EP3074406A1 - Acides siliciques silanisés hautement hydrophobes - Google Patents

Acides siliciques silanisés hautement hydrophobes

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Publication number
EP3074406A1
EP3074406A1 EP14799490.9A EP14799490A EP3074406A1 EP 3074406 A1 EP3074406 A1 EP 3074406A1 EP 14799490 A EP14799490 A EP 14799490A EP 3074406 A1 EP3074406 A1 EP 3074406A1
Authority
EP
European Patent Office
Prior art keywords
silicas
silica
silicic acids
methanol
modified
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.)
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Application number
EP14799490.9A
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German (de)
English (en)
Inventor
Achim Schneider
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.)
Wacker Chemie AG
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Wacker Chemie AG
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Filing date
Publication date
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Publication of EP3074406A1 publication Critical patent/EP3074406A1/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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon 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
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/54—Silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid

Definitions

  • the surface of unmodified silica e.g. is prepared by a wet chemical precipitation process or by hydrolysis of tetrachlorosilane in the hydrogen flame is covered with silanol groups, whereby the materials have a hydrophilic character.
  • silylation for example with hexamethyldisilazane (DE 2043 629), dichlorosilane (DE 1 163 784 B) or polydimethylsiloxane (EP 0 686 676 A1), it is possible to significantly reduce the number of silanol groups present on the surface. Due to the silicon-organic surface modification, the silica receives a more or less pronounced hydrophobic character.
  • surface-modified silicas Due to the altered surface properties associated with the modification, surface-modified silicas often behave distinctly differently from the unmodified agents in many applications.
  • surface-modified, hydrophobic silicic acids are often characterized by significantly higher thickening action in comparison to unmodified starting silicic acid, especially in systems such as solvents, polymers or resins which have polar groups, such as, for example, hydroxy, ceto, epoxy, ether -, ester, carboxyl or nitrogen-containing groups such as primary, secondary, or tertiary amino, amido or ammonium groups.
  • polar groups such as, for example, hydroxy, ceto, epoxy, ether -, ester, carboxyl or nitrogen-containing groups such as primary, secondary, or tertiary amino, amido or ammonium groups.
  • epoxy resins, polyurethanes, unsaturated polyester resins and aqueous dispersions and emulsions which are used for example as paints, coatings or adhesives application.
  • DE 44 19 234 A1 describes a process for the silylation of inorganic oxides, wherein the very finely divided inorganic oxides are treated with at least one silylating agent which has low volatility in the temperature range of the process.
  • DE 44 19 234 A1 relates to a highly nonpolar silica prepared by this process.
  • the examples given in the publication show that the thickening effect, for example, in a 25% strength aqueous ethanol solution increases with increasing hydrophobic character of the silica.
  • the hydrophobic nature of the silica was then determined by visual assessment of the wetting behavior of the samples to methanol / water mixtures of various Supremeset ⁇ tongues and (as a methanol number defined as the weight percent of methanol in water-methanol mixture, in which the Hälf ⁇ te of silica wetted and sunken in the liquid).
  • the examined samples of increasing document grade ie increasing amount of silane used for the modification based on the specific surface area corresponding to the data in Table 3 are characterized by a comparison with the non-surface-modified Aerosil® 200 starting silicic acid (Example 9) Significantly higher thickening of a liquid 1: 1 mixture of propanol / water (see table page 9). If one considers the modification with (H 3 CO) 3 S1C 16 H 33 (silane I), the increasing degree of occupation manifests itself in an increasing C content (see Table 4).
  • Examples 11 to 14 clearly show that a decreasing percentage C content of the silicas of Example 4 over Example 5 and 6 to Example 7, with a significant decrease in the thickening effect - goes.
  • the C content gives direct information about the proportion of non-polar hydrocarbons present on the silica, which are responsible for the hydrophobic character. As a result, an increasing C content is usually associated with a stronger hydrophobic character of the silicas.
  • H3CO octadecyltrimethoxysilane
  • H 3 CO octadecyltrimethoxysilane
  • the production of octadecyltrimethoxysilane proves to be rather complicated and cost-intensive, for example because of comparatively high melting and boiling points.
  • the comparatively high viscosities of said compounds in the customary manufacturing processes or product quality are also negatively noticeable (the kinematic viscosity according to DIN 51562-1 of hexadecyltrimethoxysilane (H 3 CO) 3 SiCi 6 H 3 3 is 7.2 mm 2 / s at 25 ° C).
