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WO2007060125A1 - Ecailles d'oxyde de silicium reactif - Google Patents

Ecailles d'oxyde de silicium reactif Download PDF

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Publication number
WO2007060125A1
WO2007060125A1 PCT/EP2006/068512 EP2006068512W WO2007060125A1 WO 2007060125 A1 WO2007060125 A1 WO 2007060125A1 EP 2006068512 W EP2006068512 W EP 2006068512W WO 2007060125 A1 WO2007060125 A1 WO 2007060125A1
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Prior art keywords
groups
separating agent
sio
silicon oxide
reacting
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Ceased
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PCT/EP2006/068512
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English (en)
Inventor
Holger Hoppe
Ulrich Schubert
Philipp Heinz
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Publication of WO2007060125A1 publication Critical patent/WO2007060125A1/fr
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    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0018—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings uncoated and unlayered plate-like particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/403—Low molecular weight materials, e.g. fatty acids
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/403—Low molecular weight materials, e.g. fatty acids
    • C09C2200/404—Low molecular weight materials, e.g. fatty acids comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • C09C2200/406—High molecular weight materials, e.g. polymers comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
    • 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
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/20—PVD, CVD methods or coating in a gas-phase using a fluidized bed

Definitions

  • the present invention is directed to a product, obtainable by reacting a SiO y flake, or a material comprising a SiO y layer with 0.70 ⁇ y ⁇ 1.95, especially 0.70 ⁇ y ⁇ 1.80, very especially 1.0 ⁇ y ⁇ 1.8 with a protic substance, such as water, or a protic organic solvent to generate Si-H, Si-H 2 and/or a-Si:H groups and reacting the obtained intermediate with a compound having functional groups that can react with Si-H, Si-H 2 and/or a-Si:H groups and a process for their production.
  • a protic substance such as water
  • Si-H group As anchor on the surface for organic compounds hazardous reducing agents like lithium aluminum hydride, borane or hydrogen can be avoided for reductive grafting methods.
  • Organic and inorganic compounds such as, for example, colorants, or additives, such as, for example, UV absorbers, or photoinitiators, or polymers can be immobilized.
  • the modified flakes, i.e. the product can be used in coatings, plastics, fibres etc.
  • WO03/068868 (and WO03/106569) describes a process for the production of SiO y flakes (0.95 ⁇ y ⁇ 1.8): NaCI, followed successively by a layer of silicon suboxide (SiO y ) are vapor- deposited onto a carrier, which may be a continuous metal belt, passing by way of the vaporisers under a vacuum of ⁇ 0.5 Pa.
  • porous SiO z flakes (0.70 ⁇ y ⁇ 2.0) are produced in the following manner: NaCI, followed successively by a layer of silicon suboxide (SiO y ) and NaCI, are vapor-deposited onto a carrier, which may be a continuous metal belt, passing by way of the vaporisers under a vacuum of ⁇ 0.5 Pa.
  • the mixed layer of silicon suboxide (SiO y ) and NaCI is vapor-deposited by two distinct vaporizers, wherein the separating agent is contained in the mixed layer in an amount of 1 to 60 % by weight based on the total weight of the mixed layer.
  • the carrier is immersed in water. With mechanical assistance, the NaCI rapidly dissolves in water and the product layer breaks up into flakes, which are then present in water in the form of a suspension.
  • Si- H, Si-H 2 and/or a-Si:H groups are generated.
  • Said Si-H, Si-H 2 and/or a-Si:H groups can be used to provide chemically modified SiCy
  • he present invention is directed to a product, obtainable by reacting a SiO y flake, or a material comprising a SiO y layer with 0.70 ⁇ y ⁇ 1.95, especially 0.70 ⁇ y ⁇ 1.80, very especially 1.0 ⁇ y ⁇ 1.8 with a protic substance, such as water, or a protic organic solvent to generate Si-H, Si-H 2 and/or a-Si:H groups and reacting the obtained intermediate (silicon oxide having Si-H, Si-H 2 and/or a-Si:H groups) with a compound having functional groups that can react with Si-H, Si-H 2 and/or a-Si:H groups.
  • a protic substance such as water
  • a protic organic solvent to generate Si-H, Si-H 2 and/or a-Si:H groups
  • the obtained intermediate silicon oxide having Si-H, Si-H 2 and/or a-Si:H groups
  • a compound having functional groups that can react with Si
  • separating agent II By using a separating agent, which is dissolvable in water, or a protic organic solvent (separating agent I), and optionally a separating agent, which is dissolvable in an inert solvent, which does not react with the SiO y (separating agent II), the following products are available: a) silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H (hydrogenated amorphous silicon) groups on their surface, b) porous silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups on their surface and in their pores, as well as c) porous silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups only on their surface, or only in their pores.
  • SiO y with 0.70 ⁇ y ⁇ 1.95" means that the molar ratio of oxygen to silicon at the average value of the silicon oxide substrate is from 0.70 to 1.95.
  • the composition of the silicon oxide substrate can be determined by ESCA (electron spectroscopy for chemical analysis).
  • the stoichiometry of silicon and oxygen of the silicon oxide substrate can be determined by RBS (Rutherford-Backscattering).
  • the plate-like (plane-parallel) silicon oxide structures (silicon oxide flakes), hereinafter referred to as "reactive silicon oxide flakes", used according to the present invention have a length of from 1 ⁇ m to 5 mm, a width of from 1 ⁇ m to 2 mm, and a thickness of from 20 nm to 1.5 ⁇ m, and a ratio of length to thickness of at least 2 : 1 , the particles having two substantially parallel faces, the distance between which is the shortest axis of the particles (thickness).
  • the porous reactive silicon oxide flakes are mesoporous materials, i.e. have pore widths of ca. 1 to ca. 50 nm, especially 2 to 20 nm.
