps.
  • the polymerization of the monomers MM can 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 polymer obtained in the polymerization precipitates in the form of a finely divided suspension of the particulate nanocomposite material in the solvent used for the polymerization (cf. Hereinafter also referred to as organic suspension).
  • the particulate nanocomposite material can be obtained from the organic suspension by removing the solvent in the form of a pulverulent solid which is redispersible both in organic solvents and in water.
  • the organic suspension can be converted into an aqueous suspension by replacing the organic solvent with water.
  • the nanocomposite material obtained in the polymerization is obtained by treatment with a solution of a base, preferably an inorganic base, in a protic solvent or solvent mixture, preferably in an aqueous solvent, in the presence of at least one surface-active substance, preferably in the presence at least one anionic surface-active substance is converted into a dispersion of the composite material in the aprotic solvent. From this dispersion, the particulate nanocomposite material can be isolated by removing the protic solvent as a finely divided powder.
  • preferred protic solvents are alcohols having preferably 1 to 4 C atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol or tert-butanol, aliphatic polyols having 2 to 4 C atoms and 2 to 3 OH groups, such as glycerol, ethylene glycol or propylene glycol, (poly) etherols having 3 to 6 C atoms and 1 or 2 OH groups, for example 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, diethylene glycol methyl ether and the like, as well as mixtures of these solvents.
  • alcohols having preferably 1 to 4 C atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol or tert-butanol, aliphatic
  • aqueous solvent ie water or a mixture of water with a water-miscible solvent, in particular with one of the abovementioned protic solvents, wherein water constitutes at least 50% by volume of the aqueous solvent.
  • water or a mixture of water with one of the aforementioned solvents is used, wherein water constitutes at least 90% by volume of the aqueous solvent mixture.
  • the product of the polymerization of the monomers MM is brought into contact with base and surface-active substance with a sufficient amount of protic, in particular aqueous, solvent.
  • base and surface-active substance with a sufficient amount of protic, in particular aqueous, solvent.
  • the primarily obtained dispersion of the nanocomposite material obtained in the polymerization in the aprotic solvent is brought into contact with a sufficient amount of protic, in particular aqueous, solvent and base-active substance and optionally the aprotic solvent partly or in particular substantially or completely (ie at least 95%) away.
  • the contacting takes place with intensive mixing.
  • the amount of protic solvent, in particular of aqueous solvent will generally be such that the resulting dispersion of the particulate nanocomposite material in the protic, especially aqueous solvent, 1 to 55 wt .-%, in particular 5 to 50 wt .-% , And especially 10 to 40 wt .-%, based on the total weight of the dispersion, of the particulate nanocomposite material.
  • the base is an inorganic base, for example an alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate or alkaline earth metal oxide, preferably carbonate or hydroxide of lithium or sodium, in particular an alkali metal hydroxide or alkaline earth metal hydroxide and especially lithium or sodium hydroxide.
  • an alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate or alkaline earth metal oxide preferably carbonate or hydroxide of lithium or sodium, in particular an alkali metal hydroxide or alkaline earth metal hydroxide and especially lithium or sodium hydroxide.
  • Suitable organic bases are, for example, tetra-C 1 -C 4 -alkylammonium hydroxides and hydroxy-C 1 -C 4 -alkyl-tri-C 1 -C 4 -alkylammonium hydroxides, such as tetramethylammonium hydroxide and choline hydroxide.
  • the base is used in an amount such that in the aqueous dispersion results in an alkaline pH, which is in particular in the range of 8 to 12.
  • the conversion of the polymerization product into a dispersion of the particulate nanocomposite material in the protic, especially aqueous, solvent takes place in the presence of at least one surface-active substance.
  • This may be contained in the polymerization product and / or in the aqueous solution of the base or supplied during dispersion.
  • the at least one surface-active substance is already present in the polymerization product, in particular in the dispersion of the polymerization product in the aprotic solvent.
  • the addition of the at least one surface-active substance to the polymerization product can take place before, during or after the polymerization. In a specific embodiment, the addition takes place towards the end or after the polymerization.
