WO2004054927A1 - Surface-modified, aerogel-type, structured silica - Google Patents

Surface-modified, aerogel-type, structured silica Download PDF

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Publication number
WO2004054927A1
WO2004054927A1 PCT/EP2003/012382 EP0312382W WO2004054927A1 WO 2004054927 A1 WO2004054927 A1 WO 2004054927A1 EP 0312382 W EP0312382 W EP 0312382W WO 2004054927 A1 WO2004054927 A1 WO 2004054927A1
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Prior art keywords
silica
type
water
aerogel
alkyl
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Ceased
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PCT/EP2003/012382
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French (fr)
Inventor
Jürgen Meyer
Horst Zeizinger
Manfred Ettlinger
Hans-Dieter Christian
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Evonik Operations GmbH
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Degussa GmbH
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Publication date
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Priority to AU2003276260A priority Critical patent/AU2003276260A1/en
Priority to BR0317453-0A priority patent/BR0317453A/en
Priority to CN2003801096340A priority patent/CN1747899B/en
Priority to JP2004559678A priority patent/JP2006515556A/en
Publication of WO2004054927A1 publication Critical patent/WO2004054927A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • 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
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • 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
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • 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
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/159—Coating or hydrophobisation
    • 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
    • C01P2006/10—Solid density
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values

Definitions

  • the invention concerns a surface-modified, aerogel-type, structured silica.
  • Aerogels are understood to be silica gels having a low; bulk density (appr ⁇ x. 20 to 50 g/1) and high macroporosity (DBP numbers from 200 to 400) . Due to the contraction effect described by R Her, which leads to a collapse of the pore structure during the ,drying of silica gels from the aqueous phase, silica aerogels are only obtainable by the method described b'y . Kistler in US-PS 2,249,767. To this end' Kistler partially dewaters silica sols with alcohols and then dries the water-containing alcogel in an autoclave by expansion under supercritical conditions. In this way he obtains particularly loosely constructed structures consisting of the primary particles of the silica sol, which display high volume values in the macropore range (>300 A) combined with a very low apparent density (bulk density) .
  • these substances which are classed as an aerogel, are used as fillers, support silicas, flatting agents, thickeners, etc.
  • the necessary use of organic solvents and the supercritical drying to be performed in an autoclave make the process for producing these aerogels both technically complicated and expensive.
  • the primary particles of pyrogenic silica occur in beds, loosely associated by means of electrostatic and van der aals forces. They .agglomerate into floes, which display a high air content and thus have a very high apparent pore volume and correspondingly a low bulk density.
  • a bed of these floes is best described as an air dispersion.
  • the floes are unstable, however, and unlike the secondary particles in Kistler aerogels they are broken down into primary particles under the slightest mechanical loading.
  • aerogel-type structured silica as a flatting agent in surface coatings, such as paints for example, is known (DE 24 14 478) .
  • the invention provides an aerogel-type, structured silica which is characterized in that it is surface-modified.
  • An aerogel-type, structured silica according to DE 2 414 878 for example can be used as the starting silica.
  • the starting silica for the surface modification can also be an aerogel-type structured silica having the following material parameters:
  • BET surface area between 80 and 450 m 2 /g Bulk density between 10 and 60 g/1 DBP number between 200 and 400 pH from 6 to 8
  • the aerogel-type structured silica can be produced by incorporating 5-50 wt.% water into air-dispersed pyrogenic silica with uniform dispersion and drying the powdered mixture that is obtained.
  • It can be produced by flame hydrolysis of volatile or evaporable silicon compounds, such as e.g. S ⁇ Cl 4 , methyl trichlorosilane and others, in an oxyhydrogen flame.
  • volatile or evaporable silicon compounds such as e.g. S ⁇ Cl 4 , methyl trichlorosilane and others
  • silica with large surface areas and hence small primary particles It has also proven advantageous to choose pyrogenic silica with large surface areas and hence small primary particles.
  • silica with BET surface areas of between 100 and 480, in particular 250 to 300 m 2 /g is used.
  • Complete wetting of the primary particles can be achieved by incorporating as little .as 5 to 20, in particular 7 to 15 wt.% water into the silica with uniform distribution. Since the water that is incorporated is to be removed again by drying, it is-desirable for economic reasons to minimize the amount of water. The amount required depends to a certain extent on the type of incorporation, however.
  • Structure formation by the process according to the invention can be noticeably promoted if basic-reacting compounds, such as e.g. ammonia, sodium hydroxide, potassium hydroxide, water-soluble amines, water glass or the like are added to the water.