  • the pores are randomly inter-connected in a three-dimensional way. So, when used as a support, the passage blockage, which frequently occurs in SiO 2 flakes having a two-dimensional arrangement of pores can be prevented.
  • the specific surface area of the porous reactive silicon oxide flakes depends on the porosity and ranges from ca. 400 m 2 /g to more than 1000 m 2 /g. Preferably, the porous reactive silicon oxide flakes have a specific surface area of greater than 500 m 2 /g, especially greater than 600 m 2 /g.
  • the BET specific surface area is determined according to DIN 66131 or DIN 66132 (R. Haul und G. D ⁇ mbgen, Chem.-lng.-Techn.
  • the reactive silicon oxide flakes are not of a uniform shape. Nevertheless, for purposes of brevity, the flakes will be referred to as having a "diameter.”
  • the reactive silicon oxide flakes flakes have a plane-parallelism and a defined thickness in the range of ⁇ 10 %, especially ⁇ 5 % of the average thickness.
  • the reactive silicon oxide flakes have a thickness of from 20 to
  • the diameter of the flakes is in a preferred range of about 1-60 ⁇ m with a more preferred range of about 5-40 ⁇ m and a most preferred range of about 5-20 ⁇ m.
  • the aspect ratio of the flakes of the present invention is in a preferred range of about 2.5 to 625 with a more preferred range of about 50 to 250.
  • Variant a) The silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups on their surface are obtainable by a process comprising the steps of: a) vapor-deposition of a separating agent I onto a carrier to produce a separating agent layer, b) the vapor-deposition of SiO y onto the separating agent layer (a), c) the separation of SiO y from the separating agent I, wherein 0.70 ⁇ y ⁇ 1.80, by dissolution in water, or a protic organic solvent, and d) reacting the silicon oxide flakes obtained in step c) and having Si-H, Si-H 2 and/or a-Si:H groups with a compound having functional groups that can react with the Si-H, Si-H 2 and/or a- Si:H groups.
  • the porous silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups on their surface and in their pores are obtainable by a process comprising the steps of: a) vapor-deposition of a separating agent I onto a carrier to produce a separating agent layer, b) the simultaneous vapor-deposition of SiO y and the separating agent I onto the separating agent layer (a), c) the separation of SiO y from the separating agent I, wherein 0.70 ⁇ y ⁇ 1.95, by dissolution in water, or a protic organic solvent, and d) reacting the silicon oxideflakes obtained in step c) and having Si-H, Si-H 2 and/or a-Si:H groups with a compound having functional groups that can react with the Si-H, Si-H 2 and/or a-Si:H groups.
  • Variant c) The porous silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups only on their surface are obtainable by a process comprising the steps of: a) vapor-deposition of a separating agent I onto a carrier to produce a separating agent layer, b) the simultaneous vapor-deposition of SiO y and a separating agent II, which is dissolvable in an inert organic solvent, but not in water, or the protic organic solvent, onto the separating agent layer (a), c) the separation of SiO y from the separating agent I, wherein 0.70 ⁇ y ⁇ 1.95, by dissolution in water, or the protic organic solvent, and d) reacting the silicon oxideflakes obtained in step c) and having Si-H, Si-H 2 and/or a-Si:H groups with a compound having functional groups that can react with the Si-H, Si-H 2 and/or a-Si:H groups, and
  • silicon oxide flakes having reactive centres i.e. Si-Si groups that can be cleaved, in their pores, are obtained, which can be used to chemically bond compounds having functional groups, especially organic compounds having functional groups to the silicon oxide flakes.
  • Si-Si groups that can be cleaved
  • the porous silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups only in their pores are obtainable by a process comprising the steps of: a) vapor-deposition of a separating agent Il onto a carrier to produce a separating agent layer, b) the simultaneous vapor-deposition of SiO y and a separating agent I onto the separating agent layer (a), b') the separation of SiO y from the separating agent II, wherein 0.70 ⁇ y ⁇ 1.95, by dissolution in the inert solvent, b") the removal of the reactive centres obtained in step b'), c) the dissolution of the separating agent I in water, or a protic organic solvent, and d) reacting the silicon oxideflakes obtained in step c) and having Si-H, Si-H 2 and/or a-Si:H groups with a compound having functional groups that can react with the Si-H, Si-H 2 and/or a-Si:H groups.
  • the separating agent I is dissolvable in water, or the protic organic solvent, but not in the inert solvent.
  • separating agent I is an inorganic salt soluble in water and vaporisable in vacuo, such as, for example, sodium chloride, potassium chloride, lithium chloride, sodium fluoride, potassium fluoride, lithium fluoride, calcium fluoride, sodium aluminium fluoride and disodium tetraborate, or mixtures thereof.
  • the solvent, which is used for its dissolution is water.
  • the separating agent Il is dissolvable in the inert solvent, but not in water, or the protic organic solvent.
  • the separating agent Il is an organic substance soluble in organic solvents, is inert against the reactive SiO y flakes and vaporisable in vacuo, such as anthracene, anthraquinone, acetamidophenol, acetylsalicylic acid, camphoric anhydride, benzimidazole, bis(4- hydroxyphenyl)sulfone, dihydroxyanthraquinone, hydantoin, phenolphthalein, phenothiazine, tetraphenylmethane, triphenylene, triphenylmethanol or a mixture of at least two of those substances.