  • a surface-active substance are basically the aforementioned surface-active substances, in particular anionic surface-active substances and mixtures thereof with nonionic surface-active substances into consideration. Preference is given to the abovementioned anionic emulsifiers and mixtures thereof with nonionic emulsifiers.
  • Preferred anionic emulsifiers generally have in addition to at least one hydrophobic group, for example at least one aliphatic group or araliphatic group having at least 6 C atoms, as defined above, and at least one anionic group, for example 1 or 2 anionic groups, preferably under Sulfonatgrup - 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 preferred 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 also alkyl, aralkyl and aryl phosphates, including phosphoric monoesters 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:
  • alkyl radical: Cs to C 6 alkali metal and ammonium salts of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: Cs to Cis)
  • Alkali metal and ammonium salts of sulfuric acid monoesters with ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 - to C 6),
  • Alkali and ammonium salts of alkylsulfonic acids alkyl radical: C12 to Cis
  • alkali metal and ammonium salts of alkylarylsulfonic acids alkyl radical: Cg to Cis
  • R 1 and R 2 are hydrogen or C 4 - to ds-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.
  • HAU fig technical-grade 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 the following are particularly preferred:
  • Alkali and ammonium salts of dialkyl esters of sulfosuccinic acid alkyl radical:
  • alkyl radical: Cs alkyl radical
  • Suitable surface-active substances are also the abovementioned anionic or nonionic protective colloids which can be used alone or in combination with the preferred anionic emulsifiers.
  • the procedure is preferably such that a suspension of the nanocomposite material in the aprotic solvent is treated with the protic solvent which contains the base in dissolved form.
  • the treatment is usually carried out by mixing the aprotic solvent phase with the protic solvent, for example with vigorous stirring. In this case, it is possible to proceed by directly bringing the solution of the base in the protic solvent into contact with the dispersion of the nanocomposite material in the aprotic solvent, preferably with thorough mixing.
  • the aprotic solvent is usually removed during or after the conversion of the composite material into the protic solvent, for example by distillation or by phase separation.
  • the polymerization of the monomers MM may be followed by oxidative removal of the organic polymer phase. This is done in the polymerization of mono- merech (s) B oxidized organic polymer material obtained and obtained a nanoporous oxidic, oxynitridisches or nitridic low-carbon or carbon-free material ( ⁇ 10 wt .-%, in particular ⁇ 5 wt .-% carbon, based on the total weight of the material).
  • the inventive method is particularly suitable for the twin polymerization of such monomers MM, wherein the monomer unit A contains a metal or semimetal, among the metals and semimetals of the 3rd main group (group 3 according to IUPAC), in particular B or Al, metals and semi-metals of the 4th Main group of the periodic system (group 14 according to IUPAC), in particular Si, Ge, Sn or Pb, semimetals of the 5th main group of the periodic table (group 15 according to IUPAC), in particular As, Sb and Bi, metals of the 4th subgroup of the periodic table, in particular Ti, Zr and Hf, and metals of the 5th subgroup of the Periodic Table, for example Vanadium is selected.
  • the process according to the invention is particularly suitable for the twin polymerization of monomers in which the monomer unit A contains a metal or semimetal which is among the metals and semimetals of the 4th main group of the Periodic Table, in particular Si, Ge, Sn or Pb and metals of the 4th subgroup of the Periodic Table, in particular Ti, Zr and Hf.
  • the process according to the invention is particularly preferably suitable for the twin polymerization of those monomers in which the monomer unit A contains a metal or semimetal selected from Si and Ti.
  • the process according to the invention is very particularly preferably suitable for the twin polymerization of those monomers in which, in at least a part or the total amount of the monomers, the monomer unit A comprises substantially exclusively silicon.
  • At least 90 mol% and in particular the total amount of the metals or semimetals contained in the twin monomers is silicon.
  • at least 90 mole% and especially the total amount of metals or semimetals contained in the twin monomers is boron.
  • the molar ratio of silicon to the further metal atom is preferably in the range of 10: 1 to 1:10 and especially in the range of 1: 5 to 5: 1.