  • basic-reacting compounds such as e.g. ammonia, sodium hydroxide, potassium hydroxide, water-soluble amines, water glass or the like are added to the water.
  • the amounts to be added are conveniently chosen such that a pH of 7 to 14, preferably ' 8 to 12, in particular 10 to 11, is established in the water.
  • the alkalis used act as a solution aid for silica and bring about an increase in the macroporosity of the process products .
  • alkaline compounds instead of alkaline compounds, free silica or hydrolytic silica and/or substances that release alkali can also be added to the water.
  • Free silica produced for example by acidification or ionic exchange of silicate solutions or by hydrolytic cleavage of organosilicon compounds, for example tetramethyl silicate, likewise promotes structure formation.
  • a substance that releases alkali and silica hydrolytically is sodium methyl siliconate, for example.
  • the water can be uniformly dispersed in the silica by dropping or spraying it into the silica, which is kept in motion by mixing, at silica temperatures of between 20 and 100, preferably 40 to 70, in particular 5-0 to 60 °C.
  • the mixing motion is conveniently achieved by stirring.
  • a further variant of water incorporation consists of spraying the water into a mass flux of silica fluidized in a downpipe for example.
  • the water to be incorporated can be at a temperature of between
  • Structure formation can also be promoted by brief steaming of the loaded silica in a closed room. Steaming leads to a particularly good water distribution. It has proven favorable in this respect to steam the water-loaded silica before drying for approx. 5 to 60, preferably ' 10 to 30, in particular around 20 minutes, in a closed vessel at temperatures up to the boiling point of water, preferably 50 to 80, in particular around 60 °C.
  • a further possibility for improving the water distribution consists of grinding the water-loaded silica in a pin mill or air jet mill for example.
  • the type of drying is not of critical importance.
  • the mixture of silica and water that has been produced which in phenomenological terms always resembles a dry powder, can be dried for example in chamber, disk, B ⁇ ttner, flow or microwave dryers.
  • the water-loaded silica can also be ground and dried simultaneously, avoiding a separate process stage, in a steam jet or air jet mill. If the powdered mixture obtained after loading with water is dried ' separately, this can be followed by dry grinding in a pin mill or air jet mill.
  • the invention also provides a process for the production of the surface-modified, aerogel-type, structured silica, 1 which is characterized in that an aerogel-type, structured silica is prepared, optionally sprayed first with water or with acidified'" ' water and then with the silanizing agent, which can optionally be dissolved in a solvent, post-mixed and the mixture ' conditioned.
  • Ethanol for example can be used as the solvent for the silanizing agent. Conditioning can be performed batchwise in a drying oven, for example, or continuously. Conditioning' can optionally be performed under a protective gas atmosphere.
  • the water used can be acidified with an acid, for example hydrochloric acid, to a pH of 7 to 1.
  • an acid for example hydrochloric acid
  • Silanization can be performed by spraying the silica with the silanizing agent at room temperature and then subjecting the mixture to a thermal treatment at a temperature of 105 to 400 °C for a period of 1 to 6 h.
  • An alternative method for silanizing the silica can be performed by treating the silica with the silanizing agent in vapor form and then subjecting the mixture to a thermal treatment at a temperature of 200 to 800 °C for a period of 0.5 to 6 h.
  • the thermal treatment can be performed under protective gas, such as nitrogen for example.
  • Silanization can be performed in heatable mixers and dryers with sprayers, on a continuous or batchwise basis. Examples of suitable devices include plough mixers, disk dryers, fluidized bed or moving bed dryers.
  • Halosilanes, alkoxysilanes, silazanes and/or siloxanes can be used for surface modification or silanization. Several of these compounds can also be used as a mixture or successively.