  • Suitable inert solvents are, for example, ethers, in particular those having 2 to 8 carbon atoms in the molecule, such as, for example, diethyl ether, methyl ethyl ether, di-n-propyl ether, diisopropyl ether, methyl n-butyl ether, methyl tert-butyl ether, ethyl n-propyl ether, din-butyl ether, tetrahydrofuran, 1 ,4-dioxane, 1 ,2-dimethoxyethane, bis- ⁇ -methoxyethyl ether; aliphatic hydrocarbons, such as, for example, hexane, heptane, low- and high-boiling petroleum ethers; cycloaliphatic hydrocarbons, such as, for example, cyclohexane, methylcyclohexane, tetralin, decalin; aromatic hydrocarbons,
  • Nitriles such as, for example, acetonitrile; amides, such as, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone; hexamethylphosphoric triamide; and sulfoxides, such as, for example, dimethyl sulfoxide are less preferred. Mixtures of various solvents can also be used.
  • the SiOy flakes having Si-H, Si-H 2 and/or a-Si:H groups can be used to chemically bond compounds having functional groups, especially organic compounds having functional groups to the SiO y flakes.
  • the reaction of the Si-H, Si-H 2 and/or a-Si:H with the compounds having functional groups results in the formation of chemical bonds between the compounds
  • Si-
  • a functional group is any group, which can react with the Si-H, Si-H 2 and/or a-Si:H groups to form a chemical bond:
  • the compound having the functional group is not ethanol, 1-methyl-2-pyrrolidone (NMP), or water.
  • the protic substance is different from the compounds having functional groups.
  • a mixture of, for example, an alkyl halide and the SiO y flakes having Si-H, Si-H 2 and/or a-Si:H groups is heated in the presence of tertiary amine or organic salts (quaternary organoammonium and organophosphonium halides) as catalyst.
  • tertiary amine or organic salts quaternary organoammonium and organophosphonium halides
  • the reaction of the SiO y flakes having Si-H, Si-H 2 and/or a-Si:H groups with primary or secondary hydroxyl groups to form silyl ethers can be done, for example, in a solvent, such as dimethylformamide, tetrahydrofurane, or acetonitrile, in the presence of a catalyst, such as caesium fluoride/imidazole.
  • a solvent such as dimethylformamide, tetrahydrofurane, or acetonitrile
  • HX is R 1 OH, especially R 1 CH 2 OH.
  • R 1 CH 2 OH can, for example, be derived from a polymer additive by modifying it with a -CH 2 OH group, or can be a polymer additive, which bears a -CH 2 OH group.
  • Such polymer additives can be selected from the group consisting of light stabilizers, heat stabilizers, metal deactivators, processing stabilizers, acid scavengers, anti-blocking agents, anti-fogging agents, antistatic agents, flame retardants, hydrophilic/hydrophobic surface modifiers, IR-reflectors, IR-absorbers, nucleating agents, scratch resistance additives and thermally conductive additives.
  • R 1 CH 2 OH can be derived from a UV absorber, especially for the protection of skin and hair, or it can be a fluorescent whitening agent.
  • R 1 CH 2 OH can, for example, be derived from an organic colorant by modifying it with a -CH 2 OH group, or can be an organic colorant, which bears a -CH 2 OH group.
  • the organic colorant can be or can be derived from a dye, or a pigment.
  • the organic colorant can be derived from pigments, such as 1-aminoanthraquinone, anthraquinone, anthrapyrimidine, azo, azomethine, benzodifuranone, quinacridone, quinacridone-quinone, quinophthalone, diketopyrrolopyrrole, dioxazine, flavanthrone, indanthrone, indigo, isoindoline, isoindolinone, isoviolanthrone, perinone, perylene, phthalocyanine, pyranthrone or thioindigo.
  • chromophores are described, for example, in W. Herbst, K. Hunger, lndustrielle Organische Pigmente, 2 nd completely revised edition, VCH 1995.
  • the organic colorant can be a fluorescent organic colorant which is, for example, selected from coumarins, benzocoumarins, xanthenes, benzo[a]xanthenes, benzo[b]xanthenes, benzo[c]xanthenes, phenoxazines, benzo[a]phenoxazines, benzo[b]phenoxazines and benzo[c]phenoxazines, napthalimides, naphtholactams, azlactones, methines, oxazines and thiazines, diketopyrrolopyrroles, perylenes, quinacridones, benzoxanthenes, thio-epindolines, lactamimides, diphenylmaleimides, acetoacetamides, imidazothiazines, benzanthrones, perylenmonoimides, perylenes, phthalimides, benzotriazoles, pyrimidines,
  • Suitable examples are the diketopyrrolopyrroles described in WO04/009710 of the general formula:
  • R 2 i and R 22 are independently of one another hydrogen, CrCi 8 alkyl, d-Ci 8 alkyl which is interrupted one or more times by O or S, C 7 -C-i 2 aralkyl or a group of the formula
  • R 2 3 and R 24 independently of one another are a group of formula
  • Xi is -S-, -SO 2 NH- Or -NH-, X 2 is a CrCi 8 alkylene group, and X 3 is -OH;
  • R3 1 and R 32 are independently of each other a radical of the formula
  • X 2 is Ci-Ci 8 alkylene and X 3 is -OH
  • R 3 3 and R3 4 independently of one another are Ci-Ci ⁇ alkyl, C-i-C-i ⁇ alkoxy, -NR 16 Ri7, -CONHR 18 , COOR 1 9, -SO 2 NH-R 2 O, CrCi 8 alkoxycarbonyl, Ci-Ci 8 alkylaminocarbonyl, wherein R 1 6, Ri7, Ri 8 , Rig and R 20 are CrCi ⁇ alkyl. Examples of such compounds are shown below:
  • n2 is O to 18; or ⁇ wherein n1 is 1 to 18.
  • the reactive silicon oxide flakes can be rendered hydrophobic by reacting them with an alcohol R 30 OH, or R 30 CI, wherein R 30 represents a substituted or unsubstituted C r C 20 alkyl group.
  • R 30 include methyl, ethyl, especially n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.
  • Ci-C 2 oalkyl group is a "fluoroalkyl" group.