  • Suitable monomers MM can be described by the general formula I:
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the periodic system, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or
  • R 1 , R 2 may be the same or different and each represents a radical
  • G is O, S or NH and in particular O is;
  • Q is O, S or NH and in particular O; q corresponding to the valency or charge of M is O, 1 or 2 and especially 1, X, Y may be the same or different and each represents O, S, NH or a chemical bond and in particular oxygen or a chemical bond;
  • R 1 ' , R 2' may be the same or different and each represents d-C 6 alkyl, C 3 -C 6
  • Cycloalkyl, aryl or a radical Ar'-C (R a ', R b ') - are, in which Ar 'has the meanings given for Ar and R a ', R b 'are those indicated for R a , R b
  • R 1 ', R 2 ' together with X and Y is a radical of the formula A, as defined above.
  • the moieties corresponding to the radicals R 1 and R 2 G form polymerisable moiety (s) B.
  • R 1 X and R 2 Y When X and Y are different from a chemical bond and R 1 ' X and R 2' do not represent inert moieties such as d C-alkyl, C3-C6-cycloalkyl or aryl, the radicals R 1 X and R 2 Y also form polymerizable unit (s) B.
  • the metal atom M optionally together with the groups Q and Y, the main constituent of Monomer unit A.
  • aromatic radical or aryl
  • aryl is understood in the context of the invention to mean a carbocyclic aromatic hydrocarbon radical, such as phenyl or naphthyl.
  • a heteroaromatic radical or hetaryl is understood as meaning a heterocyclic aromatic radical which generally has 5 or 6 ring members, one of the ring members being a heteroatom which is selected from nitrogen, oxygen and sulfur and, if appropriate 1 or 2 further ring members may be a nitrogen atom and the remaining ring members are carbon.
  • heteroaromatic radicals are furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrdazinyl or thiazolyl.
  • a condensed aromatic radical or ring is understood as meaning a carbocyclic aromatic, divalent hydrocarbon radical, such as o-phenylene (benzo) or 1,2-naphthylene (naphtho).
  • a fused heteroaromatic radical or ring is understood as meaning a heterocyclic aromatic radical as defined above, in which two adjacent C atoms form the double bond shown in formula A or in formulas II and III.
  • the groups R 1 Q and R 2 G together represent a radical of the formula A as defined above, in particular a radical of the formula Aa:
  • #, m, R, R a and R b have the meanings given above.
  • the variable m is, in particular, 0. If m is 1 or 2, R is in particular a methyl or methoxy group.
  • R a and R b are in particular hydrogen.
  • Q stands in particular for oxygen material.
  • a and Aa G stands in particular for oxygen or NH, in particular for oxygen.
  • twin monomers of the first embodiment preference is further given to those monomers of the formula I in which q is 0 or 1 and in which the group XR 1 'is a radical of the formula A' or Aa ':
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the Periodic Table, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, especially Si;
  • m, n are independently 0, 1 or 2, in particular 0;
  • G, G 'independently represent O, S or NH, in particular O or NH and especially O;
  • R, R ' are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl, and more particularly independently of one another- are methyl or methoxy;
  • R a , R b , R a ', R b ' are independently selected from hydrogen and methyl or R a and R b and / or R a and R b 'are each in common
  • Oxygen atom or CH 2; in particular, R a , R b , R a ' , R b' are each hydrogen;
  • L represents a group (YR 2 ') q , in which Y, R 2 ' and q have the meanings given above, and X "has one of the meanings given for Q and in particular represents
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the periodo densystems, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, particularly preferably Si, Ti, Zr or Sn, especially Si;
  • m, n are independently 0, 1 or 2, in particular 0;
  • G, G 'independently represent O, S or NH, in particular O or NH and especially O;
  • R, R ' are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and are in particular methyl or methoxy;
  • R a , R b , R a ', R b ' are independently selected from hydrogen and methyl, or R a and R b and / or R a and R b 'each is an oxygen atom; in particular, R a , R b , R a ' , R b' are each hydrogen;
  • L is a group (YR 2 ') q , wherein Y, R 2 ' and q have the meanings given above.
