EP2697314A1 - Particules hydrophobes fonctionnalisées - Google Patents

Particules hydrophobes fonctionnalisées

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Publication number
EP2697314A1
EP2697314A1 EP12715353.4A EP12715353A EP2697314A1 EP 2697314 A1 EP2697314 A1 EP 2697314A1 EP 12715353 A EP12715353 A EP 12715353A EP 2697314 A1 EP2697314 A1 EP 2697314A1
Authority
EP
European Patent Office
Prior art keywords
general formula
optionally functionalized
group
solvent
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12715353.4A
Other languages
German (de)
English (en)
Inventor
Stephan Deuerlein
Imme Domke
Alexej Michailovski
Reinhold Rieger
Piyada Charoensirisomboon
David F. Blackwood
Christian Eichholz
Robert Bayer
Dennis LÖSCH
Igor Shishkov
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
BASF Corp
Original Assignee
BASF SE
BASF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE, BASF Corp filed Critical BASF SE
Priority to EP15151195.3A priority Critical patent/EP2886611B1/fr
Priority to EP12715353.4A priority patent/EP2697314A1/fr
Publication of EP2697314A1 publication Critical patent/EP2697314A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • 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 Halbmetalloxidp which are functionalized on the surface with silicon-containing compounds are already known from the prior art.
  • WO 2009/059382 A1 discloses a hydrophobic modification of mineral fillers and mixed polymer systems.
  • the hydrophobic modification takes place by reaction of the corresponding mineral particles with silanes, for example C 3 -C 12 -alkyl-trialkoxy-silanes.
  • silanes for example C 3 -C 12 -alkyl-trialkoxy-silanes.
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • 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).
  • metal oxide particles known to the person skilled in the art, in particular metal oxide particles.
  • 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.
  • silicon oxide is not preferred as a semi-metal oxide and is therefore not included in a preferred embodiment of the present invention.
  • the present invention therefore relates to the mixture according to the invention, wherein silicon dioxide is excluded as the semi-metal oxide.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention relates to the mixture according to the invention, wherein the metal oxide or Halbmetalloxidpumble are magnetic.
  • 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 is selected from Co, Ni, Mn, Zn and mixtures thereof and
  • the metal oxide used according to the invention is a magnetic iron oxide selected from the abovementioned group.
  • 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.
  • 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 ⁇ , preferably 200 nm to 100 ⁇ , more preferably 500 nm to 10 ⁇ on.
  • the present invention particles may generally have any shape, for example, spherical, cylindrical, needle-shaped or brick-shaped.
  • 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 .
  • 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.
  • 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)
  • 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.
  • 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.
  • 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, is
  • 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.
  • 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, dec
  • 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.
  • 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.
  • 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.
  • 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.
  • R 1 is independently an optionally functionalized C 5 -C 22 aryl, more preferably C 5 -C 12 aryl.
  • preferred aryl radicals according to the invention are phenyl, naphthyl or biaryls.
  • 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.
  • R 1 is independently an optionally functionalized C 6 -C 23 arylalkyl, particularly preferably C 6 -C 13 -arylalkyl.
  • arylalkyl radicals according to the invention are toluyl, xylyl, propylbenzyl, hexylbenzyl.
  • 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.
  • R 1 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.
  • 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.
  • 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.
  • 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
  • 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.
  • alkenyl radicals 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
  • 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.
  • 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.
  • 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.
  • 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.
  • R 2 is independently an optionally functionalized C 5 -C 22 aryl, more preferably C 5 -C 12 aryl.
  • preferred aryl radicals according to the invention are phenyl, naphthyl or biaryls.
  • 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.
  • R 2 is independently an optionally functionalized C 6 -C 23 arylalkyl, particularly preferably C 6 -C 13 arylalkyl.
  • arylalkyl radicals according to the invention are toluyl, xylyl, propylbenzyl, hexylbenzyl.
  • 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.
  • 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.
  • 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.
  • 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,
  • X represents an anion, for example selected from the group consisting of CH NO3 ", SO4 2" or PO4 3 ".
  • x is 1 2 or 3 means, and thus corresponds to the negative formal charge of the anions.
  • y means 0, 1 or 2
  • p is 1, 2, 3, 4, 5, 6 or 7, more preferably p is 1, 2, or 3.
  • 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.
  • 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+ .
  • 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).
  • 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 alkali metals for example Li, Na, K, Rb, Cs, Fr, preferably Li + , Na + , K + , Rb + , Cs + , Fr, with p
  • 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).
  • MP + is selected from the group 1, 2 or 13 of the Periodic Table of the Elements (IUPAC Nomenclature).
  • 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.
  • R 2 is a group of the general formula (IIa)
  • 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.
  • R 2 in the group of the general formula (IIa) independently of one another is methyl or ethyl.
  • 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
  • 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.
  • n is generally 1, 2 or 3.
  • 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.
  • m is generally independently 0, 1, 2 or 3, preferably 1 or 2.
  • 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
  • R 1 is methyl, ethyl, butyl, pentyl, hexyl, octyl, decyl and / or dodecyl
  • R 2 is 0.5 Ca and / or 0.5 Mg
  • n is 1, 2 or 3, wherein the above applies to the divalent cations.
  • 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 ,
  • 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 Halbmetalloxidpitate 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- talloxidpumble and compounds of general formula (I) or Polysiloxanes of the general formula (I) containing groups of the general formula (IIa) are obtained.
  • a solvent for example toluene or water
  • the fixation of the silicon compounds on the metal or Halbmetalloxidober Design 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.
  • 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.
  • the stable mixture according to the invention contains at least one solvent, at least one surface-active substance or a mixture thereof.
  • 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
  • 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.
  • aromatic hydrocarbons for example
  • 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.
  • 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.
  • nonionic surfactants according to the invention are fatty alcohol polyglycol ethers, in particular fatty alcohol polyethylene glycol ethers.
  • anionic surfactants according to the invention are alkylbenzenesulfonates, secondary alkanesulfonates, .alpha.-olefinsulfonates, fatty alcohol sulfates or fatty alcohol ether sulfates.
  • 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.
  • 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.
  • the abovementioned amount of surface-functionalized metal oxide or semimetal oxide particles is adapted accordingly.
  • 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 .-%.
  • 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.
  • 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.
  • 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 Halbmetalloxidpiety
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the statements made with respect to the mixture according to the invention apply to the surface-modified particles and the solvents.
  • 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.
  • 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).
  • 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
  • specially modified magnetic nanoparticles 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.
  • the modified particles according to the invention in particular magnetic particles
  • 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.
  • surfactant surface active agent
  • 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.
  • 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.
  • the density of the component to be separated by agglomeration with another component can be increased.
  • 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.
  • 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.
  • Example 1.1 Representation of the alkali metal alkyl siliconates used
  • 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.
  • Luten sit A-ES from BASF SE (mixture of sodium alkylphenol ether sulfates)
  • the magnetite powder is applied as a layer about 1 mm thick with a 100 ⁇ 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
  • hydrophobized magnetite as a recyclable carrier for the cleaning of (heavy metal) contaminated soil.
  • 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).
  • inorganic silicatic components eg feldspars, mica, litter
  • enargite a special hydrophobized inorganic As-containing impurity
  • 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).
  • a surfactant Litensit A-ES from BASF SE.
  • 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)
  • Example 2.2 with "BuSi (OH) 2 (ONa) silanized magnetic pigment 345 from BASF SE (according to the invention)
  • Example 2.3 with (Ca 2+ ) ["Pr (Me) Si (OH) (O -)] 2 silanized magnetic pigment 345 from BASF SE (according to the invention)
  • 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.
  • OPS n-octylphosphonic acid