  • silylating agents are often preferably added in liquid form as finely divided aerosol, for example achieved by nozzle techniques, to the powdered silica.
  • nozzle techniques ie as even as possible distribution of droplets of the same size as possible in the entire area of the spray cone
  • in the Atomization is a low viscosity advantageous.
  • even distribution of the silylating agent into fine aerosol droplets can achieve a uniform distribution of the documenting agent and thus homogeneous modification of the surface of the silica even at shorter residence times.
  • Surface-modified silicic acids are used in addition to the use as agents for rheology control but also as a flow aid, anti-blocking agent or for controlling the tribo-electric charging. Of particular technical relevance here is the use as an additive in toner formulations.
  • EP 1 502 933 A2 and EP 0 713 153 A2 describe such toner formulations which, in addition to the toner particles which essentially consist of a binder resin and the corresponding pigments, also contain hydrophobic inorganic particles, such as e.g. contain fumed silica, which is crucial in the control of the flow behavior and the charging behavior.
  • EP 1 502 933 A2 describes that in order to achieve a superior flowability, a uniform chargeability and a good stability even under moist conditions, the most pronounced and uniform hydrophobic character of the inorganic particles is desired (see, for example, paragraph [0048] and [0049 ]).
  • EP 1 302 444 AI describes u.a. in paragraph [0010] and
  • the object of the present invention is to overcome the disadvantages of the current state of the art and to provide silicas which are highly hydrophobic and therefore can be used particularly well for controlling the rheological or triboelectric properties of liquid media or as a flow aid.
  • the value for m is preferably between 0 and 7 and particularly preferably between 0 and 1.
  • R are preferably short-chain alkyl groups such as e.g. Methyl, ethyl, propyl or butyl groups, more preferably methyl or ethyl groups. In a particularly preferred embodiment, R is methyl groups.
  • the general formula (R0) 3 SiR comprises the formulas (R 1 0) 3 SiR (R 2 O) 2 (R 3 O) SiR x ), (R 2 O) (R ⁇ EiR ⁇ and / or (R 4 0 (R 5 0) (R 6 O) SiR and it holds that R describes the individual radicals R 1 to R 6 , these are as defined for R defined and may be different or the same Preferably, the groups selected for R are the same ,
  • R is a monovalent, optionally mono- or polyunsaturated, optionally branched aliphatic or aromatic hydrocarbon radical having 9 to 14 carbon atoms. It is in the radicals R 1 *, for example, alkyl groups such as nonyl, decyl, undecyl, dodecyl tridecyl and Tetrade- cyl groups. If the radicals R x are unsaturated hydrocarbon radicals, they preferably have the unsaturated moiety at the end of the hydrocarbon radical on.
  • the preferred unsaturated radicals R x are ⁇ ony-8-enyl, dec-9-enyl, undec-10-enyl, dodec-11-enyl, tridec-12-enyl and tetradec-13 enyl, ⁇ -8-inyl, dec-9-ynyl, undec-10-ynyl, dodec-ll-inyl, tridec-12-ynyl and tetradec-13-ynyl groups.
  • the unsaturated units can also be present at other points of the hydrocarbon chain, for example in the dodec-9-enyl, dodec-7-enyl, dodec-5-enyl or dodec-3-enyl groups.
  • the radicals R " 1 may also be optionally polyunsaturated, such as in dodeca-7, 9, 11-triene groups.
  • radicals R A are, as in the abovementioned examples, preferably unbranched radicals. However, it is also possible to use mono- or polysubstituted groups, for example 1-methyl-nonyl or 1, 1-dimethyl-decyl radicals.
  • R "1 nantrenyl- to aromatic groups such as for example, mesityl, naphthyl, biphenyl, Phe or act anthracenyl groups.
  • radicals R can contain heteroaromatics and in this case are for example aryl, alkyl, alkenyl or alkynyl groups which are substituted by primary, secondary or tertiary amino groups.
  • radicals R "1 preferably linear unbranched alkyl, alkenyl or alkynyl groups. It is particularly preferably the radicals R 1 to decyl, dodecyl and tetradecyl groups.
  • the silicas can be modified with only one kind of the groups R Si0 3/2 on the surface. But it can also contain two or more different groups may be present on the surface of the modified silicas, which differ in the radical R 1, ie the group R'Si0 3/2 can be 1-t include the groups R SI03 / 2, where the individual R 1 , R 2 , R 3 , etc. to R fc are selected from the groups defined above for R. For example, two could contact the flat-bound R, Si0 differ 3/2 ⁇ groups in the length of their carbon chains.