  • Such monomers are known from the earlier International Patent Applications WO2009 / 083082 and PCT / EP 2008/010169 [WO2009 / 083083] or can be prepared by the methods described therein.
  • Another example of a monomer IIa is 2,2-spirobi [4H-1,2,2-benzodioxaborine] (Bull. Chem. Soc. Jap.
  • the moiety MQQ 'or MO2 forms the polymerizable unit A, whereas the remaining parts of the monomer II or IIa, i. the groups of formula A or Aa, minus the atoms Q and Q '(and minus the oxygen atom in Aa) form the polymerizable units B.
  • the monomers MM also include the monomers of the formulas III or IIIa defined below.
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the periodic system, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or
  • Bi more preferably B, Si, Ti, Zr or Sn, especially Si;
  • A is an aromatic or heteroaromatic ring fused to the double bond;
  • m is 0, 1 or 2, in particular 0;
  • G is O, S or NH, in particular O or NH and especially O;
  • Q is O, S or NH, in particular O;
  • q corresponding to the valence and charge of M, is O, 1 or 2;
  • R is independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and is in particular methyl or methoxy;
  • R c , R d are the same or different and each selected from Ci-C ⁇ -alkyl, Cs-C ⁇ -cycloalkyl and aryl and are in particular methyl.
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the Periodic Table, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, especially Si; m is 0, 1 or 2, in particular 0;
  • G is O, S or NH, in particular O or NH and especially O;
  • Radicals R are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and are in particular methyl or methoxy;
  • R c , R d are the same or different and each selected from Ci-C ⁇ -alkyl, Cs-C ⁇ -cycloalkyl and aryl and are in particular methyl.
  • Such monomers are known, for example, from Wieber et al. Journal of Organometallic Chemistry, 1, 1963, 93, 94. Further examples of monomers IIIa are 2,2-diphenyl [4H-1,2,2-benzodioxasiline] (J. Organomet. Chem. 71 (1974) 225). ; 2,2-di-n-butyl [4H-1,2,2-benzodioxastannine] (Bull. Soc. Chim., Supra 97 (1988) 873); 2,2-dimethyl [4-methylidene-1,3,2-benzodioxasiline] (J. Organomet. Chem., 244, C5-C8 (1983)); 2-methyl-2-vinyl [4-oxo-1,2,2-benzodioxazasiline].
  • the monomers of the formula III or IIIa are preferably not copolymerized alone but in combination with the monomers of the formulas II or IIa.
  • the monomers of the formula I are those which are described by the formula IV, V, Va, VI or VI.
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the Periodic Table, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, especially Si;
  • Ar, Ar ' are identical or different and each represents an aromatic or heteroaromatic ring, in particular 2-furyl or phenyl, where the aromatic or heteroaromatic ring optionally has 1 or 2 substituents which are halogen, CN, Ci-C ⁇ -alkyl C 1 -C 6 -alkoxy and phenyl are selected;
  • R a , R b , R a ' , R b' are independently selected from hydrogen and methyl, or R a and R b and / or R a 'and R b ' are each together an oxygen atom; in particular, R
  • R 1 ' , R 2' are identical or different and each represents C 1 -C 6 -alkyl, C 3 -C 6
  • R a ', R b ' have the meanings given or R 1 ', R 2 ' together with X and Y represent a radical of the formula A, in particular a radical of the formula Aa, as defined above.
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the Periodic Table, in particular B, Al, Si Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, especially Si;
  • Ar, Ar 'in formula V are identical or different and each represents an aromatic or heteroaromatic ring, in particular 2-furyl or phenyl, where the aromatic or heteroaromatic ring optionally has 1 or 2 substituents which are halogen, CN, d C 1 alkyl, C 1 -C 6 alkoxy and phenyl are selected;
  • R a , R b , R a ', R b ' are independently selected from hydrogen and methyl, or R a and R b and / or R a 'and R b ' are each together an oxygen atom; in particular, R a , R b , R a ' , R b' are each hydrogen; q stands for the valence of M for 0, 1 or 2 and especially for 1.