  • R alky ;- such as e.g. methyl, ethyl, n-propyl, i-propyl, butyl
  • R' alkyl, such ' as e.g. methyl, ethyl, n-propyl, i-propyl, butyl
  • R' alkyl, such as e.g. methyl, ethyl, n-propyl, i-propyl, butyl
  • R' alkyl, such as e.g. methyl, ethyl, n-propyl, i- propyl, butyl
  • R' methyl, aryl (e.g.-C 6 H 5 , substituted phenyl radicals)
  • R' methyl, aryl (e.g. -C 6 H 5 , substituted phenyl radicals)
  • R' methyl, aryl (e.g. -C 6 H 5 , substituted phenyl radicals)
  • Haloorganosilanes of the type (R)X 2 Si (CH 2 ) m -R' X Cl, Br
  • R' methyl, aryl (e.g. -C 6 H 5 , substituted phenyl radicals)
  • R' methyl, aryl (e.g. -CgH 5 , substituted phenyl .radicals)
  • R alkyl, vinyl, aryl
  • R' alkyl, vinyl, aryl
  • Cyclic polysiloxanes of the type D 3, D 4, D 5, whereby D ' 3, D 4 and D 5 are understood to be cyclic polysiloxanes with 3, 4 or 5 units of the type -0-Si(CH 3 ) 2 - e.g. octamethyl cyclotetrasiloxane D 4
  • 3-Methacryloxypropyl trimethoxysilane can preferably be used.
  • Trimethoxyoctyl silane and/or hexamethyl disilazane can preferably used as the silanizing agent.
  • 3-Glycidyloxypropyl trimethoxysilane can preferably be used as the silanizing agent.
  • R alkyl
  • R' alkyl, vinyl
  • Dimethyl polysiloxane can be used in particular.
  • the surface-modified, aerogel-type, structured silica according to the invention can be used as a flatting agent in surface coatings such as e.g. paints.
  • This aerogel-type structured silica is placed in a mixer and optionally sprayed first with water and then with the silanizing agent with intensive mixing . On completion of spraying, post-mixing is continued for a further 15 min and conditioning then performed in a drying oven .
  • the parameters for producing the silica according to the invention are set out in Table 1 and the physico-chemical data in Table 2 .
  • MEMO 3-methacryloxypropyl trimethoxysilane
  • OCTMO octyl trimethoxysilane
  • HMDS hexamethyl disilazane
  • GLYMO glycidyl oxypropyl trimethoxysilane
  • Paint system 1 has the following composition :
  • Irgacure 500 photoinitiator (mixture of benzophenone Ciba and 1-hydroxycyclohexyl phenyl ketone )
  • Dow Corning PA 57 silicone-containing flow-control agent Dow Corning Paint system 2 has the following composition :
  • Desmophen 800 Polyester polyol Bayer AG
  • Desmophen 1100 Polyester polyol Bayer AG CAB 381-0, 5 Cellulose Krahn Chemie acetobutyrate
  • Baysilone OL 17 Polyether siloxane Borchers BYK 361 Polyacrylate copolymer Byk Chemie Desmodur L 75 Aromatic Bayer AG polyisocyanate Determination of the physico-chemical properties
  • the BET surface area is determined with nitrogen in accordance with DIN 66 131.
  • the compacted bulk density (previously compacted bulk volume) equals the quotient of the mass and volume of a powder after tamping in a tamping volumeter under established conditions. According to DIN ISO 787/XI the compacted bulk density is stated in g/cm 3 . Due to their very low compacted bulk density, the value for oxides is stated in g/1. Drying, screening and repetition of the tamping process are omitted.
  • 200 ⁇ 10 ml oxide are introduced into the measuring cylinder of the tamping volumeter such that no voids remain and the surface is horizontal.
  • the mass of the sample introduced into the cylinder is determined to an accuracy of 0.01 g.
  • the measuring cylinder with the sample is placed in the measuring cylinder holder in the tamping volumeter and tamped 1250 times.
  • the volume of the tamped oxide is read off to an accuracy of 1 ml. Evaluating the compacted bulk density determination g weighed amount x 1000
  • the pH is determined in a 4 % aqueous dispersion, in water : methanol 1:1 in the case of hydrophobic oxides.
  • hydrophilic oxide 4 g hydrophilic oxide are placed in a 250 ml beaker with 96 g (96 ml) water using a Dispensette and, with the pH electrode immersed, stirred for five minutes with a magnetic stirrer (speed approx. 1000 rpm) .
  • 4 g hydrophobic oxide are mixed into a paste with 4 ⁇ g (61 ml) methanol in a 250 ml beaker and the suspension diluted with 48 g (48 ml) water and, with the pH electrode immersed, stirred for five minutes with a magnetic stirrer (speed approx. 1000 rpm) .
  • a weighed amount of 1 g is used to determine the loss on drying.
  • the cover is fitted before cooling. A second drying stage is not performed.
  • Deviating' from DIN 55 921, 0.3 - 1 g of the un-predried' substance is weighed to an. accuracy of 0.1 mg into a previously ignited porcelain crucible with crucible lid and ignited for 2 hours at 1000 °C in a muffle furnace.