  • fluoroalkyl means groups given by partially or wholly substituting the above-mentioned alkyl group with fluorine, such as trifluoromethyl, trifluoropropyl, especially 3,3,3-trifluoro-n-propyl, 2,2,2,2',2',2'- hexafluoroisopropyl and heptadecafluorodecyl.
  • the pores of the reactive silicon oxide flakes can first be filled, for example, with a fluorescent dye and then be rendered hydrophobic by reacting them with an alcohol R 30 OH.
  • the reactive silicon oxide flakes can be used to prepare activatable flakes:
  • wherein PG is an activatable group, LS is a linkage or spacer group, and silicon oxide flake is a silicon oxide flake derived from the reactive silicon oxide flake.
  • a linkage or spacer group joins the activable group to the
  • PG can be activated by heat or electromagnetic radiation from microwaves to ⁇ -radiation.
  • Photoinitiators from which the activatable group can be derived, are commercially available, e.g. under the trademark IRGACURE (Ciba Specialty Chemicals), ESACURE (Fratelli Lamberti), LUCIRIN (BASF), VICURE (Stauffer), GENOCURE, QUANTACURE (Rahn/Great Lakes), SPEEDCURE (Lambsons), KAYACURE (Nippon Kayaku), CYRACURE (Union Carbide Corp.), DoubleCure (Double Bond), EBECRYL P (UCB), FIRSTCURE (First Chemical), etc..
  • IRGACURE Ciba Specialty Chemicals
  • ESACURE Feratelli Lamberti
  • LUCIRIN BASF
  • VICURE Stauffer
  • GENOCURE QUANTACURE (Rahn/Great Lakes)
  • SPEEDCURE Libsons
  • KAYACURE Nippon Kayaku
  • CYRACURE Union Carbide Corp.
  • DoubleCure
  • UVe Cryl P36 frOm UCB ' and SOme copolymerisable unsaturated tertiary amines (Uvecryl P101 , Uvecryl P104, Uvecryl P105, Uvecryl P1 15 from UCB Radcure Specialties) or copolymerisable aminoacrylates (Photomer 4116 and Photomer 4182 from Ackros; Laromer LR8812 from BASF; CN381 and CN386 from Cray Valley).
  • the compounds are bonded to the silicon oxide flakes by a hydrosilylation reaction, wherein, for example, the following product is obtained:
  • photoinitiators are ⁇ -hydroxy ketones, ⁇ -alkoxyketones or ⁇ - aminoketones of the formula (II), and phenylglyoxalates of the formula (III):
  • R 2 O is hydrogen or Ci-Ci8-alkoxy
  • R 2 i is hydrogen, C r Ci 8 -alkyl, C r Ci 2 hydroxyalkyl ,C r Ci 8 -alkoxy, -(OCH 2 CH 2 ) Y -OR 25 , morpholino, di(Ci-C 20 alkyl)amino, H(Ci-C 20 alkyl)amino, NH 2 , OH, CrCi 8 alkyl-S-, a group
  • R 22 is OH, C r Ci6-alkoxy, morpholino, di(C r C 4 alkyl)amino or -O(CH 2 CH 2 O) y -Ci-Ci 6 -alkyl;
  • R 23 and R 24 independently of one another are hydrogen, d-C 6 -alkyl, CrCi 6 -alkoxy or -O(CH 2 CH 2 O) y -Ci-Ci 6 -alkyl; or unsubstituted phenyl or benzyl; or phenyl or benzyl substituted by CrCi 2 -alkyl; or R 2 3 and R 24 together with the carbon atom to which they are attached form a cyclohexyl ring;
  • a, b and c are 1-3; x is 2-10; y is 1-20;
  • Z is O, S or NR 54 ;
  • R 50 is hydrogen, CrC 50 alkyl, C 2 -C 24 alkenyl, C 3 -C 25 cycloalkyl; C 2 -C 250 alkyl interrupted by one or more Z 2 ; C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ; wherein said radicals CrC 50 alkyl, C 2 -C 24 alkenyl, C 3 -C 25 cycloalkyl; C 2 -C 250 alkyl interrupted by one or more Z 2 ; C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ;optionally are substituted by one or more A 2 ; or R 50 is phenyl, optionally substituted by A 1 ; or, when Z is NR 54 , R 54 and R 50 together with the N-atom optionally form a ring,
  • OCONR 59 R 60 , R, 66 A 1 is CrC 24 alkyl, C 2 -C 24 alkyl interrupted by one or more Z 2 ; C 2 -C 24 alkenyl, C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl; C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ; wherein said radicals CrC 24 alkyl, C 2 -C 24 alkyl interrupted by one or more Z 2 , C 2 - C 24 alkenyl; C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl; and C 3 - C 25 cycloalkyl interrupted by one or more Z 2 ; optionally are substituted by one or more C 2 - C 24 alkinyl, phenyl, OR 58 , SR 58 , -COR 58 , COOR 58 , -Z 1
  • R5 1 , R5 2 and R 53 independently of one another are hydrogen, halogen, CN, CrC 24 alkyl, C 2 - C 24 alkyl interrupted by one or more Z 2 ; C 2 -C 24 alkenyl, C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl; C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ; wherein said radicals CrC 24 alkyl, C 2 -C 24 alkyl interrupted by one or more Z 2 , C 2 -C 24 alkenyl, C 2 -C 24 alkenyl interrupted by one or more Z 2 , C 3 -C 25 cycloalkyl, and C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ; optionally are substituted by one or more C 2 -C 24 alkinyl, phenyl, halogen, OR 58 ,
  • R 51 , R 52 and R 53 are -Z 1 -
  • R 51 and R 52 together form CrC 6 alkylene or R 51 and R 52 together form a benzene ring that is condensed to the phenyl ring to which they are attached;