  • m is 0, 1 or 2 and especially 0, and R is selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and especially from methyl and methoxy.
  • Another example of the monomer V or Va is tetrafurfuryl orthotitanate: Adv. Mater. 2008, 20, 4113. This compound tetramerizes to ( ⁇ 4-oxido) hexakis (m-furfuryloxo) -octakis (furfuryloxo) tetratitanium, which is used as a zwittering monomer.
  • Another example of the monomer V or Va is
  • the monomers of the formula IV also include those monomers in which the groups XR 1 'and YR 2 ' are identical or different and are selected from C 1 -C 4 -alkyl, in particular methyl, C 5 -C 6 -cycloalkyl and aryl, for example phenyl are, ie X and Y represent a chemical bond.
  • Such monomers can be described by the following formulas VI or VIa:
  • M is a metal or semimetal, preferably a metal or semimetal of the 3rd or 4th main group or the 4th or 5th subgroup of the Periodic Table, in particular B, Al, Si Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, especially Si;
  • Ar, Ar 'in formula VI are the same or different and are each an aromatic or heteroaromatic ring, in particular 2-furyl or
  • Phenyl wherein the aromatic or heteroaromatic ring optionally has 1 or 2 substituents selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl;
  • R a , R b , R a ', R b ' are independently selected from hydrogen and methyl or R a and R b and / or R a 'and R b ' are each in common
  • Oxygen atom in particular, R a , R b , R a ' , R b' are each hydrogen; q is corresponding to the valence of M is O, 1 or 2 and especially 1;
  • R c , R d are the same or different and each selected from Ci-C ⁇ -alkyl, Cs-C ⁇ -cycloalkyl and aryl and are in particular methyl.
  • m is O, 1 or 2 and in particular O, and R is selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and especially from methyl and methoxy.
  • Such monomers of the formulas IV, V, Va, VI or VIa are known from the prior art, e.g. from the essay cited by Spange et al. and the literature cited therein, or may be prepared in an analogous manner.
  • the monomers of the formulas VI or VIa are preferably not polymerized alone but in combination with the monomers of the formulas V or Va.
  • the twin monomers MM are selected from aromatic compounds which have on average at least two trialkylsilyloxymethyl groups bound to identical or different aryl groups, in particular to benzene rings, and / or aryldialkylsilyloxymethyl groups.
  • alkyl is alkyl having 1 to 4 C atoms, in particular methyl or ethyl.
  • Aryl in this context means phenyl or naphthyl, in particular phenyl.
  • An example of a trialkylsilyloxymethyl group is trimethylsilyloxymethyl ((1-bC ⁇ Si-O-Cl-b-).)
  • An example of an aryldialkylsilyloxymethyl group is dimethylphenylsilyloxymethyl (phenyl (H3C) 2Si-O-CH2-) to which the trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups are attached have further substituents, such as, for example, C 1 -C 4 -alkoxy, such as methoxy, C 1 -C 4 -alkyl, trialkylsilyloxy or aryldialkylsilyloxy, in particular, such twin monomers are phenolic compounds, which have at least two trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups bonded to phenyl rings of the phenolic compound, it being possible for the OH groups of the phenolic compounds to be
  • aromatic compounds which on average have at least two trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups bonded to identical or different aryl groups, in particular to phenyl rings, can be homo- or copolymerized as such.
  • the invention also relates to a Nanokompositmate- rial obtainable by this process. More particularly, the invention relates to a particulate nanocomposite material wherein the particles of nanocomposite material a) comprise at least one inorganic or (half) organometallic phase A containing at least one (semi-) metal M; and b) at least one organic polymer phase P, wherein the organic polymer phase P and the inorganic or organometallic phase A form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases is 100 nm, often 40 nm, in particular 10 nm and specifically not more than 5 nm, and wherein the particle sizes of the particles of the nanocomposite material (dgo and dso values of the mass distribution) have the values given above.
