EP2697314A1

EP2697314A1 - Hydrophobic, functionalised particles

Info

Publication number: EP2697314A1
Application number: EP12715353.4A
Authority: EP
Inventors: Stephan Deuerlein; Imme Domke; Alexej Michailovski; Reinhold Rieger; Piyada Charoensirisomboon; David F. Blackwood; Christian Eichholz; Robert Bayer; Dennis LÖSCH; Igor Shishkov
Original assignee: BASF SE; BASF Corp
Current assignee: BASF SE; BASF Corp
Priority date: 2011-04-12
Filing date: 2012-04-11
Publication date: 2014-02-19
Also published as: JP2014520053A; EA201391493A1; EP2886611A1; MX2013011857A; PE20141988A1; CL2013002966A1; CA2832814A1; WO2012140065A1; CN103459517B; ZA201308412B; AR085994A1; MX344908B; CA2832814C; CN103459517A; AU2012241937A1; EP2886611B1; AU2012241937B2; BR112013024090A2; KR20140039178A

Abstract

The invention relates to a stable mixture containing surface-modified particles which are obtained by reacting metal or semimetal oxide particles with at least one compound selected from silicon-containing compounds which have at least one metal oxy radical and optionally further alkoxy and/or hydroxy radical(s), and at least one solvent, at least one surface-active substance or a mixture thereof, to a method for producing same, to the use of said particles in systems in which they are brought into contact with at least one solvent, wherein the mass ratio of solvent to modified particles is greater than 500, and to the use of said particles in agglomeration/deagglomeration cycles.

Description

The present invention relates to a stable mixture comprising surface-modified particles which are obtained by reacting metal or semimetal oxide particles with at least one compound selected from silicon-containing compounds containing at least one metalloxy radical and optionally further alkoxy and / or hydroxy radical (s), and at least one solvent, at least one surfactant or a mixture thereof, a process for their preparation, the use of these particles in systems in which they are brought into contact with at least one solvent, wherein the mass ratio of solvent to modified particle is greater than 500, and the use of these particles in agglomeration-deagglomeration cycles. Metal and / or Halbmetalloxidpartikel which are functionalized on the surface with silicon-containing compounds are already known from the prior art.

For example, WO 2009/059382 A1 discloses a hydrophobic modification of mineral fillers and mixed polymer systems. According to this document, the hydrophobic modification takes place by reaction of the corresponding mineral particles with silanes, for example C 3 -C 12 -alkyl-trialkoxy-silanes. The fact that the correspondingly hydrophobically modified particles according to WO 2009/059382 A1 are particularly stable in large amounts of solvents, if appropriate in the presence of surface-active substances, is not disclosed in this document.

The object of the present invention over the prior art is thus to provide hydrophobized particles on the surface, which are distinguished by a particularly high stability to large amounts of solvents and / or surface-active substances.

This object is achieved by a stable mixture comprising surface-modified particles which are obtained by reacting metal or semimetal oxide particles with at least one compound of the general formula (I) wherein R ¹ , R ² and n have the following meanings:

R ^{1 is} independently hydrogen, linear or branched, optionally functionalized C 1 -C 30 -alkyl, linear or branched, optionally functionalized C 2 -C 30 -functional

Alkenyl, linear or branched, optionally functionalized C 2 -C 30 -alkynyl, optionally functionalized C 3 -C 20 -cycloalkyl, optionally functionalized C 3 -C 20 -cycloalkenyl, optionally functionalized C 1 -C 20 -heteroalkyl, optionally functionalized C 5 -C 22 -aryl, optionally functionalized C 6 -C 23 -alkylaryl, optionally functionalized C 6 -C 23 -arylalkyl, optionally functionalized C 5 -C 22 -heteroyl, R ² independently of one another hydrogen, linear or branched, optionally functionalized C 1 -C 30 -alkyl, linear or branched, optionally functionalized C 2 -C 30 -alkenyl, linear or branched, optionally functionalized C 2 -C 30 -alkynyl, optionally functionalized C 3 -C 20 -cycloalkyl, optionally functionalized C 3 -C 20 -cycloalkenyl, optionally functionalized C 1 -C 20 -heteroalkyl, optionally functionalized C 5 -C 22 -aryl, optionally functionalized C 6 -C 23 -alkylaryl, optionally functionalized C 6 -C 23 -arylalkyl, optionally functionalized C 5 -C 22 -heteroyl,

NR ¹ 4 ⁺ , where R ^{1 can} independently of one another have the abovementioned meanings, group of general formula 1 / (px * y) MP ⁺ X ^x _y , where M is a metal atom selected from the group consisting of metals of the main groups and subgroups of Periodic table of the elements, X is an anion, p is an oxidation number of the metal atom M, x is an integer of 1, 2 or 3 and y is an integer of 0, 1 or 2, and / or

Group of the general formula (IIa)

-SiR ¹ _m (OR ² ) ₃ -m (Na), where R ¹ and R ² independently of one another have the abovementioned meanings and m can independently of one another denote 0, 1, 2 or 3, n is 1, 2 or 3, and at least one solvent, at least one surface-active substance or a mixture thereof, wherein in the compound of general formula (I) or in the group of general formula (IIa) at least one radical R ² NRV or one group of general formula 1 / (px * y) MP ⁺ X ^{x "} _y with the meanings given above for R ¹ , p, x, y, M and X.

If R ² in the compound of the general formula (I) has the meaning of a group of the general formula (IIa) several times, for example more than once, corresponding compounds are present which carry two, three, four or more units with Si atoms , Therefore, in the case where R ^{2 is} a group of the general formula (IIa) several times, polysiloxanes are present.

Furthermore, the object is achieved by the use of the surface-modified particles according to the invention in systems in which the modified particles have at least a solvent, wherein the mass ratio of solvent to modified particle is greater than 500.

The object according to the invention is also achieved by the use of surface-modified particles according to the invention in agglomeration-deagglomeration cycles.

The stable mixture of the present invention contains surface-modified particles obtained by reacting metal or semimetal oxide particles with at least one compound of the general formula (I) or a polysiloxane of the general formula (I) containing groups of the general formula (IIa).

In the context of the present invention, it is generally possible to use all metal or semimetal oxide particles known to the person skilled in the art, in particular metal oxide particles. Examples of metal oxides which are particularly suitable according to the invention are the oxides of the metals of the main groups and subgroups of the Periodic Table of the Elements, in particular of the subgroups of the Periodic Table of the Elements.

According to the invention, silicon oxide is not preferred as a semi-metal oxide and is therefore not included in a preferred embodiment of the present invention.

In a preferred embodiment, the present invention therefore relates to the mixture according to the invention, wherein silicon dioxide is excluded as the semi-metal oxide.

Examples of suitable metals of the main groups of the Periodic Table of the Elements are the alkali metals, for example Li, Na, K, Rb, Cs, alkaline earth metals, for example Be, Mg, Ca, Ba, Sr, the third main group of the Periodic Table of the Elements, for example Al, Ga In, TI, the fourth main group of the Periodic Table of the Elements, for example Sn, Pb or the fifth main group of the Periodic Table of the Elements, for example Sb, Bi. Examples of suitable metals of the subgroups of the Periodic Table of the Elements are Sc, Y, the lanthanides, the Actinide, Ti, Zr, Hf, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn and Cd.

In a preferred embodiment, the metal oxide used according to the invention is an oxide of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Ba, Sr, Al, Ga, In, Tl, Sn, Pb , Sb, Bi, Sc, Y, the lanthanides, the actinides, Ti, Zr, Hf, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn , Cd and mixtures thereof, most preferably selected from the group consisting of Mn, Fe, Co, Ni, Cu and combinations thereof. Furthermore, according to the invention, mixed oxides of these metals, in particular Mn, Fe, Co, Ni or Cu, with at least one alkaline earth metal, for example Mg, Ca, Sr and / or Ba, are also suitable. The present invention therefore preferably relates to the mixture according to the invention, wherein the metal oxide used is an oxide of a metal selected from the group consisting of Mn, Fe, Co, Ni, Cu, combinations thereof and mixed oxides of these metals with at least one alkaline earth metal, for example Mg, Ca , Sr and / or Ba is.