  • R 54 has one of the meanings as given for R 50 , or R 54 is — Z 1 -C-C — C-R 66 ; Z 1 is a direct bond, O, S or NR 61 ; Z 2 is O, S, NR 61 , CO, COO, OCO, CONR 61 , NR 61 CO, OCONR 61 , NR 61 COO, NR 61 CONR 62 ,
  • R55, R56 and R 57 independently of one another have the same meanings as given for R 51 , R 52 and R 53 ;
  • R 58 , R 59 and R 60 independently of one another are hydrogen, CrC 24 alkyl; C 2 -C 24 alkyl interrupted by one or more Z 2 ; C 2 -C 24 alkenyl; C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl; C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ; wherein said radicals C 1 - C 24 alkyl; C 2 -C 24 alkyl interrupted by one or more Z 2 ; C 2 -C 24 alkenyl; C 2 -C 24 alkenyl interrupted by one or more Z 2 ; C 3 -C 25 cycloalkyl; and C 3 -C 25 cycloalkyl interrupted by one or more Z 2 ; optionally are substituted by one or more C 2 -C 24 alkinyl, phenyl, halogen, CN, OR 61 , SR 61 ,
  • COR 61 , COOR 61 , -Z 1 - and/or . or R 58 , R 5 9 and R 60 independently of one another are unsubstituted phenyl or phenyl substituted by one or more COR 61 , COOR 61 , OCOR 61 , CONR 62 R 63 , OCONR 62 R 63 , C 1 -
  • R 58 , R 5 g and R 60 independently of one another are phenyl-C- ⁇ -C 4 -alkyl substituted by one or more COR 61 , COOR 61 , OCOR 61 , CONR 62 R 63 , OCONR 62 R 63 , C r C 24 alkyl, C 3 -C 25 cycloalkyl,
  • R 61 , R 62 and R 63 independently of one another are hydrogen, phenyl, CrC 24 alkyl; C 2 - C 24 alkyl, interrupted by one or more Z 3 ; C 2 -C 24 alkenyl; C 2 -C 24 alkenyl interrupted by one or more Z 3 ; C 3 -C 25 cycloalkyl; C 3 -C 25 cycloalkyl interrupted by one or more Z 3 ; wherein said radicals phenyl, CrC 24 alkyl; C 2 -C 24 alkyl, interrupted by one or more Z 3 ; C 2 -C 24 alkenyl; C 2 - C 24 alkenyl interrupted by one or more Z 3 ; C 3 -C 25 cycloalkyl; and C 3 -C 25 cycloalkyl interrupted by one or more Z 3 optionally are substituted by one or more OH or halogen; Z 3 is O, S Or NR 54 ; and R6 4 , Res and R ⁇ independently of one
  • alkoxyamine initiators useful for the preparation of complex polymeric architectures starting from a wide range of monomers, such as for example styrenic, acrylic, methacrylic and diene-type monomers.
  • Alkoxyamine initiators from which the activatable group can be derived are compounds of formula (Xl), (XII) and (XIII):
  • R 2 oo is independently H or d-C 4 alkyl
  • A is O Or NR 203 ;
  • B 1 is C- ⁇ -C 25 alkylene, which may be interrupted by O or NR 203 groups, C 5 -C 7 cycloalkylene which can contain O and or NR 203 groups in the ring, which both are unsubstituted or substituted by C-i-C ⁇ alkoxy, halogen or a group -COO(CrC-i8alkyl) or phenylene; additionally -A-B 1 - can be a direct bond; or if A is -O- and D is NR 203 , B 1 can be a direct bond; or if A is NR 203 and D is O or NR 203 , B 1 can be a direct bond;
  • E is a direct bond or a -C(O)- group
  • R 2011 R 202 and R 203 are independently H, C- ⁇ -C 18 alkyl, which is unsubstituted or substituted by
  • A is as defined above; and if A is O, E 1 is -CH 2 - if A is NR 203 , E 1 is -C(O)-, -CH 2 - or a direct bond;
  • R 204 , R 205 , R 206 are independently CrC 18 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 9 phenylalkyl or phenyl;
  • R 7 , R 8 are independently H, CrC 18 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 9 phenylalkyl or CrC 18 acyl;
  • L is a direct bond, O or NR 207 ;
  • R209, R2K are independently H or CrC 18 alkoxy, if R 209 is H, R 210 is additionally OH, -O-(C r C 18 )acyl, -NR 203 -(C 1 -C 18 )BCyI or N(R 203 ) 2 ; or
  • k is 0, 1 or 2 and R 15 is C r C 18 alkyl, -CH 2 -OH or
  • A is O, NR 2 03 or a direct bond and E, R 2 oi and R 2 0 2 are as defined above;
  • B 3 is H, CrC 2 5alkyl, which may be interrupted by O or NR 2 03 groups, C 5 -C 7 cycloalkyl, which can contain O and or NR 2 03 groups in the ring, which both are unsubstituted or substituted by CrC 8 alkoxy, halogen or a group -COO(CrCi 8 alkyl) or d-Ci 8 alkoxy or phenyl;
  • L 1 is a divalent group derived from an aliphatic dicarboxylic acid having 2 to 18 carbon atoms from an aromatic dicarboxylic acid or from an aliphatic-aromatic dicarboxylic acid; in formula (III)
  • X 1 is a group wherein B 2 is a direct bond, C- ⁇ -C 2 5alkylene, which may be interrupted by O or NR 2 03 groups, C 5 -C 7 cycloalkylene which can contain O and or NR 2 03 groups in the ring, which both are unsubstituted or substituted by C-i-C ⁇ alkoxy, halogen or a group -COO(CrC-i8alkyl) or phenylene, wherein when B 2 is a direct bond one A is O and the other is NR 2 03; A, B 1 , R 2 O 1 and R202 are as defined above and
  • Q is preferably , wherein R 22 0 is independently H or CrC 4 alkyl; and D is O or NR 203 .