  • the surface of the metal oxide is preferably modified exclusively with one type of the abovementioned groups R x .
  • the surface of the silicic acids may have other groups in addition to the above-mentioned groups. Preference is given here tri- (MeSi0 3/2) are methylsiloxy- (Me 3 SIOI / 2), dimethylsiloxy (Me 2 Si0 2/2) or mono- methylsiloxy. Me stands for a methyl group.
  • the other groups present on the surface are not limited to those mentioned. It sämtli ⁇ che can rather well-known in the prior art, surface pendant groups on the silica be present.
  • slip agent may be particularly suitable, C n H 2n + i wear the organic groups, with the chain length is grown ⁇ an increase in the hydrophobicity to be expected.
  • the hydrophobic Cha ⁇ rakter a pyrogenic silica by examining the loading netzungsverhaltes of the respective samples with a mixture of water and methanol can be determined.
  • the sinking of the sample becomes noticeable in an increasing turbidity of the solution and can be monitored photometrically. As less and less light passes through the solution, the transmission drops rapidly as the sample wets.
  • Fig. 1 of EP 1502933 A2 shows exemplary titration curves of two different?
  • methanol number ge ⁇ aforementioned value corresponds to the methanol concentration in percent by volume, in which the Transmission decreases to 80% of the original value and is referred to as MeOH 80 .
  • MeOH 80 a higher number of methanol thus reflects a more pronounced hydrophobicity of the sample investigated.
  • Silica according to the invention means oxygen acids of silicon and, according to the invention, comprises both
  • Precipitated silicas which are produced by wet chemical means, as well as pyrogenic silicic acids, which are obtained by means of a flame process. These are essentially Si0 2 particles, ie oxide particles of silicon which carry acidic silanol groups on the surface.
  • the silica is preferably pyrogenically prepared silica.
  • the silicas of the invention specific Oberflä ⁇ chen of 1 to 800 m 2 / g f preferably 40 to 400 m 2 / g and particularly preferably 90 to 270 m 2 / g (determined by the BET method according to DIN 9277/66131 and DIN 9277 / 66132).
  • the tamped densities of the silicas according to the invention can be in the range from 10 to 500 g / l, preferably from 20 to 200 g / l, more preferably from 30 to 60 g / l (determined according to DIN EN ISO 787-11).
  • the silicas of the invention are characterized in that they aufwei ⁇ sen a residual silanol content of less than 70%, preferably less than 40% and particularly preferably less than 25%.
  • the residual silanol content after the modification can be determined, for example, by acid-base titration, as described, for example, in GW Sears et al. Analytical Chemistry 1956, 28, 1981ff.
  • the silicas of the invention have a carbon content ⁇ determined according to DIN ISO 10694 of 0-20%, preferably 5-15%, on. In a particularly preferred embodiment, the carbon content of the silicas according to the invention is 8-12%.
  • n is preferably even and is preferably 10, 12 or 14, since organotrialkoxysilanes and thus also the corresponding upper surface-modified silicas, where n is a ungeradzah ⁇ liger value, are uneconomical to manufacture.
  • Be ⁇ Sonders n is preferably 12 or 14, which means that the chain length of the radical comprising 12 or 14 carbon atoms.
  • the silicas of the invention are preferably characterized in that the groups introduced by the modification are firmly bound to the surface of the silicic acid. ' A firm bond stands for a good chemical binding and is inventively by the with solvents
  • the extractable fraction is particularly preferably at most 6% by weight, particularly preferably at most 3% by weight, and in a particular embodiment of the invention at most 2% by weight.
  • a suitable method for evaluating the bond strength of a modification is the quantitative determination of
  • a solvent (also solvent or solvent) is a
  • Substance that can dissolve or dilute gases, liquids or solids, without taking into chemical reactions Zvi ⁇ rule solute-dissolving substance is.
  • the solvent tetrahydrofuran used for the investigation of the silicas according to the invention does not dissolve any chemical bonds of the modifiers to the surface of the silica.
  • the extractable hereby components are thus connected only by weaker interactions such as Van der Waals forces with the silica.
  • a low reading for the extractable fraction indicates a better chemical, that is, stronger binding of the
  • the silicas according to the invention have the advantage that they are distinguished by a very high hydrophobicity.
  • the silicas of the invention preferably have a methanol number (MeOH 80 ) of more than 65% by volume, in particular more than 70% by volume. % on. In a particularly preferred embodiment be ⁇ transmits the methanol number of the silicas of the invention.% 73 or more by volume.