In a particularly preferred embodiment, the present invention relates to the mixture according to the invention, wherein the metal oxide or Halbmetalloxidpartikel are magnetic.

Very particularly preferred metal oxides are iron oxides, for example Fe 2 O 3, magnetic iron oxides, for example magnetite, maghemite, hematite, cubic ferrites of the general formula (III)

M ²⁺ _x Fe ²⁺ i- _x Fe ³⁺ ₂ 04 (III) with

M is selected from Co, Ni, Mn, Zn and mixtures thereof and

x <1, hexagonal ferrites, for example calcium, barium or strontium ferrite MFeβOig with M = Ca, Sr, Ba, and combinations thereof.

In a preferred embodiment, the metal oxide used according to the invention is a magnetic iron oxide selected from the abovementioned group. In a very particularly preferred embodiment, the at least one metal oxide used according to the invention is magnetite. Magnetite has the formula Fe30 ₄ , in particular Fe ^M Fe ^m 204, and is known in the art. Magnetite can be prepared by known methods and is commercially available. If appropriate, the metal oxide particles used according to the invention may also contain further dopants, for example further metals in oxidic or elemental form, for example noble metals such as platinum.

The present invention particles generally have a particle size of 50 nm to 500 μιτι, preferably 200 nm to 100 μιτι, more preferably 500 nm to 10 μιτι on.

The present invention particles may generally have any shape, for example, spherical, cylindrical, needle-shaped or brick-shaped. In the stable mixture according to the invention, modified particles are present on the surface, which are obtained by reacting metal or semimetal oxide particles with at least one compound of the general formula (I) RVSi (OR ² ) ₄ . (L) wherein R ¹ , R ² and n have the abovementioned meanings, it being essential to the invention that in the compound of the general formula (I) or in the group of the general formula (IIa) at least one radical R ² NRV or a group of the general formula 1 / (px * y) MP ⁺ X ^X _Y having the abovementioned meanings for R ¹ , p, x, y, M and X.

Furthermore, the present invention relates to a stable mixture comprising surface-modified particles which are obtained by reacting metal or semimetal oxide particles with at least one compound of the general formula (I)

RVSi (OR ² ) ₄ k. in which R ¹ , R ² and n have the abovementioned meanings, it being essential to the invention that in the compound of general formula (I) or in the group of general formula (IIa) at least one radical R ² NRV or a Group of general formula 1 / (px * y) MP ⁺ X ^X _Y with the meanings given above for R ¹ , p, x, y, M and X is. R ^{1 is} independently of one another a linear or branched, optionally functionalized C 1 -C 30 -alkyl, particularly preferably C 1 -C 20 -alkyl, very particularly preferably C 1 -C 12 -alkyl. In a preferred embodiment, R ^{1 is} a linear or branched, non-functionalized C 1 -C 30 -alkyl, particularly preferably C 1 -C 20 -alkyl, very particularly preferably C 1 -C 12 -alkyl. Examples of linear or branched C ₄ -C 12 -alkyl radicals are butyl, in particular n-butyl, isobutyl, tert-butyl, pentyl, in particular n-pentyl, isopentyl, tert-pentyl, hexyl, in particular n-hexyl iso-hexyl, tert-hexyl, heptyl, especially n-heptyl, iso-heptyl, tert-heptyl, octyl, especially n-octyl, iso-octyl, tert-octyl, nonyl, in particular n-nonyl, iso Nonyl, tert-nonyl, decyl, in particular n-decyl, isodecyl, tert-decyl, undecyl, in particular n-undecyl, iso-undecyl, tert-undecyl, or dodecyl, in particular n-dodecyl, iso- Dodecyl, tert-dodecyl.

More preferably, R ^{1 is} independently a linear or branched, optionally functionalized C ₂ -C 30 -alkenyl, more preferably C ₂ -C 20 -alkenyl, very particularly preferably C ₂ -C 3 or C ₄ -C 12 -alkenyl. Examples of alkenyl radicals which are particularly preferred according to the invention are ethenyl (vinyl), propenyl, in particular n-propenyl, isopropenyl, butenyl, in particular n-butenyl, isobutene, tert-butenyl, pentenyl, in particular n-pentenyl, iso-pentenyl, tert-pentenyl, hexenyl, especially n-hexenyl, iso-hexenyl, tert-hexenyl, heptenyl, in particular n-heptenyl, iso-heptenyl, tert-heptenyl, octenyl, in particular n-octenyl, iso- Octenyl, tert-octenyl, nonenyl, especially n-nonenyl, isonononyl, tert-nonenyl, decenyl, in particular n-decenyl, iso-decenyl, tert-decenyl, undecenyl, in particular n-undecenyl, iso-undecenyl, tert-undecenyl, or dodecenyl, especially n-dodecenyl, iso-dodecenyl, tert-dodecenyl. More preferably, R ^{1 is} independently a linear or branched, optionally functionalized C 2 -C 30 -alkynyl, more preferably C 2 -C 20 -alkynyl, very particularly preferably C 2 -C 3 or C 4 -C 12 -alkynyl. Examples of particularly preferred alkenyl radicals according to the invention are ethynyl, propynyl, in particular n-propynyl, isopropynyl, butynyl, in particular n-butynyl, isobutynyl, tert-butynyl, pentynyl, in particular n-pentynyl, isopentynyl, tert. Pentynyl, hexynyl, especially n-hexynyl, iso-hexynyl, tert-hexynyl, heptynyl, in particular n-heptynyl, iso-heptynyl, tert-heptinyl, octynyl, especially n-octynyl, iso-octynyl, tert-octynyl, Nonenyl, in particular n-nonynyl, isononinyl, tert-nonynyl, decynyl, in particular n-decynyl, isodecyl, tert-decynyl, undecynyl, in particular n-undecynyl, iso-undecynyl, tert-undecynyl or dodecyl - nyl, especially n-dodecynyl, iso-dodecynyl, tert-dodecynyl.

More preferably, R ^{1 is} independently an optionally functionalized C 3 -C 20 -cycloalkyl, more preferably C 3 -C 12 -cycloalkyl, most preferably C 3 -C 6 -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

More preferably, R ^{1 is} independently an optionally functionalized C 3 -C 20 -cycloalkenyl, particularly preferably C 3 -C 12 -cycloalkenyl, very particularly preferably C 3 -C 6 -cycloalkenyl, for example cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl. More preferably, R ^{1 is} independently an optionally functionalized C 1 -C 20 heteroalkyl, particularly preferably C 1 -C 12 heteroalkyl. The heteroaromatic radicals present in accordance with the invention are derived from the abovementioned alkyl radicals, where at least one carbon atom is replaced by a heteroatom selected from N, O, P or S. More preferably, R ^{1 is} independently an optionally functionalized C 5 -C 22 aryl, more preferably C 5 -C 12 aryl. Examples of preferred aryl radicals according to the invention are phenyl, naphthyl or biaryls.

More preferably, R ^{1 is} independently an optionally functionalized C 6 -C 23 alkylaryl, particularly preferably C 6 -C 13 alkylaryl. An example of a preferred alkylaryl radical according to the invention is benzyl.

More preferably, R ^{1 is} independently an optionally functionalized C 6 -C 23 arylalkyl, particularly preferably C 6 -C 13 -arylalkyl. Examples of preferred arylalkyl radicals according to the invention are toluyl, xylyl, propylbenzyl, hexylbenzyl.