  • the nanocomposite material obtainable by the process according to the invention is particulate, i.
  • the polymer is in the form of discrete particles with dimensions in the micrometer or even nanometer range. It typically has mean particle sizes below 5 ⁇ m, often not more than 2 ⁇ m, in particular not more than 1000 nm and especially not more than 500 nm.
  • the mean particle sizes are understood here and below to mean the weight-average particle diameter (d.sub.50 value of the mass distribution of the particle diameter).
  • At least 90% by weight of the particles of the nanocomposite material obtainable according to the invention have particle diameters of less than 8 ⁇ m, often not more than 3 ⁇ m or less, in particular not more than 1500 nm or less and especially not more than 700 nm or less (so-called dgo- Value of the mass distribution of the particle diameter: particle diameter which is less than 90% by weight of the particles).
  • the particles of the nanocomposite materials obtainable according to the invention are preferably characterized by a particle size distribution (mass distribution of the particle diameters) whose d 50 value is in the range from 2 to 5000 nm, frequently in the range from 5 to 2000 nm, in particular in the range from 8 to 1000 nm and especially in Range of 10 to 500 nm.
  • the particles of the nanocomposite materials obtainable according to the invention are preferably characterized by a particle size distribution (mass distribution of the particle diameters) whose dgo value is in the range from 5 to 8000 nm, frequently in the range from 10 to 3000 nm, in particular in the range from 15 to 1500 nm and especially in the range of 20 to 700 nm.
  • the particle sizes and particle size distributions given here relate to the determined by ultracentrifugation, discriminated by mass of particle diameter at 23 0 C.
  • the determination is performed typically by means of an ultracentrifuge according to standard methods, for example by the H. Cölfen, "Analytical ultra- centrifugation of Nanoparticles” in Encyclopedia of Nanoscience and Nanotechnology, (American Scientific Publishers, 2004), pp. 67-88, or W. Switzerland and L. Borger in “Analytical Ultracentrifugation of Polymers and Nanoparticles” (Springer, Berlin, 2006).
  • the particles of the nanocomposite material according to the invention generally consist of the material formed in the polymerization, consisting of the phases A and P, of the optionally used particulate material and optionally a partial amount or the total amount of surface-active substance used, in particular if it is a polymerizable Emulsifier acts.
  • the total amount of phases A and P based on the total amount of the particulate material, is at least 50% by weight, in particular at least 70% by weight.
  • the total amount of the phases A and P, based on the total amount of the particulate material from 1 to 50 wt .-%, in particular 2 to 35 wt .-% of.
  • the particles of the nanocomposite material according to the invention may have a regular or irregular shape.
  • the particles may have a uniform shape, e.g. Spherical shape or the shape of ellipsoids. However, they can also have irregular shapes, e.g. Shapes made up of several interpenetrating spheres or ellipsoids, including raspberry morphology.
  • the particles may also have a core-shell structure, the shell usually being formed by a polymer consisting of phases A and P, but the core need not necessarily be a material selected from phases A and P but may also be a material which corresponds to the particulate material optionally used in the polymerization.
  • the inorganic or (semi) organometallic phase formed by polymerization of the monomer unit A and the organic polymer phase formed by polymerization of the monomer unit B are present in extremely fine distribution.
  • the dimensions of the phase domains in the composite material thus obtained are in the range of a few nanometers.
  • the phase domains of the inorganic or (semi) organometallic phase A and the phase domains of the organic polymer phase B have a co-continuous arrangement in the particles, ie both the organic phase and the inorganic or (semi) organometallic phase penetrate each other mutually and form essentially no discontinuous areas.
  • the distances between adjacent phase boundaries, or the distances between the domains of adjacent identical phases are extremely small and become usually a mean value of 100 nm, often 40 nm, in particular 10 nm and especially not exceed 5 nm. A macroscopically visible separation into discontinuous domains of the respective phase does not occur.
  • the distance between adjacent identical phases is, for example, the distance between two domains of the inorganic or (semi) organometallic phase, which are separated by a domain of the organic polymer phase or the distance between two domains of the organic polymer phase, which by a domain of the inorganic or (semi) organometallic phase are separated from each other, to understand.