  • the slow heating of the furnace avoids any major air turbulence in the porcelain crucible.
  • Plastic beaker 250 ml
  • the metering unit delivers 4 ml DBP/min until the preset cutoff point (1000) is reached.
  • the consumption of DBP can then be read from the display of the metering unit.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

A surface-modified, aerogel-type, structured silica is produced by spraying an aerogel-type, structured silica with a silanizing agent, post-mixing and conditioning. It can be used as a flatting agent.

Description

Surface-modified, aerogel-type, structured silica
The invention concerns a surface-modified, aerogel-type, structured silica.
Aerogels are understood to be silica gels having a low; bulk density (apprόx. 20 to 50 g/1) and high macroporosity (DBP numbers from 200 to 400) . Due to the contraction effect described by R Her, which leads to a collapse of the pore structure during the ,drying of silica gels from the aqueous phase, silica aerogels are only obtainable by the method described b'y.Kistler in US-PS 2,249,767. To this end' Kistler partially dewaters silica sols with alcohols and then dries the water-containing alcogel in an autoclave by expansion under supercritical conditions. In this way he obtains particularly loosely constructed structures consisting of the primary particles of the silica sol, which display high volume values in the macropore range (>300 A) combined with a very low apparent density (bulk density) .
Depending on their degree of porosity and bulk density, these substances, which are classed as an aerogel, are used as fillers, support silicas, flatting agents, thickeners, etc. The necessary use of organic solvents and the supercritical drying to be performed in an autoclave make the process for producing these aerogels both technically complicated and expensive.
It is known that the stated disadvantages of the methods available until now for the production of aerogels can be avoided if primary particles of pyrogenically produced silicas are used in place of the silica sol particles and recovery from the liquid phase is omitted.
The primary particles of pyrogenic silica occur in beds, loosely associated by means of electrostatic and van der aals forces. They .agglomerate into floes, which display a high air content and thus have a very high apparent pore volume and correspondingly a low bulk density.
A bed of these floes is best described as an air dispersion. The floes are unstable, however, and unlike the secondary particles in Kistler aerogels they are broken down into primary particles under the slightest mechanical loading.
The use of aerogel-type structured silica as a flatting agent in surface coatings, such as paints for example, is known (DE 24 14 478) .
The invention provides an aerogel-type, structured silica which is characterized in that it is surface-modified.
An aerogel-type, structured silica according to DE 2 414 878 for example can be used as the starting silica.
The starting silica for the surface modification can also be an aerogel-type structured silica having the following material parameters:
BET surface area between 80 and 450 m2/g Bulk density between 10 and 60 g/1 DBP number between 200 and 400 pH from 6 to 8
The aerogel-type structured silica can be produced by incorporating 5-50 wt.% water into air-dispersed pyrogenic silica with uniform dispersion and drying the powdered mixture that is obtained.
Since the volume of silica reduces only slightly as the water is incorporated, it can be assumed that the originally existing association of the primary particles of the air-dispersed pyrogenic silica is substantially retained. The loading with water probably leads to a partial dissolution of the silica surface, such that dissolved silica is present here.
During the subsequent drying process this bonds the primary particles to their points of contact.
Selective loading with water and subsequent drying from a pyrogenic silica thus produces a dispersible substance corresponding to the Kistler aerogels, having a high macropore volume and very low apparent density (bulk density) .
It was also established that the apparent structure existing before incorporation of the water, determined by the packing density of the pyrogenic silica in air and expressed by its apparent density (bulk density) , has a marked influence on the product that can be obtained by the process according to the invention: the more voluminous the starting product, the more voluminous the end product.
Pyrogenically produced silica is known from Ullmanns Enzyklopadie der technischen Chemie 4th Edition, Volume 21, page 462 ff.
It can be produced by flame hydrolysis of volatile or evaporable silicon compounds, such as e.g. SϊCl4, methyl trichlorosilane and others, in an oxyhydrogen flame.
It has proven convenient to use pyrogenic silica with a bulk density of 10 to €0,. preferably 15 to 30, in particular around 20 g/1, to produce the products according to the invention.
It has also proven advantageous to choose pyrogenic silica with large surface areas and hence small primary particles. According to a favorable embodiment of the process according to the invention, silica with BET surface areas of between 100 and 480, in particular 250 to 300 m2/g, is used. Complete wetting of the primary particles can be achieved by incorporating as little .as 5 to 20, in particular 7 to 15 wt.% water into the silica with uniform distribution. Since the water that is incorporated is to be removed again by drying, it is-desirable for economic reasons to minimize the amount of water. The amount required depends to a certain extent on the type of incorporation, however.