More preferably, R ^{1 is} independently an optionally functionalized C 5 -C 22 heteroaryl, particularly preferably C 5 -C 12 heteroaryl. The radicals R ^{1 mentioned} may optionally be functionalized. Suitable functional groups are, for example, selected from amino, amido, imido, hydroxyl, ether, aldehyde, keto, carboxylic acid, thiol, thioether, hydroxamate or carbamate groups. The GE- R ¹ radicals may be mono- or polyfunctionalized. In the case of multiple functionalization, a functional group may be present several times, or different functional groups are present at the same time. The radicals mentioned for R ¹ can moreover be monosubstituted or polysubstituted by the abovementioned alkyl, alkenyl, alkynyl, aryl, alkylaryl, arylalkyl, heteroalkyl or heteroaryl radicals.

Very particularly preferred radicals R ¹ are octyl, especially n-octyl, hexyl, especially n-hexyl and / or butyl, especially n-butyl, decyl, especially n-decyl, or dodecyl, especially n-dodecyl.

"Independently" that, if in the compound of the general formula (I) and the group of the general formula (IIa) means in the context of the present invention, a plurality of R ¹ are present, they may be the same or different. Preferably, R ² is independently of one another hydrogen, a linear or branched, optionally functionalized C 1 -C 30 -alkyl, particularly preferably C 1 -C 20 -alkyl, very particularly preferably C 1 -C 12 -alkyl. In a preferred embodiment, R ^{2 is} a linear or branched, non-functionalized C 1 -C 4 -alkyl radical. C 30 -alkyl, particularly preferably C 1 -C 20 -alkyl, very particularly preferably C 1 -C 12 -alkyl, examples of linear or branched C 1 -C 12 -alkyl radicals are methyl, ethyl, propyl, in particular n-propyl, isopropyl, butyl, in particular n-butyl, isobutyl, tert-butyl, pentyl, in particular n-pentyl, isopentyl, tert-pentyl, hexyl, in particular n-hexyl, iso-hexyl, tert-hexyl, heptyl, especially n- Heptyl, iso-heptyl, tert-heptyl, octyl, i in particular n-octyl, isooctyl, tert-octyl, nonyl, in particular n-nonyl, isononyl, tert-nonyl, decyl, in particular n-decyl, isodecyl, tert-decyl, undecyl, in particular n -Nedecyl, iso-undecyl, tert-undecyl, or dodecyl, especially n-dodecyl, iso-dodecyl, tert-dodecyl.

More preferably, R ^{2 is} independently a linear or branched, optionally functionalized C 2 -C 30 -alkenyl, particularly preferably C 2 -C 20 -alkenyl, very particularly preferably C 2 -C 12 -alkenyl. Examples of particularly preferred alkenyl radicals according to the invention are ethenyl (vinyl), propenyl, in particular n-propenyl, isopropenyl, butenyl, in particular n-butenyl, isobutyl, tert-butenyl, pentenyl, in particular n-pentenyl, isopentenyl, tert-pentenyl, hexenyl, in particular n-hexenyl, iso-hexenyl, tert-hexenyl, heptenyl, in particular n-heptenyl, iso-heptenyl, tert-heptenyl, octenyl, in particular n-octenyl, iso-octenyl, tert-hexenyl Octenyl, nonenyl, in particular n-nonenyl, isonononyl, tert-nonenyl, decenyl, in particular n-decenyl, isodecenyl, tert-decenyl, undecenyl, in particular n-undecenyl, iso-undecenyl, tert-undecenyl, or dodecenyl, especially n-dodecenyl, iso-dodecenyl, tert-dodecenyl.

More preferably, R ^{2 is} independently a linear or branched, optionally functionalized C 2 -C 30 -alkynyl, particularly preferably C 2 -C 20 -alkynyl, very particularly preferably C 2 -C 12 -alkynyl. Examples of particularly preferred alkenyl radicals according to the invention are ethynyl, propynyl, in particular n-propynyl, isopropynyl, butynyl, in particular n-butynyl, isobutynyl, tert-butynyl, pentynyl, in particular n-pentynyl, isopentynyl, tert. Pentynyl, hexynyl, in particular Re n-hexynyl, iso-hexynyl, tert-hexynyl, heptynyl, especially n-heptynyl, iso-heptynyl, tert-heptynyl, octynyl, especially n-octynyl, iso-octynyl, tert-octynyl, nonynyl, especially n Nonynyl, isononinyl, tert-nonynyl, decynyl, especially n-decynyl, isodecynyl, tert-decynyl, undecynyl, especially n-undecynyl, iso-undecynyl, tert-undecynyl, or dodecynyl, in particular n-dodecynyl, iso-dodecynyl, tert-dodecynyl.

More preferably, R ^{2 is} independently an optionally functionalized C 3 -C 20 -cycloalkyl, more preferably C 3 -C 12 -cycloalkyl, more preferably C 3 -C 6 -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

More preferably, R ^{2 is} independently an optionally functionalized C 3 -C 20 -cycloalkenyl, particularly preferably C 3 -C 12 -cycloalkenyl, very particularly preferably C 3 -C 6 -cycloalkenyl, for example cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl. More preferably, R ^{2 is} independently an optionally functionalized C 1 -C 20 heteroalkyl, more preferably C 4 -C 12 heteroalkyl. The heteroaromatic radicals present in accordance with the invention are derived from the abovementioned alkyl radicals, where at least one carbon atom is replaced by a heteroatom selected from N, O, P or S. More preferably, R ^{2 is} independently an optionally functionalized C 5 -C 22 aryl, more preferably C 5 -C 12 aryl. Examples of preferred aryl radicals according to the invention are phenyl, naphthyl or biaryls.

More preferably, R ^{2 is} independently an optionally functionalized C 6 -C 23 alkylaryl, more preferably C 6 -C 13 alkylaryl. An example of a preferred alkylaryl radical according to the invention is benzyl.

More preferably, R ^{2 is} independently an optionally functionalized C 6 -C 23 arylalkyl, particularly preferably C 6 -C 13 arylalkyl. Examples of preferred arylalkyl radicals according to the invention are toluyl, xylyl, propylbenzyl, hexylbenzyl.

More preferably, R ^{2 is} independently an optionally functionalized C5-C22 Heterorayl, more preferably C5-Ci2-heteroaryl. The radicals R ^{2 mentioned} may optionally be functionalized. Suitable functional groups are, for example, selected from amino, amido, imido, hydroxyl, ether, aldehyde, keto, carboxylic acid, thiol, thioether, hydroxamate or carbamate groups. The radicals R ^{1 mentioned} may be mono- or polyfunctionalized. In the case of multiple functionalization, a functional group may be present several times, or different functional groups are present at the same time. The radicals mentioned for R ² can also be mono- or polysubstituted by the abovementioned alkyl, alkenyl, alkynyl, aryl, alkylaryl, arylalkyl, heteroalkyl or heteroaryl radicals. It is essential to the invention that in the compound of the general formula (I) or in the group of the general formula (IIa) at least one radical R ² NRV or a group of the general formula 1 / (px * y) MP ⁺ X ^x _y with the above meanings for R ¹ , p, x, y, M and X is.

In one embodiment, at least one R ^{2 is} NRV. In this case, R ¹ independently of one another can have the abovementioned meanings, in which case R ¹ is preferably hydrogen, methyl, ethyl, propyl, especially n-propyl, octyl, especially n-octyl, hexyl, especially n-hexyl and / or butyl, especially n-butyl, decyl, especially n-decyl, or dodecyl, especially n-dodecyl.

In a further preferred embodiment, at least one R ^{2 is} a group of the general formula 1 / (px * y) MP ⁺ X ^X _Y , where M metal atom is selected from the group consisting of metals of the main groups and subgroups of the Periodic Table of the Elements, X an anion, p is an oxidation number of the metal atom M, x is an integer of 1, 2 or 3 and y is an integer of 0, 1 or 2,

In said general formula, in general, X represents an anion, for example selected from the group consisting of CH NO3 ^", SO4 ^2" or PO4 ^{3 ".} For these preferred embodiments, x is 1 2 or 3 means, and thus corresponds to the negative formal charge of the anions.

The number of anions present in said group is described by y. Preferably, y therefore means 0, 1 or 2, d. H. there are no, one or two further anion (s) in the grouping mentioned.