  • methanol number (MeOH 8 o) in the context of the invention, the methanol content of an aqueous methanol solution in volume percent to understand that causes sinking of the sample under investigation, whereby the transmission decreases to 80% of its original value. This value read from the titration curve is used for identification. WE ⁇ niger good hydrophobic material which wets already at a lower methanol content and therefore sinks. This less well hydrophobized material can be sorted out.
  • Deviating residual silanol contents can not be used for explanation, since Examples 2 and 3 according to the invention have an identical residual silanol content as Comparative Examples 5 or 4, but the methanol numbers are significantly higher according to the invention.
  • methanol half value (MeOH 50 ) should additionally be introduced here.
  • MeOH 50 one methanol content in volume per ⁇ -center, which causes a decrease of the transmission to 50% of the original value. If the two values MeOH 8 o and MeOH 50 this is very close to each other due to a rapid drop of the transmission with increasing methanol content and indicates therefore indicate a homogeneous Modifi ⁇ cation of the surface of the corresponding silicic acid, since the floating material at a certain Methanolge ⁇ stop sinking quickly.
  • the half-methanol numbers (MeOH 50) according to the invention by less than 2 vol.%, Preferably less than 1 vol.% Smaller than the numbers of methanol (MeOH 8 o) of ent ⁇ speaking silicas.
  • non-inventive silicas as shown in the comparative examples, often exhibit a more inhomogeneous modification of the surface, which is expressed in a larger difference of the MeOH 50 value compared to the MeOH 8 value.
  • Another object of the present invention relates to a process for the surface modification of silicas, which with a modifying agent selected from one or more Organotrialkoxysilanen of the general formula
  • the modifying agents used are preferably monoalkyltrialkoxysilanes, such as, for example, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyltrialkoxysilane, particularly preferably the corresponding methoxy or ethoxy derivatives, nonyl, Decyl, undecyl, dodecyl, tridecyl, tetradecyltrimethoxysilane or nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyltriethoxysilane.
  • monoalkyltrialkoxysilanes such as, for example, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyltrialkoxysilane, particularly preferably the corresponding methoxy or ethoxy derivatives, nonyl, Decyl, undec
  • the silicas of the invention may be modified with only one of the above-mentioned proofing agents, but it is also possible to use a mixture of two or more of the aforementioned proofing agents.
  • one or more other surface modifying slip agents may be used.
  • the comparatively higher viscosities of longer-chain silane compounds are negatively noticeable in the production process as well as in product quality.
  • the kinematic viscosity (according to DIN 51562-1) of hexadecyltrimethoxysilane (H 3 CO) 3 SiCi 6 H33 at 25 ° C., as already stated at the outset, is 7.2 mm 2 / s.
  • the kinematic viscosity of tetradecyltrimethoxysilane (H 3 CO) 3 SiCi 4 H 2 9 at 25 ° C only 5.4 mm 2 / s. Therefore, the use of the silane compounds according to the invention in the process according to the invention, as well as for the product quality of advantage.
  • the preparation of the surface-modified silica environmentally summarizes the reaction of the silica with the slip agent in egg ⁇ ner thermal treatment.
  • the silica is mixed with the slip agent, wherein the mixing is in particular be ⁇ preferably before the reaction.
  • the mixing process is also referred to as occupancy.
  • a purification of the modified silica ⁇ SUC gene, wherein particularly preferred excess Modisersa ⁇ gene and byproducts are removed.
  • the manufacturing process is carried out in separate steps comprising (1) mixing the silica with the modifying agents (occupancy), (2) reacting the silica with the proofing agent, and (3) purifying the modified silica.
  • the surface modification (reaction) is preferably carried out in an atmosphere which does not lead to oxidation of the upper ⁇ surface-modified silica, ie, preferably less than 10 vol.% Oxygen, more preferably less than 2.5 vol.%, Best results are achieved with less as 1 vol.% oxygen.
  • the pressure during the process steps ranges from a slight underpressure of 0.2 bar to an overpressure of 100 bar, wherein for technical reasons normal pressure, that is to say pressure-free working in relation to outside / atmospheric pressure, is preferred.
  • protic solvents may be added.
  • a protic solvent is when one Molecule has a functional group from which hydrogen atoms in the molecule can be split off as protons (dissociation). Due to the high polarity of the OH bond, it can be cleaved comparatively easily with elimination of a positively charged hydrogen atom, the proton.