Structure formation by the process according to the invention can be noticeably promoted if basic-reacting compounds, such as e.g. ammonia, sodium hydroxide, potassium hydroxide, water-soluble amines, water glass or the like are added to the water. The amounts to be added are conveniently chosen such that a pH of 7 to 14, preferably' 8 to 12, in particular 10 to 11, is established in the water.
The alkalis used act as a solution aid for silica and bring about an increase in the macroporosity of the process products .
Instead of alkaline compounds, free silica or hydrolytic silica and/or substances that release alkali can also be added to the water.
Free silica produced for example by acidification or ionic exchange of silicate solutions or by hydrolytic cleavage of organosilicon compounds, for example tetramethyl silicate, likewise promotes structure formation.
A substance that releases alkali and silica hydrolytically is sodium methyl siliconate, for example.
The water can be uniformly dispersed in the silica by dropping or spraying it into the silica, which is kept in motion by mixing, at silica temperatures of between 20 and 100, preferably 40 to 70, in particular 5-0 to 60 °C. The mixing motion is conveniently achieved by stirring. A further variant of water incorporation consists of spraying the water into a mass flux of silica fluidized in a downpipe for example.
It has further proven advantageous to perform the water loading at moderately elevated temperatures.
This can be done by preheating either the water to be incorporated or the silica or both components. Thus the water to be incorporated can be at a temperature of between
20 and 100, preferably 50 to 100, in particular 90 to
100 °C.
Structure formation can also be promoted by brief steaming of the loaded silica in a closed room. Steaming leads to a particularly good water distribution. It has proven favorable in this respect to steam the water-loaded silica before drying for approx. 5 to 60, preferably ' 10 to 30, in particular around 20 minutes, in a closed vessel at temperatures up to the boiling point of water, preferably 50 to 80, in particular around 60 °C.
A further possibility for improving the water distribution consists of grinding the water-loaded silica in a pin mill or air jet mill for example.
It is then dried, whereby the preformed structure is presumably fixed by primary particles that are partially dissolved at the surface or that are coated at the surface with free silica.
The type of drying is not of critical importance. The mixture of silica and water that has been produced, which in phenomenological terms always resembles a dry powder, can be dried for example in chamber, disk, Bϋttner, flow or microwave dryers. However, the water-loaded silica can also be ground and dried simultaneously, avoiding a separate process stage, in a steam jet or air jet mill. If the powdered mixture obtained after loading with water is dried 'separately, this can be followed by dry grinding in a pin mill or air jet mill.
The invention also provides a process for the production of the surface-modified, aerogel-type, structured silica,1 which is characterized in that an aerogel-type, structured silica is prepared, optionally sprayed first with water or with acidified'"'water and then with the silanizing agent, which can optionally be dissolved in a solvent, post-mixed and the mixture' conditioned.
Ethanol for example can be used as the solvent for the silanizing agent. Conditioning can be performed batchwise in a drying oven, for example, or continuously. Conditioning' can optionally be performed under a protective gas atmosphere.
Once spraying has been completed, post-mixing is continued for a further 15 to 30 min and conditioning then performed for 1 to 4 h at 100 to 400 °C.
The water used can be acidified with an acid, for example hydrochloric acid, to a pH of 7 to 1.
Silanization can be performed by spraying the silica with the silanizing agent at room temperature and then subjecting the mixture to a thermal treatment at a temperature of 105 to 400 °C for a period of 1 to 6 h.
An alternative method for silanizing the silica can be performed by treating the silica with the silanizing agent in vapor form and then subjecting the mixture to a thermal treatment at a temperature of 200 to 800 °C for a period of 0.5 to 6 h.
The thermal treatment can be performed under protective gas, such as nitrogen for example. Silanization can be performed in heatable mixers and dryers with sprayers, on a continuous or batchwise basis. Examples of suitable devices include plough mixers, disk dryers, fluidized bed or moving bed dryers.
Halosilanes, alkoxysilanes, silazanes and/or siloxanes can be used for surface modification or silanization. Several of these compounds can also be used as a mixture or successively.