In a preferred embodiment, p is 1, 2, 3, 4, 5, 6 or 7, more preferably p is 1, 2, or 3.

Since in the compound of general formula (I), optionally containing at least one group of general formula (IIa) at least one R ² NRV or one group of general formula 1 / (px * y) MP ⁺ X ^x _y , this means in that, according to the invention, a salt is used as compound of the general formula (I). The positive formal charge (s) of the ammonium cation NRV or the grouping 1 / (px * y) MP ⁺ X ^x _y is / are compensated in this embodiment by the negative formal charge of the oxygen atom. Compounds of general formula (I), in which at least one R ² NRV or a group of the general formula 1 / (px * y) ⁺ X ^x MP _y is used in the invention are neutrally charged in a particularly preferred embodiment.

The factor 1 / (px * y) is essential to the invention since the molar amount of metal is dependent on the valence of the metal present and the number and valence of the possibly present lying anions. If, for example, Meta II atoms are used which are present in the oxidation state +3, ie p is equal to 3, then in the absence of further anions X, the molar amount of compound of the general formula (I) corresponds to three times the molar amount of metal to form a neutrally charged Si -containing salt. If, for example, metal atoms are used which are present in the oxidation state +2, ie p is equal to 2, then in the absence of further anions X the molar amount of compound of the general formula (I) corresponds to twice the molar amount of metal to give a neutral charge To obtain Si-containing salt. If, for example, metal atoms are used which are present in the oxidation state +1, ie p is equal to 1, then in the absence of further anions X the molar amount of compound of the general formula (I) corresponds to the molar amount of metal to form a neutrally charged Si -containing salt. In the case of mixtures of metal atoms with different valences or if certain amounts of anions with certain charges are present, the ratio is calculated accordingly. According to the invention, several embodiments are possible:

Is used as a K cation MP ⁺ is a monovalent cation such as Na ⁺ ⁺ etc., then there is of the general formula 1 / (px * y) ⁺ X ^x MP _y such a cation in each group. If the cation MP ^{+ used is} a divalent cation such as Ca ^2+, etc., the factor 1 / (p - x * y) in the absence of further anions, ie y is equal to zero, has the value 0.5, ie per group R ² is calculated to contain 0.5 equivalents of Ca ²⁺ . This can either be realized according to the invention by having in a compound of the general formula (I) or (IIa) two negatively charged oxygen atoms whose two total negative charges are neutralized by a Ca ²⁺ cation, so that each oxygen anion is calculated from 0 , 5 Ca ^{2+ is} neutralized. It is also possible in accordance with the invention that in two compounds of the general formula (I) or (IIa) there is in each case a negatively charged oxygen atom whose two total negative charges are neutralized by a Ca ²⁺ cation, so that each oxygen anion is calculated from 0 , 5 Ca ^{2+ is} neutralized. According to the invention, mixed forms of these embodiments are also possible.

In the case of polyvalent cations or mixtures of different cations, if appropriate with different oxidation numbers, the same applies. In general, M is selected from metals of the main groups and subgroups of the Periodic Table of the Elements, preferably from Groups 1, 2 and 13 (IUPAC nomenclature). Preferably, M is selected from the group of the alkali metals, for example Li, Na, K, Rb, Cs, Fr, preferably Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Fr, with p in each case equal to 1, from Group of alkaline earth metals, for example Be, Mg, Ca, Sr, Ba, Ra, preferably Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ²⁺ , where p is 2 in each case, and / or from group 13 of the Periodic Table of the Elements, for example B, Al, Ga, In, Tl, preferably B ³⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , with p in each case equal to 3. The present invention therefore preferably relates to the mixture according to the invention, wherein MP ^{+ is} selected from the group 1, 2 or 13 of the Periodic Table of the Elements (IUPAC Nomenclature). In a particularly preferred embodiment, in the compound of general formula (I) or in the group of general formula (IIa) at least one R ^{2 is} independently a group of the general formula 1 / (px * y) MP ⁺ X ^x _y with p is equal to 1, y is 0 and M is Na and / or K. The present invention therefore preferably relates to the mixture according to the invention, wherein in the compound of the general formula (I) or in the group of the general formula (IIa) at least one R ² independently each other is a group of the general formula 1 / (px * y) MP ⁺ X ^X _y where p is equal to 1, y is 0 and M is Na and / or K. In a further preferred embodiment, R ^{2 is} a group of the general formula (IIa)

-SiR ¹ _m (OR ² ) ₃ -m (Na), where R ¹ and R ² independently of one another have the abovementioned meanings and m can independently of one another denote 0, 1, 2 or 3, preferably 1 or 2. The connection of this group of general formula (IIa) to the compound of general formula (I) takes place via the free bond on the Si atom.

In a particularly preferred embodiment, R ¹ in the group of the general formula (IIa) independently of one another denotes hydrogen, methyl, ethyl, octyl, especially n-octyl, hexyl, especially n-hexyl and / or butyl, especially n-butyl, Decyl, especially n-decyl, or dodecyl, especially n-dodecyl.

In a particularly preferred embodiment, R ² in the group of the general formula (IIa) independently of one another is methyl or ethyl.

In a particularly preferred embodiment, in the group of the general formula (IIa) at least one R ² independently of one another is a group of the general formula 1 / (px * y) MP ⁺ X ^X _y where p is 1, y is 0 and M is Na and / or K.

The present invention therefore preferably relates to the mixture according to the invention, wherein in the group of the general formula (IIa) at least one R ^{2 is} independently a group of the general formula 1 / (px * y) MP ⁺ X ^x _y where p is equal to 1, y 0 and M is Na and / or K

If groups of the general formula (IIa) are present repeatedly in the compound of the general formula (I), polysiloxanes according to the invention are used as compounds of the general formula (IIa) Formula (I) used. If according to the invention polysiloxanes containing groups of the general formula (IIa) are used, these may be linear or branched. Polysiloxanes containing groups of the general formula (IIa) used according to the invention generally have a molecular weight of 250 to 200,000 g / mol, preferably 250 to 20,000 g / mol, more preferably 300 to 5,000 g / mol.

"Independent from each other" in the context of the present invention means that, if in the compound of general formula (I) or (IIa) several radicals R ² are present, they may be the same or different.

In the compound of general formula (I) n is generally 1, 2 or 3. Preferably n in the compound of general formula (I) is 1 or 2. More preferably n in the compound of general formula (I) 1. Therefore, the present invention preferably relates to the mixture according to the invention, wherein in the compound of the general formula (I) n is 1 or 2, more preferably 1.

In the polysiloxanes of the general formula (I) containing groups of the general formula (IIa), m is generally independently 0, 1, 2 or 3, preferably 1 or 2.

Compounds of the general formula (I) which are particularly preferred according to the invention are selected from the group of salts consisting of

RVSi (OR ² ) ₄ -n where R ¹ is methyl, ethyl, butyl, pentyl, hexyl, octyl, decyl and / or dodecyl, R ² is Na, K and / or NH ₄ and n is 1, 2 or 3, or

RVSi (OR ² ) ₄ - _n where R ¹ is methyl, ethyl, butyl, pentyl, hexyl, octyl, decyl and / or dodecyl, R ² is 0.5 Ca and / or 0.5 Mg and n is 1, 2 or 3, wherein the above applies to the divalent cations. In these particularly preferred embodiments, there are no further anions X ^x_ , ie in the formula 1 / (px * y) y is equal to zero.