  • protic solvent water, which (in simplified terms) dissociates into a proton and a hydroxide ion.
  • Other protic solvents provide z. Alcohols and carboxylic acids.
  • protic solvents may preferably be e.g. vaporizable liquids such as isopropanol, ethanol or methanol or water are added. It is also possible to add mixtures of the abovementioned protic solvents.
  • 1 to 50% by weight of protic solvent, based on the silica, are added, more preferably 5 to 25%.
  • Particularly preferred is the addition of water as a protic solvent.
  • the modification reaction of the invention is preferably carried out in a gas phase process, i.
  • the slip agent is added to the pure, largely dry (therefore powdery) silica.
  • the silica is presented in a liquid phase process in liquid phase.
  • the modifying agents are preferably added to the silica in liquid form.
  • the modifying agents can be admixed in pure form or as solutions in known solvents used industrially, for example, alcohols such as methanol, ethanol, or i-propanol, ethers such as diethyl ether, tetrahydrofuran, or dioxane, or hydrocarbons such as hexanes or toluene.
  • the concentration of the modifying agents in the solution is 5 to 95% by weight, preferably 50 to 95% by weight.
  • the addition in pure form is particularly preferred. According to the invention, the amounts of the liquid constituents are preferably chosen so that the reaction mixture is always a dry powder bed.
  • Dry powder-spillage in this context means that the mixture is substantially as the silica particles in the Gaspha ⁇ se is present.
  • the process control is in the liquid phase, ie the reaction of a silicic acid dispersed in the liquid phase.
  • the amounts by weight of liquid constituents used do not exceed the amount by weight of the silicic acid used. From 5 to 50, particularly preferably from 20 to 35, parts by weight of liquid constituents based on 100 parts of the silica are particularly preferably used.
  • inventive silicas substances are used which allow to shorten the necessary for the reaction of silica with the modifying agent response times and / or to lower the ⁇ necessary process temperatures beyond.
  • auxiliaries are optionally preferably in amounts of up to 10 ⁇ per m 2 surface to be modified
  • Silica added Preference is given to up to 5 pmol per m 2 surface of the silica to be modified, more preferably 0.5 to 2.5 ⁇ adjuvant per m 2 surface of the silica to be modified.
  • Surface of the unmodified silica may be measured from its mass and that measured by the BET method (see above)
  • Excipients to substances which have acidic or basic reactive functional groups include, for example Brönsted acids such as organic acids such as formic or acetic acid or inorganic acids such as hydrochloric acid, hydrochloric acid, phosphoric acid, sulfuric acid. It is also possible Lewis acids such as boron trichloride or aluminum trichloride are used.
  • the adjuvants used include bases such as hydroxides of alkali and alkaline earth metals, e.g. ,
  • Potassium hydroxide and sodium hydroxide as well as their derived from the corresponding alcohols or carboxylic acids salts, eg sodium, sodium or sodium acetate.
  • the basic, reactive compounds can be selected from nitrogen-containing compounds such as ammonia or organically substituted primary, secondary or tertiary amines.
  • the monovalent organic ⁇ substituents of said amines include saturated and unsaturated, branched and unbranched hydrocarbon radicals, which additionally further heteroatoms or fun-technischelle. Groups may have.
  • Compounds can be added in bulk but also as a solution in inert or reactive solvents. Preference is given to aqueous sodium hydroxide or potassium hydroxide solution, aqueous ammonia solution, i-propylamine, n-butylamine, i-butylamine, .alpha.-t-butylamine, cyclohexylamine, triethylamine, morpholine, piperidine or
  • the slip means are added as finely divided aerosol, characterized in that the aerosol has a sink rate of 0.1 to 20 cm / s.
  • An aerosol is a mixture (dispersion) of solid or liquid suspended particles and a gas.
  • the mixing (coating) of the silica with the said modifying agents is preferably carried out by nozzle techniques or similar techniques.
  • Effective atomization techniques can be, for example, atomization in 1-fluid nozzles under pressure (preferably at 5 to 20 bar), spraying in 2-fluid nozzles under pressure (preferably with gas and liquid at 2-20 bar), ultrafine distribution with atomizers or gas-solid exchange units with movable, rotating or static internals be a homogeneous Allow distribution of the slip agent with the powdered silica.