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compounds Of Iron (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un mélange stable, contenant des particules modifiées en surface, obtenues par mise en réaction de particules de métal ou d'oxydes de semi-métaux avec au moins un composé choisi parmi des composés contenant du silicium, qui portent au moins un radical métaloxy et le cas échéant d'autres radicaux alcoxy et/ou hydroxy, et au moins un solvant, au moins une substance à activité de surface ou un mélange de ces éléments, un procédé de fabrication dudit mélange, l'utilisation de ces particules dans des systèmes dans lesquels lesdites particules sont mises en contact avec un solvant, le rapport de masse du solvant aux particules modifiées étant supérieur à 500, ainsi que l'utilisation de ces particules dans des cycles d'agglomération-désagrégation.
EP12715353.4A 2011-04-12 2012-04-11 Particules hydrophobes fonctionnalisées Withdrawn EP2697314A1 (fr)

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EP15151195.3A EP2886611B1 (fr) 2011-04-12 2012-04-11 Particules fonctionnalisées hydrophobes
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PCT/EP2012/056555 WO2012140065A1 (fr) 2011-04-12 2012-04-11 Particules hydrophobes fonctionnalisées
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US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
WO2015104324A1 (fr) 2014-01-08 2015-07-16 Basf Se Procédé pour réduire par élutriation le débit volumique d'un flux comprenant des agglomérats magnétiques
CN106132551B (zh) 2014-03-31 2019-08-27 巴斯夫欧洲公司 用于输送磁化材料的磁体装置
FI3223952T3 (fi) 2014-11-27 2024-03-27 Basf Se Energiansyöttö agglomeraation aikana magneettierottelua varten
MX2017006699A (es) 2014-11-27 2017-08-21 Basf Se Mejora de la calidad del concentrado.
EP3181230A1 (fr) 2015-12-17 2017-06-21 Basf Se Ultraflottation avec des particules support magnétiquement réactives
WO2019025524A1 (fr) 2017-08-03 2019-02-07 Basf Se Séparation d'un mélange à l'aide de particules de support magnétique
CA3208646A1 (fr) 2021-03-05 2022-09-09 Oliver Kuhn Separation magnetique de particules supportees par des tensioactifs specifiques
DE102021121584A1 (de) * 2021-08-19 2023-02-23 Wakol Gmbh Verfahren zur Entfernung von Klebstoffresten von einem Klebstoffauftragsmittel

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EA201391493A1 (ru) 2014-04-30
BR112013024090A2 (pt) 2016-12-06
CA2832814C (fr) 2019-04-02
MX344908B (es) 2017-01-11
EP2886611B1 (fr) 2020-11-18
CA2832814A1 (fr) 2012-10-18
EP2886611A1 (fr) 2015-06-24
CL2013002966A1 (es) 2014-05-16
KR20140039178A (ko) 2014-04-01
AU2012241937B2 (en) 2015-06-18
PE20141988A1 (es) 2014-12-24
WO2012140065A1 (fr) 2012-10-18
CN103459517A (zh) 2013-12-18
AU2012241937A1 (en) 2013-11-07
JP2014520053A (ja) 2014-08-21
MX2013011857A (es) 2013-11-01
ZA201308412B (en) 2015-08-26
CN103459517B (zh) 2015-08-05

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