Very particular preferred compounds of the general formula (I) are selected from the group consisting of (NaO) (CH ₃ ) Si (OH) ₂ , (NaO) (C ₂ H ₅ ) Si (OH) ₂ , (NaO) (C ₅ Hn) Si (OH) ₂ , (NaO) (C ₈ Hi 7) Si (OH) ₂ , (KO) (CH ₃ ) Si (OH) ₂ , (KO) (C ₂ H ₅ ) Si (OH) ₂ , (KO) (C ₅ Hn) Si (OH) ₂ ,

(KO) (C ₈ Hi 7) Si (OH) ₂ , (NH ₄ O) (CH ₃ ) Si (OH) ₂ , (NH ₄ O) (C ₂ H ₅ ) Si (OH) ₂ , (NH 0) (C ₅ Hn) Si (OH) ₂ , (NH ₄ O) (C ₈ Hi ₇ ) Si (OH) ₂ , (NaO) ₂ (CH ₃ ) Si (OH), (NaO) ₂ (C ₂ H ₅ ) Si (OH), (NaO) ₂ (C ₅ Hn) Si (OH), (NaO) ₂ (C ₈ Hi 7) Si (OH), (KO) ₂ (CH ₃ ) Si (OH), (KO) ₂ (C ₂ H ₅ ) Si (OH), (KO) ₂ (C ₅ Hn) Si (OH),

(KO) ₂ (C ₈ Hi ₇ ) Si (OH), (NH ₄ O) ₂ (CH ₃ ) Si (OH), (NH ₄ O) ₂ (C ₂ H ₅ ) Si (OH), (NH ₄ 0) ₂ (C ₅ Hn) Si (OH), (NH ₄ O) ₂ (C ₈ Hi ₇ ) Si (OH), (NaO) ₃ (CH ₃ ) Si, (NaO) ₃ (C ₂ H ₅ ) Si, (NaO) ₃ (C ₅ Hn) Si, (NaO) ₃ (C ₈ Hi ₇ ) Si, (KO) ₃ (CH ₃ ) Si, (KO) ₃ (C ₂ H ₅ ) Si, (KO) ₃ (C ₅ Hn) Si, (KO) ₃ (C ₈ Hi ₇ ) Si, (NH ₄ O) ₃ (CH ₃ ) Si, (NH ₄ O) ₃ (C ₂ H ₅ ) Si, (NH ₄ O) 3 (C ₅ Hii) Si, (NH ₄ O) ₃ (C ₈ Hi ₇ ) Si, (NaO) (CH ₃ ) ₂ Si (OH), (NaO) (C ₂ H ₅ ) ₂ Si (OH)

(KO) (CH ₃ ) ₂ Si (OH), (KO) (C ₂ H ₅ ) ₂ Si (OH), (NaO) ₂ (CH ₃ ) ₂ Si, (NaO) ₂ (C ₂ H ₅ ) ₂ Si, (KO) ₂ (CH ₃ ) ₂ Si, (KO) ₂ (C ₂ H ₅ ) ₂ Si, Ca ⁺ [(O) (CH ₃ ) Si (OH) ₂ ] ₂ , Ca ⁺ [(0) (C ₂ H ₅ ) Si (OH) ₂ ] ₂ , Ca ⁺ [(O) (C ₅ Hn) Si (OH) ₂ ] ₂ , Ca ⁺ [(O) (C ₈ Hi ₇ ) Si (OH) ₂ ] ₂ , Ca ⁺ [(O) (CH ₃ ) ₂ Si (OH)] ₂ , Ca ⁺ [(O) (C ₂ H ₅ ) ₂ Si (OH)] ₂ ,

Ca ⁺ [(O) ₂ (CH ₃ ) Si (OH)], Ca ⁺ [(O) ₂ (C ₂ H ₅ ) Si (OH)], Ca ⁺ [(O) ₂ (C ₅ Hn) Si ( OH)],

Ca ⁺ [(O) ₂ (C ₈ Hi ₇ ) Si (OH)], Ca ⁺ [(O) ₂ (CH ₃ ) ₂ Si], Ca ⁺ [(O) ₂ (C ₂ H ₅ ) ₂ Si] .

A preferred class of polysiliconates of the general formula (I) according to the invention containing groups of the general formula (IIa) are polymethylsiliconates and polydimethylsilicoates with sodium, potassium, magnesium, calcium or ammonium as cation.

The present invention also relates to a process for producing a surface-modified particle as defined above by contacting the metal or semi-metal oxide particle to be modified and a compound of the general formula (I) as defined above.

The reaction of said metal or Halbmetalloxidpartikel with the compounds of general formula (I) or the polysiloxanes of the general formula (I) containing groups of the general formula (IIa) can be carried out by methods known in the art, for example by contacting the substrates in a solvent, for example toluene or water, at a temperature from room temperature to the boiling point of the solvent. In addition, under certain circumstances, in the same or a separate step, the contacting with other reactants or accelerators, such as acids, C0 ₂ , etc. After conventional workup, the reaction product of metal or Halbmet- talloxidpartikel and compounds of general formula (I) or Polysiloxanes of the general formula (I) containing groups of the general formula (IIa) are obtained.

The fixation of the silicon compounds on the metal or Halbmetalloxidoberfläche takes place preferably by a condensation of the surface hydroxyl groups of the oxide M-OH with silanol groups of the silicon compound (Si-OH + M-OH Si-OM + H ₂ 0). The silanol groups may already be present in the starting silicon compound of the formula (I) or a subunit (IIa) or may be formed in situ. This can be done for example by the hydrolysis of the silicon ether (Si-OR + H ₂ 0) to the silanol (Si-OH + ROH). SiOR ² can be hydrolyzed, R ¹ and all other radicals mentioned can not be hydrolyzed.

The process according to the invention can be carried out, for example, by spraying a reagent solution comprising the compound of the general formula (I) onto the metal oxide or semimetal oxide particles. Another method of contacting the metal or semimetal oxide particles to be modified and a compound of general formula (I) as defined above is, for example, the metal or semimetal oxide particles in a compound of general formula (I) or in a solution of a compound the general my formula (I) in a suitable solvent to suspend. Corresponding methods are known per se to the person skilled in the art.

After the compound of formula (I) has been contacted with the metal or semimetal oxide particle, a further treatment step may be necessary to complete the fixation reaction. This can be z. B. by adjusting the pH, temperature treatment, treatment with various gas atmospheres, eg. As CO2 or SO2, or a combination of such steps. In addition to the above-mentioned functionalized metal or metalloid oxide particles, the stable mixture according to the invention contains at least one solvent, at least one surface-active substance or a mixture thereof.

It has surprisingly been found that the reaction products of the invention, d. H. the surface-functionalized metal oxide or semimetal oxide particles are particularly stable in mixtures with solvent and / or surface-active compounds, d. H. there is no cleavage of superficially bound silicon compounds.

The at least one solvent present in the mixture according to the invention is preferably selected from the group consisting of aromatic hydrocarbons, for example benzene, toluene, xylene, alcohols, for example methanol, ethanol, propanols, such as n-propanol, isopropanol, butanols, such as n-butanol, isobutanol, tert-butanol, ethers, such as diethyl ether, methyl tert-butyl ether, isobutyl tert-butyl ether, cyclic ethers, such as tetrahydrofuran, dioxane, esters, cyclic esters , Alkanes such as hexane, cycloalkanes such as cyclohexane, olefins, cycloolefins, water and mixtures thereof. If mixtures of solvents are used according to the invention, preference is given to using solvents which are completely miscible with one another, ie. H. form a phase during mixing.

Therefore, the present invention preferably relates to the mixture according to the invention, wherein the at least one solvent is selected from the group consisting of aromatic hydrocarbons, for example benzene, toluene, xylene, alcohols, for example methanol, ethanol, propanols, such as n-propanol, isopropanol, Butanols, such as n-butanol, isobutanol, tert-butanol, ethers, such as diethyl ether, methyl tert-butyl ether, isobutyl tert-butyl ether, cyclic ethers, such as tetrahydrofuran, dioxane, esters, cyclic Esters, alkanes, such as hexane, cycloalkanes, such as cyclohexane, olefins, cycloolefins, water and mixtures thereof.

In a preferred embodiment, the mixture according to the invention is found in processes in which the superficially modified particles are brought into contact with particularly large amounts of solvent.