  • the aerosol can be applied via nozzles from above onto the agitated pulverulent solid, the nozzles being located above the fluid level and surrounded by the homogeneous gas phase, or into the fluidized solid, the metering openings being below the fluid level and are therefore surrounded by the heterogeneous particle / gas mixture are introduced. Preference is given to spraying from above.-,.
  • the addition of the silanes, the protic compound and the excipient-acting basic compounds can be carried out simultaneously or sequentially.
  • the coverage is such that first a homogeneous mixture of the silica with the excipient and the protic compound is prepared, which is then mixed with the silane.
  • the reaction (step 2) is a thermal treatment and is preferably carried out at temperatures of 30 ° C to 350 ° C, more preferably at 40 ° C to 250 ° C, more preferably at 50 ° C to 150 ° C and in a specific Embodiment at 100 ° C to 120 ° C.
  • the temperature profile can be kept constant during the reaction or, as described in EP 1 845 136, have an increasing gradient.
  • the residence time of the reaction (step 2) is preferably 1 minute to 24 hours, particularly preferably 15 minutes to 300 minutes and, for reasons of space-time yield, particularly preferably 15 minutes to 240 minutes.
  • Assignment (1) and reaction (2) are preferably carried out under me ⁇ chanic or gas-borne fluidization. While in the mechanical fluidization, the particulate powder by moving a body (for example, a stirring blade) in the bed or the fluid is placed in the fluid state, this is in the case of gas-borne fluidization only by introducing a gas, preferably from below (eg in a fluidized bed).
  • a gas-borne fluidization can be carried out by any inert gases that do not react with the modifying agents, the silica and the modified silica, so not to side reactions, Abbaure ⁇ actions.
  • Nitrogen, argon and other noble gases as well as carbon dioxide are preferably used here.
  • the supply of the gases for fluidization is preferably carried out in the range of Gasleerrohr Oberen of 0.05 to 5 cm / s, more preferably from 0.5 to 2.5 cm / s.
  • gas empty tube velocity is the quotient of the volume flow of the flowing gas which is present in the region in which the steps (1) occupancy, (2) reaction or (3) purification are carried out and the free cross-sectional area of the corresponding area through which it flows to understand.
  • the mechanical fluidization which takes place without additional ⁇ union beyond the inerting gas used by Fiügelragiter, anchor stirrer, and other suitable stirring elements is.
  • the purification step (3) is preferably ge by movement ⁇ features, slow movement and slight mixing is particularly preferred.
  • the stirring elements are preferably adjusted and moved so that mixing and fluidizing, but not complete turbulence, occurs.
  • the process temperature be raised if necessary.
  • the cleaning is preferably carried out at a temperature of 100 ° C to 350 ° C, preferably ⁇ 105 ° C to 180 ° C, more preferably from 110 ° C to 140 "C.
  • the cleaning step the supply of larger amounts of an inert gas, preferably nitrogen, argon and other noble gases and carbon dioxide, corresponding to a superficial gas velocity of preferably 0.001 to 10 cm / s, preferably 0.01 to 1 cm / s.
  • an inert gas preferably nitrogen, argon and other noble gases and carbon dioxide
  • Assignment, reaction and purification may be carried out as a batch process whereby a quantity of material limited by the capacity of the production vessel is supplied as a whole to the work system and removed as a whole upon completion of the production process, or as a continuous process i.e.. without interruptions.
  • a continuous reaction procedure as described, for example, in EP 1 845 136.
  • Modification coating and / or reaction
  • continuous or discontinuous methods of mechanical densification of the silica are used following the cleaning, such as presses, press rolls, grinding units, such as edge mills or ball mills, compaction by screws or screw mixers, screw compressors, briquetting, or compaction by aspiration of the air or gas content by suitable vacuum methods.
  • step (1) Particularly preferred is the mechanical compaction by pressing rollers, grinding units such as ball mills, screws, screw mixers, screw compressors or briquetting during the assignment in step (1). Occupancy and mechanical compaction Thus, in an aggregate at the same time, which for reasons of space / time yield and to save a separate pro-. positive step.
  • processes for the mechanical densification of the silica are used following the purification, such as compression by suction of the air or gas contents by suitable vacuum methods or pressure rollers or a combination of both methods.
  • the silicas may be ground in a particularly preferred procedure following purification.
  • aggregates such as pin mills, hammer mills, countercurrent mills, impact mills or devices for grinding sifting can be used.