  • the average distance between the domains adjacent identical phases can by means of combined X-ray small angle scattering (SAXS - Small Angle X-ray Scattering) are determined by the scattering vector q (measurement in transmission at 20 0 C, monochromated CuK ⁇ radiation, 2D detector (Image- Plate), cleavage collimati- on).
  • continuous phase domain discontinuous phase domain and co-continuous phase domain
  • co-continuous phase domain it is also referred to W. J. Work et al. Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), Pure Appl. Chem., 76 (2004), pp. 1985-2007, in particular S. 2003.
  • a co-continuous arrangement of a two-component mixture is understood as meaning a phase-separated arrangement of the two phases, wherein within a domain of the respective phase, each region of the phase interface of the domain can be connected by a continuous path without the path passing through a phase interface / crosses.
  • the regions in which the organic phase and the inorganic or (semi-) organometallic phase form substantially co-continuous phase domains constitute at least 80% by volume, in particular 90% by volume, of the nanocomposite materials , as can be determined by combined use of TEM and SAXS.
  • organic polymer phase P in the materials of the invention is naturally dictated by the nature of the monomer unit. According to a preferred embodiment, it is formally condensation products of aromatics such as furan, thiophene, pyrrole and condensable aldehydes such as formaldehyde, in particular a furan-formaldehyde condensation product, pyrrole-formaldehyde condensation product, thiophene-formaldehyde condensation product or a phenol condensation product, the aromatics, in particular the furan, pyrrole, thi Ophen- or phenol units, optionally substituted in the condensation product in the manner described below.
  • aromatics such as furan, thiophene, pyrrole and condensable aldehydes
  • formaldehyde in particular a furan-formaldehyde condensation product, pyrrole-formaldehyde condensation product, thiophene-formaldehyde condensation product or a phenol condensation product
  • the inorganic phase or (semi-) organometallic phase a) in the nanocomposite materials according to the invention contains the metal or semimetal M of the polymerizable unit A.
  • the metal M of the monomer unit A in the monomers MM and thus also in phase a) is preferably selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof.
  • M is especially selected from B, Al, Si, Ti and Sn, especially B, Al and S.
  • the phase a) of the nanocomposite material obtainable according to the invention may be an inorganic or an organometallic or semimetal-organic phase.
  • the phase a) can e.g. an oxidic, sulphidic or nitridic phase or a mixed form of the aforementioned phases or mixtures of the aforementioned phases, oxidic and nitridic phases, mixed forms thereof (oxynitrides), or mixtures of oxides and nitrides being preferred.
  • the metal atoms in addition to oxygen, nitrogen and / or sulfur, may also have organic radicals which are bonded directly to the metal atom.
  • the phase a) is an organometallic or semi-organometallic phase.
  • the phase a) is an oxidic phase, e.g. a silica, titania, alumina or boria phase.
  • phase a) is silicon dioxide.
  • the particulate nanocomposite materials according to the invention can be converted in a manner known per se into nanoporous particulate inorganic materials which are low in carbon and in particular largely free of carbon by oxidatively removing the organic constituents of the nanocomposite material according to the invention.
  • both the particle sizes and the nanostructure of the inorganic phase contained in the nanocomposite material of the invention are obtained, and it results, depending on the monomers selected, a particulate nitride, oxynitride or oxide of the (semi-) metal M or a mixed form which due to removed organic constituents have a nanoporous structure within the particles.
  • the oxidation is typically carried out by calcination in an oxygen-containing atmosphere as in the above cited essay by Spange et al. described.
  • Such materials are new and also subject of the present Invention.
  • the particle sizes are in the ranges given above for the nanocomposite material.
  • the carbon content in such materials is generally ⁇ 10 wt .-%, in particular ⁇ 5 wt .-%, especially ⁇ 1 wt .-% carbon, based on the total weight of the material.
  • the calcination is carried out under oxygen access at a temperature in the range of 400 to 1500 0 C, in particular in the range of 500 to 1000 0 C by.