In the mixture according to the invention is generally a solids content of up to 70 wt .-%, preferably up to 60 wt .-% before. It follows that the content of at least a solvent in the mixture according to the invention is generally at least 30% by weight, preferably at least 40% by weight, ie in general from 30 to 99.9% by weight, preferably from 40 to 99.9% by weight of solvent. According to the invention, solids content is understood to mean the content of particles modified according to the invention on the surface and optionally further solids present.

The at least one surface-active substance present in the mixture according to the invention is preferably selected from the group consisting of nonionic, anionic, cationic or zwitterionic surfactants and mixtures thereof.

Preferred examples of nonionic surfactants according to the invention are fatty alcohol polyglycol ethers, in particular fatty alcohol polyethylene glycol ethers.

Preferred examples of anionic surfactants according to the invention are alkylbenzenesulfonates, secondary alkanesulfonates, .alpha.-olefinsulfonates, fatty alcohol sulfates or fatty alcohol ether sulfates.

Examples of cationic surfactants which are preferred according to the invention are stearyltrimethylammonium salts. Preferred examples of zwitterionic surfactants according to the invention are sultaines, fatty acid amidoalkylhydroxysultaine or alkylbetaines.

Particularly preferred surface-active substances according to the invention are sodium alkylphenol ether sulfates.

In the mixture according to the invention, the at least one surface-active substance is generally in an amount of 0.001 to 20 wt .-%, preferably 0.01 to 15 wt .-%, particularly preferably 0.1 to 10 wt .-%, each based on the entire mix, in front. If according to the invention at least one surface-active substance is present, the abovementioned amount of at least one solvent is adapted accordingly.

The surface-functionalized metal oxide or semimetal oxide particles are generally present in the mixture according to the invention in an amount of from 0.1 to 70% by weight, preferably from 0.1 to 60% by weight.

If further solids are present in the mixture according to the invention, the abovementioned amount of surface-functionalized metal oxide or semimetal oxide particles is adapted accordingly. In all possible embodiments, the amounts of surface-functionalized metal oxide or semimetal oxide particles, at least one solvent, add up. optionally present surface-active substances and optionally present further solids to 100 wt .-%.

In addition to the functionalized particles, the at least one solvent and / or the at least one surface-active substance, further components may be present in the mixture according to the invention, for example oxidic or metallic solids and further hydrophobic components. The sum of the amounts of the components present in the mixture according to the invention add up to 100% by weight in each case. In the mixture according to the invention, the mass ratio of solvent to modified particle is generally greater than 500, preferably 1000, more preferably greater than 5000, most preferably greater than 10000.

In the context of the present invention, the term "stable mixture" means that the superficially functionalized metal oxide or semimetal oxide particles present in the mixture according to the invention are not changed in the mixture, ie the surface silyl groups do not become from the surface of the metal oxide or Halbmetalloxidpartikel The mixture according to the invention as a whole does not change or only slightly changes that a mixture containing surface-modified particles is stable in the sense of the present invention can be demonstrated, for example, by using appropriate particles which are in contact with solvent and / or surface-active substance in a mixture according to the invention, remain chemically and / or physically unchanged, for example by an elemental analysis or determination of the hydrophobic properties, for example by Bes the buoyancy or the contact angle.

The present invention also relates to a process for the treatment of surface-modified particles of the invention with at least one solvent, wherein the mass ratio of solvent to modified particle is greater than 500.

With regard to the surface-modified particles and the solvents, what has been said with regard to the mixture according to the invention applies to the process according to the invention.

In the process according to the invention, the mass ratio of surface-modified particles and the at least one solvent is generally greater than 500, preferably greater than 1000, more preferably greater than 5000, most preferably greater than 10000.

In this process according to the invention, the surface-modified particles according to the invention are brought into contact, ie treated, with a relatively large amount of solvent. Corresponding systems according to the invention in which this treatment can take place are, for example, flowing systems in which the novel Surface modified particles are brought into contact with other materials, particles, materials, etc., for example in continuous processes, for example, continuous processes for agglomeration with other materials, particles, materials, etc. in solution or dispersion. The process according to the invention also relates to the deagglomeration of agglomerates of the surface-modified particles and further substances, particles or materials according to the invention or of agglomerates of the surface-modified particles to themselves, for example likewise in flowing systems.

The present invention also relates to the use of surface-modified particles of the invention in systems in which the modified particles are contacted with at least one solvent, wherein the mass ratio of solvent to modified particle is greater than 500.

With regard to the surface-modified particles and the solvent, the statements made regarding the mixture according to the invention apply.

The mass ratio of surface-modified particles and the at least one solvent is generally greater than 500, preferably greater than 1000, more preferably greater than 5000, most preferably greater than 10000.

In this use according to the invention, the surface-modified particles according to the invention are brought into contact with a relatively large amount of solvent. Corresponding systems according to the invention in which this contacting can take place are, for example, flowing systems in which the surface-modified particles according to the invention are brought into contact with further substances, particles, materials etc. in, for example, continuous processes, for example continuous agglomeration processes with other substances, particles, materials etc. in solution or dispersion. The use according to the invention also relates to the deagglomeration of agglomerates of the surface-modified particles and further substances, particles or materials according to the invention or of agglomerates of the surface-modified particles to themselves, for example also in flowing systems.

The present invention also relates to the use of surface-modified particles according to the invention, in particular magnetic particles, in agglomeration-deagglomeration cycles.

Also in this case, the statements made with respect to the mixture according to the invention apply to the surface-modified particles and the solvents. Under an agglomeration-deagglomeration cycle is understood according to the invention a method in which the inventive surface-functionalized particles, in particular magnetic particles, with itself or other particles, materials, materials, etc. in Solution or dispersion are brought into contact and agglomerate due to hydrophobic interaction, ionic, van der Waals interactions and / or other attractive forces. These agglomerates are then processed in the further process, for example separated from other components and / or the solution or dispersion. After this further processing, the agglomerates are then separated again, ie deagglomerated, so that the particles functionalized on the surface and the other particles, substances, materials, etc. are again present individually (deagglomeration). Examples of preferred agglomeration-deagglomeration cycles according to the invention are chemical, physical or biological test or separation processes, the cleaning of contaminated, for example heavy metal contaminated, soil, a water purification, recycling of electronic waste or a

Gravity separation.

In chemical, physical or biological test or separation methods, for example, specially modified magnetic nanoparticles are used which have on their surface anchor groups for a specific antigen or virus, for. Borrelia, HIV, hepatitis. These special anchor groups correspond in particular to the abovementioned group R ¹ , which is formed correspondingly, depending on the particular separation or test task, for example by the presence of the abovementioned functional groups. By attaching these antigens / viruses to the modified particle surface (agglomeration), these components can be separated from a solution by magnetic separation and detected accordingly. The functionalized magnetic particles are then recycled by surfactants which redissolve the electrostatic, adhesive or van der Waals interaction between functionalized magnetic particle and antigen / virus (deagglomeration). In this way, the functionalized magnetite particles can be used again.

In the purification of water, the modified particles according to the invention, in particular magnetic particles, can be used. Here you can z. B. use functionalized magnetite particles that remove organic matter, suspended solids or fat droplets from the water in which a hydrophobic agglomeration between the functionalized Magnetitparti- kel and the hydrophobic impurity takes place. These hydrophobic agglomerates can be separated by magnetic separation. In order to make water purification economical, it makes sense to "discharge" the hydrophobic magnetite particles back from the contaminant and recirculate it again, which can be reconstituted by deagglomeration with a special surface active agent (surfactant) and / or special solvent or solvent mixture take place.