  • the invention further provides for the use of the surface-modified silicas according to the invention or the surface-modified silicic acids prepared by the process according to the invention for controlling the flow properties of media such as adhesives, sealants and coating materials, for improving the mechanical properties of
  • Elastomers and for controlling the charge and flow properties of powders such as toners or powder coatings are preferred. Preferred is the use for controlling the rheological properties of liquid media and the use in toners.
  • the silicas of the invention give dispersions of silicas in liquids with strongly basic groups, which are distinguished by an excellent storage stability of the viscosity.
  • the elemental analysis on carbon was carried out according to DIN ISO 10694 using a CS-530 elemental analyzer from Eitra GmbH (D-41469 Neuss).
  • the determination of the residual silanol content was carried out analogously to G.W. Sears et al. ⁇ nalytical Chemistry 1956, 28, 1981ff by acid-base titration of the silica suspended in a 1: 1 mixture of water and methanol. The titration took place in the region above the isoelectric point and below the pH range of the dissolution of the silica.
  • the residual silanol content in% (% SiOH) can therefore be calculated according to the following formula:
  • SiOH (silyl) titration volume from the titration of silylated silica. Determination of the proportion of extractable silylating agent
  • Silicon content by atomic absorption spectroscopy (Atom Absorption Spectrometer 2100, Perkin Elmer Waltham, MA, USA) and weighed.
  • the extractables in% can be calculated as follows:
  • the transmission can Company Rhesca Company, Ltd be monitored and recorded and from the titration curve, the Me ⁇ thanoliere (MeOHeo) can be read, for example, with a powder-wetting tester WET-100P.
  • the methanol half-value (MeOH 50 ) is read as the methanol content in volume percent, which causes a decrease in the transmission to 50%. Examples Example 1:
  • Two-fluid nozzle (hollow cone nozzle, model 121, the company nozzles Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° spray angle, 0.1 mm bore, operated with 5 bar nitrogen) 6.2 g of a
  • Reaction mixture was for three. Hours under vigorous
  • a continuous apparatus in a mixing vessel under a nitrogen atmosphere at a temperature of 41 ° C to a mass flow of 1000 g / h of a hydrophilic silica having a specific surface area of 200 m 2 / g, determined by the BET method according to DIN 66131 and 66132 ( receives ⁇ well below the name HDK ® N20 from Wacker Chemie AG, Kunststoff, Germany) by spraying via two-component nozzles 52.g / sodium h of a 25% ammonia solution (hollow cone nozzle, model 121, the company jet-Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° Sprühwin ⁇ kel, 0.1 mm bore, operated with nitrogen at 5 bar), and 220 g / h tetradecyltrimethoxysilane (hollow-cone nozzle, model 121, the company Düsen-Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° spray angle
  • the so charged silica is reacted in a stirred reaction vessel by heating to 97 ° C for 1.4 h and then in a heated to 140 ° C dryer for 20 min under mechanical agitation and a nitrogen flow of 0.3 Nm 3 / h cleaned.
  • a continuous apparatus In a continuous apparatus are in a mixing vessel under a nitrogen atmosphere at a temperature of 41 ° C to a mass flow of 1200 g / h of a hydrophilic silica having a specific surface area of 200 m 2 / g, determined by the BET method according to DIN 66131 and 66132 ( receives ⁇ well below the name HDK ® N20 from Wacker Chemie AG, Kunststoff, Germany) by spraying via two-component nozzles 62 g / h of a 25% ammonia solution (hollow cone nozzle, model 121, the company jet-Schlick GmbH, D-96253 Untersiemau / Coburg , 30 ° spray angle, 0.1 mm bore, operated with 5 bar nitrogen) and 264 g / h tetradecyltrimethoxysilane (Hohlkegeldüse, Model 121, the company Düsen-Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° spray angle
  • the so charged silica is reacted in a stirred reaction vessel by heating to 103 ° C for 1.2 h and then cleaned in a heated to 140 ° C dryer for 17 min mechanical movement and a nitrogen flow of 0.3 Nm 3 / h ,
  • a continuous apparatus In a continuous apparatus are in a mixing vessel under a nitrogen atmosphere at a temperature of 45 ° C to a mass flow of 1000 g / h of a hydrophilic Kiesel ⁇ acid having a specific surface area of 200 m 2 / g, determined by the BET method according to DIN 66131 and 66132 (obtained ⁇ well below the name of HDK ® N20 from Wacker Chemie AG, Kunststoff, Germany) by spraying through two-fluid nozzles 44 g / h of a 25% ammonia solution (hollow-cone nozzle, model 121, the company nozzle-Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° Sprühwin ⁇ angle, 0.1 mm bore, operated with 5 bar nitrogen) and 209 g / h hexadecyltrimethoxysilane (hollow cone nozzle, model 121, the company nozzles Schlick GmbH, D-96253 Untersiemau / Coburg
  • the silica loaded, in a stirred reaction vessel by heating at 120 ° C for 1.4 h to re ⁇ action and then brought in a heated dryer at 140 ° C for 20 min mechanical agitation and a nitrogen flow of 0.2 Nm 3 / h cleaned.