  • the calcining 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 particulate nanocomposite materials according to the invention can also be converted into a particulate electroactive nanocomposite material which, in addition to an inorganic phase of a (semi-) metal oxide, oxynitride or nitride of the (semi-) metal M, has a carbon phase C.
  • a (semi-) metal oxide, oxynitride or nitride of the (semi-) metal M has a carbon phase C.
  • Such materials are obtainable by calcination or carbonation of the nanocomposite material obtainable according to the invention with substantial or complete exclusion of oxygen.
  • the present invention relates to a carbonaceous nanocomposite material which comprises a) a carbon phase C; b) and at least one inorganic phase of a (semi-) metal oxide, oxynitride or nitride of the (semi-) metal M comprises, and in particular consists of these phases; which is obtainable by calcination of the novel nanocomposite material obtained by copolymerization with substantial or complete exclusion of oxygen. Again, phase arrangement and particle size are largely retained during calcining. Such materials are new and also the subject of the present invention.
  • the particle sizes of the particulate nanocomposite material are in the ranges given above for the nanocomposite material obtainable according to the invention.
  • the carbon phase C and the inorganic phase form substantially co-continuous phase domains, with the average spacing of two adjacent domains of identical phases typically not averaging 100 nm, often 40 nm, especially 10 nm and especially not more than 5 nm will exceed.
  • the calcination or carbonization is carried out at a temperature in the range from 400 to 1500 ° C., in particular in the range from 500 to 1000 ° C.
  • the calcination or carbonization 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 (Hb), hydrocarbon gases such as methane, ethane or propane, or ammonia (NH3), optionally as a mixture with inert gases such as nitrogen or argon , contains.
  • Hb hydrogen
  • hydrocarbon gases such as methane, ethane or propane
  • NH3 ammonia
  • inert gases such as nitrogen or argon
  • the 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 nanocomposite material according to the invention can also be converted into particulate carbon.
  • the particulate nanocomposite material obtainable by the polymerization process according to the invention is calcined or carbonized in the manner described above with the substantial exclusion of oxygen.
  • the oxide phase be dissolved out, for example, by treatment with aqueous hydrogen fluoride solution.
  • gases e.g. Hydrogen, natural gas, especially methane, is particularly suitable.
  • Emulsifier 1 sodium salt of bis (2-ethylhexyl) -2-sulfosuccinic acid (Aerosil OT 100)
  • Emulsifier 2 sodium lauryl sulfate
  • Pyrogenic silica primary particle size 7 nm, BET surface area 300 m 2 / g (Aerosil® 300 SP, Evonik)
  • Oligoisobutenyldichloromethylsilane Alkyldichloromethylsilane in which the alkyl radical is an oligoisobutenyl radical having a number-average molecular weight of about 1000 DaIton (about 17.8 isobutene repeat units).
  • Comparative Example 1 500 mg of methanesulfonic acid Comparative Example 2: 1000 mg of methanesulfonic acid COMPARATIVE EXAMPLE 3 200 mg of methanesulfonic acid COMPARATIVE EXAMPLE 4 75 mg of methanesulfonic acid
  • the aqueous phase was centrifuged. This gave a dark brown aqueous dispersion whose particles had a weight-average particle size of 13.3 nm (measured with the aid of light scattering). The solids content of the dispersion was 12.9 wt .-%.
  • the dispersion thus obtained was examined by cryo-TEM.
  • samples of the dispersion were flash-frozen and first analyzed by means of a transmission electron microscope (CM120, LaB6 cathode). This confirmed the particle size.
  • CM120, LaB6 cathode transmission electron microscope
  • Another TEM study was performed as HAADF-STEM (High Angle Annular Darkfield - Scanning Transmission Electron Microscopy) with a FEG-TEM Tecnai F20 (FEI, Eindhoven, NL) at a working voltage of 200 kV. Nearly round particles with diameters of about 5-30 nm were observed. The particles are partially isolated, but usually they form a kind of network, which is probably caused by freezing by ice crystallization, so represents a freezing artifact.

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