Recycling of electronic waste, for example, by the magnetic recovery of valuable materials (Ir, Pt, Ru) made of electronic waste, again preferably modified magnetite particles can be used, which - after a hydrophobization of recyclables to be separated - agglomerate with them and can be separated. After separation, the present agglomerates are deagglomerated again, so that the modified magnetic particles can be reused. Another example is gravity separation, e.g. B. over the expert known cyclones. As a result, denser components of less dense can be separated via a gravity separation. If the individual components differ only slightly in their density, eg. As Pt-doped hematite and undoped hematite, the density of the component to be separated by agglomeration with another component can be increased. As a modified particle in this case, for example, the Pt-doped hematite component is hydrophobized according to the invention, so that after addition of hydrophobized barium sulfate, an agglomerate of the modified hematite and barium sulfate is formed, which has a greater density difference to the undoped hematite. After separation, the agglomerate can be deagglomerated again.

The present invention therefore also preferably relates to the use according to the invention, wherein the agglomeration-deagglomeration cycle comprises a chemical, physical or biological test or separation process, water purification, cleaning of contaminated, for example heavy metal contaminated soil, recycling of electronic waste or a Gravity separation is.

An inventive advantage is that the superficially modified particles according to the invention are stable under the conditions present in the agglomeration and, above all, deagglomeration, and therefore can preferably be reused.

Examples Example 1: General Methods

Example 1.1: Representation of the alkali metal alkyl siliconates used

The preparation of the alkali metal alkyl siliconates is carried out according to the procedure in R. Murugavel et al., Solid State Sciences 2001, 3 (1-2), 169-182. Alternatively, according to the examples in

GB675188A.

For example, for "OctSi (ONa) 3 representation within 30 min 1 mol" OctSi (OMe) 3 of the company. ABCR (97% strength) in a solution of 10 mol NaOH in 400 g of water. Subsequently, the reaction is completed under reflux within 4 h. By distilling off the solvent, a concentrated solution or, when fully dried, the product is obtained as a solid.

Example 1.2: repeated treatment of the solid with surfactant solution 10 g of the solid to be investigated are stirred in 1 l of a 0.2% strength by weight solution of Luten sit A-ES from BASF SE (mixture of sodium alkylphenol ether sulfates) in water at room temperature for 2 h. The solid is then filtered off and washed with 1 l of water, 100 ml of ethanol and 100 ml of acetone. The filter cake is dried at 120 ° C. for 4 h in vacuo. Subsequently, samples are taken for analysis. For the new washes, the remaining product is used.

Example 1.3: Quick Test Floatability on water

3 ml of water are introduced into a 5 ml sample vial. The spatula is then carefully placed on the water surface with the spatula. Subsequently, it is observed whether the solid sinks or floats permanently. For floating solids, shake the sealed container for 10 s. It is then observed whether the solid floats again or remains under water.

Example 1.4: Contact angle measurement Contact angle measurement on powders:

Contact angles are measured using a standard instrument (Dropshape Analysis Instrument, Kruss DAS 10). A silhouette of the drop is captured by a CCD camera and the drop shape is determined by computer-aided image analysis. The measurements are carried out unless otherwise specified, as described in DIN 5560-2. a) Preparation of a homogeneous powder layer

The magnetite powder is applied as a layer about 1 mm thick with a 100 μιτι thick BASF Acronal V215 adhesive dispersion on a PET film. Using a spatula, the powder is pressed into the adhesive and non-adherent excess material is removed by shaking. Finally, any remaining, loose material is removed by blowing with purified nitrogen under pressure over the sample. This process gives a clean, homogeneous powder surface over the entire surface of the substrate of 75mm x 25mm.

Powder surfaces normally show some roughness and contact angles or their measurement are sensitive to this roughness. Therefore, a direct comparison of the hydrophobicity can only be carried out on powders with the same particle size distribution and particle shape. Careful surface analysis using ToF-SIMS has shown that the surface of the powder layer produced by this process has no traces of adhesive and is representative of the powder. b) Dynamic, progressive contact angle measurement

One milliliter of water is placed as drops on the surface and 2 μΙ / min of water are continuously added. Thus, 20 μΙ of liquid volume are continuously fed. Starting from a minimum volume of approximately 3 μΙ, contact angles are measured, while the syringe needle used for metering remains in the drop. Contour measurements are taken at a rate of approximately 0.5 Hz, evaluated by a tangent method to determine the contact angle that is directly adjacent to the three-phase contact line. These contact angles are averaged over time, for each sample, five progressive drops are measured at different positions and the average value is determined with one standard deviation.

Example 1.5: Recycle attempts

An attempt is made, according to the particular example, to use hydrophobized magnetite as a recyclable carrier for the cleaning of (heavy metal) contaminated soil. For this purpose, 3 g of magnetite are dispersed in a system containing 100 g of a sand mixture (solids content: 1 wt .-%). This sand mixture contains at least 99% by weight of inorganic silicatic components (eg feldspars, mica, litter) and 1% by weight of a special hydrophobized inorganic As-containing impurity (enargite). The hydrophobization of this inorganic contaminant takes place with butyl xanthate. After vigorous passage through the hydrophobized magnetite with this sand mixture, the arsenic component is separated via hydrophobic flocculation with the magnetite. The hydrophobic constituents are collected and treated with a 0.1% strength by weight solution of a surfactant (Lutensit A-ES from BASF SE). In a next magnetic separation step, the magnetic components are separated from the non-magnetic As-containing impurities. The hydrophobic magnetite is washed with a 1: 1 mixture of water and EtOH, filtered off and mixed again with a newly prepared sand mixture. The process is repeated a total of ten times.

Example 2 Preparation of Hydrophobised Magnetite Example 2.1: with "OctSi (OK) 3 silanized magnetic pigment 345 from BASF SE (according to the invention)

Synthesis: 10 g of magnetic pigment 345 (magnetite Fe ^M (Fe ^m ) 204) from BASF SE are added to a solution of 370 mg of "OctSi (OK) 3 in 30 ml of water." The solution is stirred for 30 minutes at room temperature dried at 40 ° C. in vacuo, followed by storage at 40 ° C. in air for 7 days The resulting solid is washed with water until no more change in the pH of the wash water occurs, then the mixture is transferred at 40 ° C. Air dried overnight. The dried product is after precomminution by a test sieve (400 μιτι) deleted and thus deagglomerated and homogenized.

analytics:

Float test: fresh and ten times washed solid swim equally on water (even after shaking);

Contact angle: fresh 146 °, washed ten times 139 °; Recycle attempt: If the yield of the As component is detected, the yield of 92% in the first cycle drops only to 90% in the tenth cycle when using the "OctSi (OK) 3 silanized magnetic pigment 345 from BASF SE.

Example 2.2: with "BuSi (OH) 2 (ONa) silanized magnetic pigment 345 from BASF SE (according to the invention)

Synthesis: The synthesis is carried out according to the scheme described in Example 2.1. However, 350 mg ⁿ BuSi (OH) 2 (ONa) are used and storage is carried out at 120 ° C in a CO2 atmosphere.

analytics:

Contact angle: fresh 154 °, washed ten times 152 °;

Recycling experiment: If the yield of the As component is detected, the yield of 95% in the first cycle drops to only 91% in the tenth cycle when BASFS SE is used with ⁿ BuSi (OH) 2 (ONa) silanized magnetic pigment 345 ,

Example 2.3: with (Ca ²⁺ ) ["Pr (Me) Si (OH) (O -)] 2 silanized magnetic pigment 345 from BASF SE (according to the invention)

Synthesis: The synthesis is carried out according to the scheme described in Example 2.1. However, 340 mg (Ca ²⁺ ) [ ⁿ Pr (Me) Si (OH) (O)] 2 are used as the silanization reagent.

analytics:

Float test: fresh and ten times washed solid swim equally on water (even after shaking); Contact angle: fresh 142 °, washed ten times 136 °;

Recycling experiment: If the yield of the As component is detected, the yield of 89% im decreases when using the (Ca ²⁺ ) [ ⁿ Pr (Me) Si (OH) (O)] ₂ silanized magnetic pigment 345 from BASF SE first cycle only at 87% in the tenth cycle.