  • a continuous apparatus in a mixing vessel under a nitrogen atmosphere at a temperature of 50 ° C to a mass flow of 600 g / h of a hydrophilic silica having a specific surface area of 200 m 2 / g, determined by the BET method according to DIN 66131 and 66132 ( available under the name HDK® N20 from Wacker Chemie AG, Kunststoff, Germany) by atomizing over two-component nozzles 26 g / h of a 25% ammonia solution (Hohlkegelüse, Model 121, the company Düsen-Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° Sprühwin ⁇ kel, 0.1 mm bore, operated at 5 bar nitrogen) and 125 g / h hexadecyltrimethoxysilane (hollow cone nozzle, model 121, the company Düsen-Sehlick GmbH, D-96253 Untersiemau / Coburg, 30 ° ⁇
  • the silica loaded is brought to re ⁇ action, and then in a heated dryer at 140 ° C for 34 min mechanical agitation and a nitrogen flow of 0.2 Nm 3 / h in a stirred reaction vessel by heating at 240 ° C for 2.4 h cleaned.
  • Example 7 To 120 g of a hydrophilic silica having a specific surface area of 200 in 2 / g, determined by the BET method according to DIN - 66131 and 66132 (available under the name HDK ® N20 from Wacker Chemie AG, Kunststoff, Germany) under nitrogen atmosphere by spraying over one
  • Two-fluid nozzle (hollow cone nozzle, model 121, the company nozzles Schlick GmbH, D-96253 Untersiemau / Coburg, 30 ° spray angle, 0.1 mm bore, operated at 5 bar nitrogen) 6.3 g of a
  • SiOH [%] indicates the content of unmodified silanol silanol groups (residual silanol content)
  • C [%] indicates the carbon content.
  • Konti denotes a continuous production process, batch a discontinuous one.

Abstract

L'invention concerne des acides siliciques silanisés hautement hydrophobes. L'invention vise à proposer des acides siliciques qui soient hautement hydrophobes et donc qui puissent être particulièrement bien utilisés pour la gestion des propriétés rhéologiques ou triboélectriques de milieux liquides ou en tant qu'agents antiagglomérants. A cet effet, l'invention propose des acides siliciques qui sont modifiés en surface avec un composé du groupe (RO)3SiR`, où R` = CnH2 (n-m)+1, n = 9 à 14, m = 0 à n et R = CqH2q+1 avec q = 1 à 4. En outre, l'invention concerne un procédé de modification en surface d'acides siliciques choisis avec un agent de modification parmi un ou plusieurs organotrialcoxysilanes de formule générale (RO)3SiR` où R` = CnH2 (n-m)+1 avec n = 9 à 14 et = 0 à n et R = CqH2q+1 avec q = 1 à 4, qui sont traités dans une réaction thermique. Les acides siliciques modifiés en surface proposés selon l'invention peuvent être utilisés pour la gestion des propriétés rhéologiques ou triboélectriques de milieux fluides tels que par exemple, des épaississants et des anti-adhérents ou antiagglomérants.
EP14799490.9A 2013-11-27 2014-11-19 Acides siliciques silanisés hautement hydrophobes Withdrawn EP3074406A1 (fr)

Applications Claiming Priority (2)

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DE102013224210.7A DE102013224210A1 (de) 2013-11-27 2013-11-27 Silanisierte hochhydrophobe Kieselsäuren
PCT/EP2014/075011 WO2015078744A1 (fr) 2013-11-27 2014-11-19 Acides siliciques silanisés hautement hydrophobes

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JP (1) JP2017503759A (fr)
KR (1) KR20160075691A (fr)
CN (1) CN105793271A (fr)
DE (1) DE102013224210A1 (fr)
WO (1) WO2015078744A1 (fr)

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US20160263540A1 (en) 2016-09-15
CN105793271A (zh) 2016-07-20
KR20160075691A (ko) 2016-06-29
JP2017503759A (ja) 2017-02-02
WO2015078744A1 (fr) 2015-06-04

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