The following substances in particular can be used: a) Organosilanes of the type (RO) 3Si (CnH2n+ι) and
(RO)3Si(CnH2n-ι)
R = alkyl, such as e.g. methyl, ethyl, n-propyl, i-propyl, butyl n = 1 - 20 b) Organosilanes of the type R'x(RO) ySi (CnH2n+ι) and
(RO)3Si(CnH2n+1)
R = alky ;- such as e.g. methyl, ethyl, n-propyl, i-propyl, butyl R' = alkyl, such 'as e.g. methyl, ethyl, n-propyl, i-propyl, butyl R'= cycloalkyl n = 1 - 20 x+y = 3 x = 1.2 y = l'.2 c) Haloorganosilanes of the type X3Si (CnH2n+ ) and
XaSKCnHzn-i )
X = Cl, Br n = 1 - 20 ' d) Haloorganosilanes of the type X (R? ) Si (CnH2n+ι) and X2(R')Si(CnH2n.1)
X = Cl, Br
R' = alkyl, such as e.g. methyl, ethyl, n-propyl, i-propyl, butyl R'= cycloalkyl n = 1 - 20 e) Haloorganosilanes of the type X (R' ) 2Si (CnH2rl+i) and
X(R')2Si(CnH2n-ι)
X = Cl, Br
R' = alkyl, such as e.g. methyl, ethyl, n-propyl, i- propyl, butyl
R'= cycloalkyl n = 1 - 20 f) Organosilanes of the type (RO) 3Si'(CH2)m-R'
R = alkyl, such as methyl, ethyl, propyl m = 0.,1 - 20
R' = methyl, aryl (e.g.-C6H5, substituted phenyl radicals)
-C4F9, OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 -NH2, ~ 3r -SCN, -CH=CH2, -NH-CH2-CH2-NH2,
-N-(CH2-CH2-NH2)2 -OOC(CH3)C = CH2
-OCH2-CH(0)CH2
-NH-CO-N-CO-(CH2)5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH-(CH2)3Si(OR)3
-Sχ-(CH2)3Si(OR)3
-SH'
-NR'R' 'R* '■ (R* = alkyl, aryl; R" = H, alkyl, aryl; R' ' ' = H, alkyl, aryl, benzyl, C2H4NR' ' ' ' R' • ' " where R1 ' ' ' = A, alkyl and R" ' " = H, alkyl) g) Organosilanes of the type (R") x (RO) ySi (CH2)Itl-RI
R" = alkyl x+y = 3 = cycloalkyl x = 1.2 y = 1.2 = 0.1 to 20 R' = methyl, aryl (e.g. -C6H5, substituted phenyl radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-NH2, -N3, -SCN, -CH=CH2, -NH-CH2-CH2-NH2,
-N-(CH2-CH2-NH2)2 -OOC(CH3)C = CH2
-OCH2-CH(0)CH2
-NH-CO-N-CO-(CH2)5
-NH^CQO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3
-Sx-(CH2)3Si(OR)3
-SH -
- R^'R'" (R» = alkyl, aryl; R" = H, alkyl, aryl; R' ' ' = H, alkyl, aryl, benzyl, C2H4NR' ' ' » R" ' ' ' where R1 ' ' ' = A, alkyl and R" " ' = H, alkyl) h) Haloorganosilanes of the type X3Si (CH2) m-R '
X = Cl, Br m = 0. 1 - 20
R' = methyl, aryl (e.g. -C6H5, substituted phenyl radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-NH2, -N3, -SCN, -CH=CH2,
-NH-CH2-CH2-NH2 -N-(CH2-CH2-NH2)2 -OOC(CH3)C = CH2
-OCH2-CH(0)CH2
-NH-CO-N-CO-(CH2)5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3
-Sx-(CH2)3Si(OR)3 -SH i) Haloorganosilanes of the type (R)X2Si (CH2)m-R' X = Cl, Br
R = alkyl, such as methyl, ethyl, propyl m = 0.1 - 20 R' = methyl, aryl (e.g. -C6H5, substituted phenyl radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-NH2, -N3, -SCN, -CH=CH2,-NH-CH2-CH2-NH2,
-N-(CH2-CH2-NH2)2 -00C(CH3)C = CH2
-OCH2-CH(0)CH2
-NH-CO-N-CO-(CH2)5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3, whereby R can be methyl, ethyl, propyl, butyl -Sx- (CH2) 3Si (OR) 3, whereby R can be methyl, ethyl, propyl, butyl -SH
j) Haloorganosilanes of the type (R)2X Si(CH2)rri-R'
X = Ci;'. Br
R = .alkyl m = 0.1 - 20
R' = methyl, aryl (e.g. -CgH5, substituted phenyl .radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-NH2,, -N3, -SCN, -CH=CH2, -NH-CH2-CH2-NH2,
-N-'(CH2-CH2-NH2)2 -OOC(CH3)C = CH2
-OCH2-'CH(0)CH2
-NH-C0-N-C0-.(CH2) 5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3
-Sx-(CH2)3Si(OR)3. -SH
k) Silazanes of the type R'R2Si-N-SiR2R'
I
H
R = alkyl, vinyl, aryl R' = alkyl, vinyl, aryl
1) Cyclic polysiloxanes of the type D 3, D 4, D 5, whereby D' 3, D 4 and D 5 are understood to be cyclic polysiloxanes with 3, 4 or 5 units of the type -0-Si(CH3)2- e.g. octamethyl cyclotetrasiloxane = D 4
Figure imgf000013_0001
CH, CH.