Example 3 Comparative Examples Comparative Example 3.1 Commercially available, hydrophobic magnetite Bayoxide E8707 H from Lanxess (not according to the invention)

analytics:

Float test: fresh solid floats even after shaking it on water, already twice washed solid no longer floats;

Contact angle: fresh 158 °, washed ten times 1 16 °

Recycling: Comparative tests with an already hydrophobic magnetite from Lanxess (product: Bayoxide E8707 H) show a dramatic yield loss of over 40% already after the fourth cycle. The experiments with this product will be stopped afterwards.

Comparative Example 3.2: With ^n- OctMe2SiCl silanized magnetic pigment 345 from BASF SE (not according to the invention)

Synthesis: Under an inert gas atmosphere, 10 g of magnetic pigment 345 from BASF SE are suspended in 20 ml of toluene. The suspension is heated to 70 ° C. before 0.3 g of octMe2SiCl (97% strength, ABCR) are added, the reaction mixture is then kept at 70 ° C. with stirring for 4 hours, after which the solid is filtered off , washed first with 50 ml of toluene, then 50 ml of methanol and finally with water until the washing solution is free of chloride The product is dried in vacuo at 120 ° C. for 4 h The dried product is after precomminution by an analytical sieve (400 μιτι) painted and thus deagglomerated and homogenized.

analytics:

Float test: solid floats on water (even after shaking), already simply washed solid no longer floats on water; Contact angle: fresh 148 °, simply washed 120 °, washed ten times 98 ° Comparative Example 3.3: with ⁿ BuMe2SiCl silanized magnetic pigment 345 from BASF SE (not according to the invention)

Synthesis: The synthesis is carried out according to the scheme described in Example 2.1. However, 0.3 g of "BuMe2SiCl (97% from ABCR) is used as the silanization reagent.

analytics:

Float test: solid floats on water (not after shaking), already simply washed solid no longer floats on water;

Contact angle: fresh 103 °, washed ten times 89 °

Comparative Example 3.4: Hydrophobised magnetic pigment 345 from BASF SE (not according to the invention) hydrophobicized with octylphosphonic acid

Synthesis: In an apparatus consisting of a 12 L plastic bucket with spout as a stirred tank and a metal stirrer, 8.0 kg of water are introduced. Subsequently, 2 kg of magnetic pigment 345 of BASF SE are metered in and the stirring speed of the metal stirrer is selected such that the pigment does not sediment and likewise no air is drawn in (no foam crown is formed). Subsequently, 12.5 g of n-octylphosphonic acid (OPS, 80% strength) from Albright & Wilson are added in one portion and all starting materials are mixed for 1.5 h in air at room temperature. After the stirring time has ended, the suspension is poured onto a porcelain cannula (d = 24 cm with a paper filter MN 85/90 from Macherey-Nagel). Any cracks in the filter cake are deleted to improve the washing effect. Overnight in a convection oven at 1 10 ° C dried. The dried product is after precomminution by a test sieve (400 μιτι) deleted and thus deagglomerated and homogenized. analytics:

Elemental analysis: in the final product 0.06% P;

Recycle attempt: After the third cycle, only a deficient yield of the As-containing impurity of less than 50% is detected. The experiments are subsequently aborted.

Claims

claims

1 . Stable mixture comprising surface-modified particles obtained by reacting metal or semimetal oxide particles with at least one compound of general formula (I)

RVSi (OR ² ) ₄ . (I) wherein R ¹ , R ² and n have the following meanings:

R ^{1 is} independently hydrogen, linear or branched, optionally functionalized C 1 -C 30 -alkyl, linear or branched, optionally functionalized C 2 -C 30 -alkenyl, linear or branched, optionally functionalized C 2 -C 30 -alkynyl, optionally functionalized C 3 -C 20 -alkyl Cycloalkyl, optionally functionalized C 3 -C 20 -cycloalkenyl, optionally functionalized C 1 -C 20 -heteroalkyl, optionally functionalized C 3 -C 22 -aryl, optionally functionalized C 6 -C 23 -alkylaryl, optionally functionalized C 6 -C 23 -arylalkyl, optionally functionalized C 5 -C 22 -heteroryl,

R ^{2 is} independently hydrogen, linear or branched, optionally functionalized C 1 -C 30 -alkyl, linear or branched, optionally functionalized C 2 -C 30 -alkenyl, linear or branched, optionally functionalized C 2 -C 30 -alkynyl, optionally functionalized C 3 -C 20 -cycloalkyl, optionally functionalized C 3 -C 20 -cycloalkenyl, optionally functionalized C 1 -C 20 -heteroalkyl, optionally functionalized C 3 -C 22 -aryl, optionally functionalized C 6 -C 23 -alkylaryl, optionally functionalized C 6 -C 23 -arylalkyl, optionally functionalized C 5 -C 22 -heteroyl,

NR ¹ 4 ⁺ , where R ^{1 can} independently of one another have the abovementioned meanings,

Group of the general formula 1 / (px * y) MP ⁺ X ^x _y , where M metal atom selected from the group consisting of metals of the main and subgroups of the Periodic Table of the Elements, X an anion, p oxidation number of the metal atom M, x a whole Number from 1, 2 or 3 and y is an integer from 0, 1 or 2, and / or

Group of the general formula (IIa)

-SiR ¹ _m (OR ² ) ₃ ! .- m (IIa), wherein R ¹ and R ² independently of one another have the abovementioned meanings and m independently of one another can denote 0, 1, 2 or 3, n 1, 2 or 3, and at least one solvent, at least one surface-active substance or a mixture thereof in that in the compound of the general formula (I) or in the group of the general formula (IIa) at least one radical R ² NRV or a group of the general formula 1 / (px * y) MP ⁺ X ^x _y with the above meanings for R ¹ , p, x, y, M and X is.

Mixture according to Claim 1, characterized in that M is selected from the group 1, 2 or 13 of the Periodic Table of the Elements (IUPAC Nomenclature).

Mixture according to claim 1 or 2, characterized in that the mass ratio of solvent to modified particle is greater than 500.

Mixture according to one of claims 1 to 3, characterized in that in the compound of general formula (I) n is 1 or 2, preferably 1.

Mixture according to one of claims 1 to 4, characterized in that in the compound of general formula (I) or in the group of general formula (IIa) at least one R ^{2 is} independently methyl or ethyl.

Mixture according to one of claims 1 to 5, characterized in that in the compound of the general formula (I) or in the group of the general formula (IIa) at least one R ^{2 is} independently a group of the general formula 1 / (px * y) MP ⁺ X ^X _y with p equal to 1, y is 0 and M is Na and / or K.

Mixture according to one of claims 1 to 6, characterized in that the at least one solvent is selected from the group consisting of aromatic hydrocarbons, alcohols, ethers, cyclic ethers, esters, cyclic esters, alkanes, cycloalkanes, olefins, cycloolefins, water and mixtures thereof.

Mixture according to one of claims 1 to 7, characterized in that the at least one surface-active substance is selected from the group consisting of nonionic, anionic, cationic or zwitterionic surfactants and mixtures thereof.

9. A mixture according to any one of claims 1 to 8, characterized in that the metal oxide used is an oxide of a metal selected from the group consisting of Mn, Fe, Co, Ni, Cu, combinations thereof and mixed oxides of these metals with at least one alkaline earth metal ,

10. A process for producing a surface-modified particle as defined in claim 1 by contacting the metal or Halbmetalloxidpar- tikels to be modified and a compound of general formula (I) as defined in claim 1. 1 1. Process for the treatment of surface-modified particles as defined in claim 1 with at least one solvent, characterized in that the mass ratio of solvent to modified particle is greater than 500.

Use of surface-modified particles as defined in claim 1 in systems in which the modified particles are brought into contact with at least one solvent, characterized in that the mass ratio of solvent to modified particle is greater than 500.

Use of surface-modified particles as defined in claim 1 in agglomeration-deagglomeration cycles.

14. Use according to claim 13, characterized in that the agglomeration-deagglomeration cycle is a chemical, physical or biological test or separation process, the purification of contaminated soil, a water purification, recycling of electronic waste or gravity separation.