  • the present invention relates to polymerizable compositions comprising a) at least one ethylenically unsaturated monomer; b) a radical polymerization initiator; and c) silicon oxide flakes having bonded thereto a compound of formula (Xl), (XII) or (XIII).
  • the ethylenically unsaturated monomer is preferably selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinyl halides or vinylidene halides.
  • the present invention relates to a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block, random or graft) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of a) a free radical initiator; and b) silicon oxide flakes having bonded thereto a compound of formula (Xl), (XII) or (XIII), a polymeric or oligomeric macroinitiator obtainable by the process and the use of the polymeric macroinitiator obtainable in the process as radical initiator for the polymerization of ethylenically unsaturated monomers.
  • the polymerization is carried out by applying heat or electromagnetic radiation from microwaves to ⁇ -radiation, especially by heating and takes place at a temperature between 0°C and 160°C.
  • the polymeric macroinitiator can be used in a process for preparing a comb, star, tapered or branched polymer or copolymer by controlled free radical polymerization (CFRP).
  • the process comprises polymerizing at least one ethylenically unsaturated monomer in the presence of the polymeric macroinitiator.
  • the compounds are bonded to the silicon oxide flakes by a hydrosilylation reaction, wherein, for example, the following product is obtained:
  • any compound having a reactive double bond can be bonded to the reactive silicon oxide flakes by a hydrosilylation reaction:
  • R 100 , R 101 , R 102 and R 103 are independently of each other hydrogen, or an organic group.
  • the hydrosilylation can be initiated by UV radiation and can be catalysed by radical formers, transition metal complexes, or Lewis bases.
  • hydrosilylation catalysts are metallic and finely divided platinum which may be disposed on supports such as silica, alumina or activated carbon, compounds or complexes of platinum such as platinum halides, for example H 2 PtCIe 6H 2 O, PtCI 4 , Na 2 PtCI 4 4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H 2 PtCI 6 6H 2 O and cyclohexanone, platinum-vinylsiloxane complexes such as platinum-1 ,3-divinyl-1 ,1 ,3,3-tetramethyldisiloxane complexes with or without content of detectable inorganically bonded halogen, bis( ⁇ -picoline)platinum dichloride, trimethylenedipyridineplatinum dichloride, dicyclopentad platinum
  • the hydrosilylation process may be carried out with or without solvent as a 1 -phase or 2- phase reaction, or in dispersion, for example as micro- or macroemulsions.
  • the process according to the invention is preferably carried out at a pressure of the surrounding atmosphere, i.e. from about 900 to 1 100 hPa, but it can also be carried out at higher and lower pressures, and is preferably carried out at a temperature of from 20 to 200 °C, more preferably from 50 to 180°C and most preferably from 60 to 130°C.
  • reaction products obtained may be isolated by any suitable process steps, these being well known to the skilled artisan. If desired, volatile components and any solvent used may be removed by distillation after the reaction.
  • the poly(n-butyl acrylate) macromonomer with acrylate endgroup is synthesized with ATRP technology according to A. M ⁇ hlebach, F. Rime J. Polym. Sci., Polym. Chem. Ed., 2003, 41 ,
  • the reactive silicon oxide flakes can be reacted with organic groups, which comprise polymerizable groups.
  • organic groups which comprise polymerizable groups.
  • R 41 is hydrogen, or a substituent
  • R 42 is a linkage or spacer group
  • R 43 are hydrogen, d-C ⁇ alkyl, and C 6 -Ci 2 aryl, which can be substituted.
  • R 44 is hydrogen, or Ci-C 4 alkyl, or halogen
  • R 45 is hydrogen, Ci-C 4 alkyl, or halogen
  • R 46 is hydrogen, CrC 4 alkyl, or C 6 -Ci 2 aryl.
  • R 42 are substituted and unsubstituted alkylene groups, arylene groups, cycloalkylene, arylenealkylene groups and alkylenearylene groups each having 1 to 10 ccaarrbboonn aattoommss,, wwhhiicchh ccaarn be interrupted by an oxygen atom, a sulfur atom, or an NR 43 group, especially an NH group.
  • alkylene (spacer) is typically CrC3oalkylene, preferably C-i-C-i ⁇ alkylene, and embraces the linear as well as the branched representatives and can be, for example, -CH 2 - and C 2 -C 30 alkylene, such as -(CHz) 2 -, -CH(Me)-, -(CHz) 3 -, -CH 2 -CH(Me)-, -C(Me) 2 -, -(CHz) 4 -, -(CH 2 )S-, -(CHz) 6 -, -(CH 2 )7-,-(CHz) ⁇ -, -(CHz) 9 -, -(CH 2 ) 10 -, -(CH 2 )n-, -(CH 2 )iz-, -(CH 2 ) 13 -, -(CH 2 )i 4 -, -(CH 2 )i 5 -, -(CH 2
  • alkylene spacer can optionally comprise one or more, in particular one or two groups selected from -O-, -S-, -NR 43 -, -CO-, -CONH-, -CON 43 -, or - COO- as linking group.
  • CrC 30 alkylene can, for example, be interrupted several times by -O-, -S-, -NH- Or -C(O)NH-, such as -(CH 2 ) 2 -O-(CH 2 )-, -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 ) 2 -S-(CH 2 ) 2 -, - CH 2 -CH-CH 2 -O-(CH 2 )p-CH 3 , wherein p is an integer from 1 to 10; or -CHX 13 CH 2 -(X 14 ) n3 -OH, wherein X 13 is C-i-C ⁇ alkyl, X 14 is an alkylene oxide monomer, preferably ethylene oxide or propylene oxide, or alkylene amino monomer, preferably amino ethylene or amino propylene, and n3 is an integer from 1 to 10, preferably 1 to 5; or -(CH 2 ) 2 -NH-(CH 2
  • Arylene (spacer) is an unsubstituted or substituted carbocylic or heterocyclic arylene group, preferably containing 6 to 14 carbon atoms, typically phenylene, naphthylene, anthracenylene, anthraquinonylene, pyridinylene, quinolinylene, preferably a group
  • X 11 is a single bond in ortho-, meta- or para-position, or -O-, -S-, -NR 43 -, -CO-, - CONH-, -CONR 43 -, or -COO- in ortho-, meta- or para-position; para-phenylene and para- phenylenoxy are preferred.