m) Polysiloxanes or silicone oils of the type
Y-0
Figure imgf000013_0002
3) Si(CH3)2(CnH2n+1) n=l-20
R = alkyl, such as CnH2n+1, whereby n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, (CH2)n-NH2, H
R' = alkyl, such as CnH2n+1, whereby n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, (CH2)n-NH2, H
R! alkyl, such as CnH2n+1, whereby n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, (CH2)n-NH2, H
R"" = alkyl, such as CnHn+1, whereby n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, (CH2)n-NH2, H
3-Methacryloxypropyl trimethoxysilane can preferably be used.
Trimethoxyoctyl silane and/or hexamethyl disilazane can preferably used as the silanizing agent. 3-Glycidyloxypropyl trimethoxysilane can preferably be used as the silanizing agent.
The following' substances in particular can be used as silazanes:
Silazanes of the type R'R2Si-N-SiR2R'
H
R = alkyl
R' = alkyl, vinyl
as well as hexamethyl disilazane for example. Dimethyl polysiloxane can be used in particular.
The surface-modified, aerogel-type, structured silica according to the invention can be used as a flatting agent in surface coatings such as e.g. paints.
Examples
Production of the silica according to the invention
An aerogel-type structured silica with the following physico-chemical properties is used:
BET surface area m2/g: 264 pH: 6.8
Loss on drying %: 2.3
Ignition loss %: 2.4 Compacted bulk density g/1: 48
Carbon content % : 0
DBP number %: 380
This aerogel-type structured silica is placed in a mixer and optionally sprayed first with water and then with the silanizing agent with intensive mixing . On completion of spraying, post-mixing is continued for a further 15 min and conditioning then performed in a drying oven . The parameters for producing the silica according to the invention are set out in Table 1 and the physico-chemical data in Table 2 .
Table 1 : Production of the silica according to the invention
Figure imgf000015_0001
Silanizing agent : AMEO = 3-aminopropγl triethoxysilane
MEMO = 3-methacryloxypropyl trimethoxysilane
OCTMO = octyl trimethoxysilane
HMDS = hexamethyl disilazane
GLYMO = glycidyl oxypropyl trimethoxysilane
**SA = silanizing agent ***sil = silica Table, 2: Physico-chemical data for the silica according to the invention
Figure imgf000016_0001
Applicational advantages
The silicas according to the invention are tested in two paint systems1. In paint system 1 and paint system 2 the following advantages are demonstrated:
- easier and faster to incorporate
- reduced thickening action, as a result of which lower- viscosity paints are possible
- reduced thickening action, as a result of which a higher flatting agent concentration is possible .
In paint system 2 the following advantages are also established:
- improved' transparency with comparable flatting
- improved chemical resistance with comparable flatting
Paint system 1 has the following composition :
Weighing factor: 25
Figure imgf000017_0001
Laromer PO 83 F amine-modified oligoether acrylate BASF
TPGDA tripropylene glycol diacrylate BASF
Irgacure 500 photoinitiator (mixture of benzophenone Ciba and 1-hydroxycyclohexyl phenyl ketone )
Dow Corning PA 57 silicone-containing flow-control agent Dow Corning Paint system 2 has the following composition :
Weighing factor : x40
Figure imgf000018_0001
Cure in the ratio 100 : 50 with Desmodur L 75
Desmophen 800 Polyester polyol Bayer AG Desmophen 1100 Polyester polyol Bayer AG CAB 381-0, 5 Cellulose Krahn Chemie acetobutyrate
Mowilith 20 Vinyl acetate Synthomer homopolymer
Baysilone OL 17 Polyether siloxane Borchers BYK 361 Polyacrylate copolymer Byk Chemie Desmodur L 75 Aromatic Bayer AG polyisocyanate Determination of the physico-chemical properties
BET surface area
The BET surface area is determined with nitrogen in accordance with DIN 66 131.