  • Alkylene (spacer) is an unsubstituted or substituted carbocylic or heterocyclic aralkylene
  • X 11 is a single bond in ortho-, meta- or para-position, or -O-, -S-, -NR 43 -, -CO-, -CONH-, -CONR 43 -, or -COO- in ortho-, meta- or para-position
  • X 12 is alkylene, or a
  • X 11 is a single bond, -0-, -S-, -NR 43 -, -CO-, -CONH-, -CONR 43 -, or -COO-.
  • Cycloalkylene (spacer) is an unsubstituted or substituted carbocylic or heterocyclic cycloalkylene group, preferably containing 6 to 14 carbon atoms, typically cyclohexylene,
  • X 11 is a single bond in 2-, 3- or 4-position, or -0-, -S-, -NR 43 -, -CO-, -CONH-, -CONR 43 -, or -COO- in 2-, 3- or 4-position; 4-cyclohexylene and 4-cyclohexylenoxy are preferred. Examples of particularly suitable compounds, from which the polymerizable group can be derived are listed below:
  • the silicon oxides having polymerizable groups according to the invention, together with other copolymerizable components as needed, are polymerized to form an organic network.
  • the polymerization can occur, e.g. thermally, in a redox induced manner, covalent- nucleophilically and/or photochemically using methods described, e.g. DE-A-3143820, 3826715 and 3835968.
  • a preferred embodiment of the present invention is the use of the silicon oxides having polymerizable groups as reinforcer of coatings and improver of scratch resistance in coating compositions for surfaces.
  • the present invention also relates to a process for protecting a substrate, which comprises applying thereto a coating composition comprising silicon oxides having polymerizable groups and then drying and/or curing it.
  • the present invention likewise relates to a process for preparing a reinforced coating with improved scratch resistance on a surface, which comprises treating this surface with a coating composition comprising silicon oxides having polymerizable groups, and then drying and/or curing it.
  • the product obtainable by reacting a SiO y flake, or a material comprising a SiO y layer with 0.70 ⁇ y ⁇ 1.95, especially 0.70 ⁇ y ⁇ 1.80, very especially 1.0 ⁇ y ⁇ 1.8 with a protic substance, such as water, or a protic organic solvent to generate Si-H, Si-H 2 and/or a-Si:H groups can be used as reductive agent, such as, for example, the hydrogenation of organic compounds.
  • a protic substance such as water
  • a protic organic solvent to generate Si-H, Si-H 2 and/or a-Si:H groups
  • reductive agent such as, for example, the hydrogenation of organic compounds.
  • the present invention is illustrated in more detail on the basis of the porous silicon oxide flakes having Si-H, Si-H 2 and/or a-Si:H groups on their surface and in their pores, but not limited thereto.
  • the porous silicon oxide flakes are, in principal, obtainable by a process described in WO04/065295.
  • Said process comprises the steps of: a) vapor-deposition of a separating agent I onto a carrier to produce a separating agent layer, b) the simultaneous vapor-deposition of SiO y and the separating agent I onto the separating agent layer (a), c) the separation of SiO y from the separating agent I, wherein 0.70 ⁇ y ⁇ 1.95, by dissolution in water, or a protic organic solvent.
  • the platelike porous material can be produced in a variety of distinctable and reproducible variants by changing only two process parameters: the thickness of the mixed layer of SiO y and the separating agent and the amount of the SiO y contained in the mixed layer.
  • the separating agent vapor-deposited onto the carrier in step a) may be an organic substance soluble in protic organic solvents, or water and vaporisable in vacuo, such as anthracene, anthraquinone, acetamidophenol, acetylsalicylic acid, camphoric anhydride, benzimidazole, benzene-1 ,2,4-tricarboxylic acid, biphenyl-2,2-dicarboxylic acid, bis(4- hydroxyphenyl)sulfone, dihydroxyanthraquinone, hydantoin, 3-hydroxybenzoic acid, 8- hydroxyquinoline-5-sulfonic acid monohydrate, 4-hydroxycoumarin, 7-hydroxycoumarin, 3- hydroxynaphthalene-2-carboxylic acid, isophthalic acid, 4,4-methylene-bis-3-hydroxy- naphthalene-2-carboxylic acid, naphthalene-1 ,8-dicarboxylic anhydride
  • the separating agent is preferably an inorganic salt soluble in water and vaporisable in vacuo (see, for example, DE 198 44 357), such as sodium chloride, potassium chloride, lithium chloride, sodium fluoride, potassium fluoride, lithium fluoride, calcium fluoride, sodium aluminium fluoride and disodium tetraborate, or a mixture of at least two of those substances.
  • inorganic salt soluble in water and vaporisable in vacuo (see, for example, DE 198 44 357), such as sodium chloride, potassium chloride, lithium chloride, sodium fluoride, potassium fluoride, lithium fluoride, calcium fluoride, sodium aluminium fluoride and disodium tetraborate, or a mixture of at least two of those substances.
  • protic substances are water, alcohols and phenols.
  • Preferred protic organic solvents are CrC 8 alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, tert- butanol, pentanol, tert-amyl alcohol or hexanol and also mixtures of these with water.
  • Suitable protic organic solvents are also mixtures of ethers or glycol ethers, such as, for example, diethyl ether, dibutyl ether, ethyl methyl ether, diisopropyl ether, tert-butyl methyl ether, anisole, dioxane, tetrahydrofuran, monoglyme, diglyme and formaldehyde dimethylacetal, with water or with one of said alcohols, such as a mixture of a C-i-C ⁇ alcohol with an ether or glycol ether, in particular a mixture of methanol, ethanol or water with diethyl ether, tetrahydrofuran, dioxane, glyme or diglyme.
  • the C-i-C ⁇ alcohol can also be a polyvalent d- C 8 alcohol, which can be chosen from diols such as butanediol, and triols such as glycerol.
  • an organic separating agent for example pentaerythritol (C(CH 2 OH) 4 ), followed successively by a layer of silicon suboxide (SiO y ) and an organic separating agent, pentaerythritol, is vapor-deposited onto a carrier, which may be a continuous metal belt, passing by way of the vaporisers under a vacuum of ⁇ 0.5 Pa.
  • a carrier which may be a continuous metal belt
  • the mixed layer of silicon suboxide (SiO y ) and separating agent is vapor-deposited by two distinct vaporizers, which are each charged with one of the two materials and whose vapor beams overlap, wherein the separating agent is contained in the mixed layer in an amount of 1 to 60 % by weight based on the total weight of the mixed layer.
  • the thicknesses of organic separating agent vapor-deposited are about 20 nm to 100 nm, especially 30 to 60 nm, those of the mixed layer from 20 to 2000 nm, especially 50 to 500 nm depending upon the intended characteristics of the product.
  • the carrier is immersed in a dissolution bath, i.e. water.
  • a dissolution bath i.e. water.
  • the separating agent layer rapidly dissolves and the product layer breaks up into flakes, which are then present in water in the form of a suspension.
  • the porous silicon oxide flakes can advantageously be produced using an apparatus described in US-B-6,270,840.
  • the suspension then present in both cases, comprising product structures and solvent (water), and the separating agent dissolved therein, is then separated in a further operation in accordance with a known technique.
  • the product structures are first concentrated in the liquid and rinsed several times with fresh solvent in order to wash out the dissolved separating agent.
  • the product in the form of a solid that is still wet, is then separated off by filtration, sedimentation, centrifugation, decanting or evaporation.
  • a SiOi oo- 1 8 layer is formed preferably from silicon monoxide vapour produced in the vaporiser by reaction of a mixture of Si and Si ⁇ 2 at temperatures of more than 1300°C.
  • a SiOo 7o-o 99 layer is formed preferably by evaporating silicon monoxide containing silicon in an amount up to 20 % by weight at temperatures of more than 1300°C.
  • porous SiO y flakes with y > 1 can be achieved by providing additional oxygen during the evaporation.
  • the vacuum chamber can be provided with a gas inlet, by which the oxygen partial pressure in the vacuum chamber can be controlled to a constant value.

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Abstract

La présente invention concerne un produit qui peut être obtenu en faisant réagir une écaille de SiOy ou un matériau qui comprend une couche de SiOy avec 0,70 ≤ y ≤ 1,95, en particulier 0,70 ≤ y ≤ 1,80 et de manière toute particulière 1,0 ≤ y ≤ 1,8 avec une substance protonée, par exemple l'eau, ou un solvant organique protoné, pour produire des groupes SI-H, SI-H2 et/ou a-Si:H et en faisant réagir l'intermédiaire ainsi obtenu avec un composé qui présente des groupes fonctionnels capables de réagir avec les groupes Si-H, Si-H2 et/ou a-Si:H, ainsi qu'un procédé pour sa production. En utilisant le groupe Si-H comme ancrage de surface pour des composés organiques, on peut éviter d'utiliser des agents réducteurs dangereux tels que l'hydrure d'aluminium et de lithium, le borane ou l'hydrogène dans des procédés de greffage par réduction. On peut immobiliser des composés organiques ou minéraux, par exemple des colorants, ou des additifs, par exemple des agents d'absorption des UV, des photo-initiateurs ou des polymères. Les écailles modifiées peuvent être utilisées dans des revêtements, des matières plastiques, des fibres, et autres.
PCT/EP2006/068512 2005-11-25 2006-11-15 Ecailles d'oxyde de silicium reactif Ceased WO2007060125A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4245811A4 (fr) * 2021-08-27 2024-07-24 Resonac Corporation Composition thermoconductrice

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US6270840B1 (en) * 1998-09-28 2001-08-07 Weinert Vakuum Verfahrenstechnik Gmbh Apparatus and method for producing plane-parallel flakes
WO2004065295A1 (fr) * 2003-01-17 2004-08-05 Ciba Specialty Chemicals Holding Inc. Procede de production de materiaux inorganiques poreux ou d'un materiau de base contenant des nanoparticules
US20050161678A1 (en) * 2002-02-18 2005-07-28 Hilmar Weinert Methods of producing plane-parallel structures of silicon suboxide, silicon dioxide and/or silicon carbide, plane-parallel structures obtainable by such methods, and the use thereof

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US6270840B1 (en) * 1998-09-28 2001-08-07 Weinert Vakuum Verfahrenstechnik Gmbh Apparatus and method for producing plane-parallel flakes
US20050161678A1 (en) * 2002-02-18 2005-07-28 Hilmar Weinert Methods of producing plane-parallel structures of silicon suboxide, silicon dioxide and/or silicon carbide, plane-parallel structures obtainable by such methods, and the use thereof
WO2004065295A1 (fr) * 2003-01-17 2004-08-05 Ciba Specialty Chemicals Holding Inc. Procede de production de materiaux inorganiques poreux ou d'un materiau de base contenant des nanoparticules

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EP4245811A4 (fr) * 2021-08-27 2024-07-24 Resonac Corporation Composition thermoconductrice

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