Compacted bulk density
Determination of compacted bulk density by reference to DIN ISO 787/XI
Principles of' determining compacted bulk density The compacted bulk density (previously compacted bulk volume) equals the quotient of the mass and volume of a powder after tamping in a tamping volumeter under established conditions. According to DIN ISO 787/XI the compacted bulk density is stated in g/cm3. Due to their very low compacted bulk density, the value for oxides is stated in g/1. Drying, screening and repetition of the tamping process are omitted.
Equipment for determining compacted bulk density
Tamping volumeter
Measuring cylinder
Laboratory balance (sensitive to 0.01 g)
Method for determining compacted bulk density
200 ± 10 ml oxide are introduced into the measuring cylinder of the tamping volumeter such that no voids remain and the surface is horizontal.
The mass of the sample introduced into the cylinder is determined to an accuracy of 0.01 g. The measuring cylinder with the sample is placed in the measuring cylinder holder in the tamping volumeter and tamped 1250 times.
The volume of the tamped oxide is read off to an accuracy of 1 ml. Evaluating the compacted bulk density determination g weighed amount x 1000
Compacted bulk density (g/1) = ml volume read off pH
The pH is determined in a 4 % aqueous dispersion, in water : methanol 1:1 in the case of hydrophobic oxides.
Reagents for determining pH
Distilled or demineralized water, pH > 5.5
Methanol, reagent grade
Buffer solutions pH 7.00 pH 4.66
Equipment for determining pH
Laboratory balance, (sensitive to 0.1 g)
Beaker, 250 ml
Magnetic stirrer
Magnetic rod, length 4 cm
Combined pH electrode pH meter
Dispensette, 100 ml
Procedure for determining pH
The determination is performed by reference to DIN/ISO
787/IX:
Calibration: Before measuring the pH the meter is calibrated with the buffer solutions. If several measurements are performed successively, a single calibration is sufficient.
4 g hydrophilic oxide are placed in a 250 ml beaker with 96 g (96 ml) water using a Dispensette and, with the pH electrode immersed, stirred for five minutes with a magnetic stirrer (speed approx. 1000 rpm) .
4 g hydrophobic oxide are mixed into a paste with 4β g (61 ml) methanol in a 250 ml beaker and the suspension diluted with 48 g (48 ml) water and, with the pH electrode immersed, stirred for five minutes with a magnetic stirrer (speed approx. 1000 rpm) .
After turning off the stirrer the pH is read after a standing time of one minute. The result is expressed to one decimal place.
Loss on drying
In contrast to the weighed amount of 10 g as stated in DIN ISO 787 II, a weighed amount of 1 g is used to determine the loss on drying.
The cover is fitted before cooling. A second drying stage is not performed.
Avoiding dust formation, approx. 1 g of the sample is weighed to an accuracy of 0.1 mg into a weighing pan with a ground-glass cover, said pan having been dried at 105 °C, and dried in a drying oven for two hours at 105 °C. It is reweighed after being cooled in the desiccator over blue gel with the lid in place.
g weight loss
% loss on drying at 105 °C = x 100 g weighed amount
The result is expressed to one decimal place.
Ignition loss
Equipment for determining ignition loss
Porcelain crucible with crucible lid
Muffle furnace
Analytical balance (sensitive to 0.1 mg)
Desiccator Method for determining ignition loss
Deviating' from DIN 55 921, 0.3 - 1 g of the un-predried' substance is weighed to an. accuracy of 0.1 mg into a previously ignited porcelain crucible with crucible lid and ignited for 2 hours at 1000 °C in a muffle furnace.
Care should be taken to avoid dust formation. It has proven favorable for the weighed samples to be placed into the muffle furnace when it is still cold.
The slow heating of the furnace avoids any major air turbulence in the porcelain crucible.
Once a temperature of 1000 °C is reached, ignition is continued for a further 2' hours. The crucible is then covered with a lid and the weight loss determined over blue gel in the desiccator.
Evaluating the, ignition loss determination
Since the ignition loss relates to the sample dried for 2 h at 105 °C, the following calculation formula is obtained:
100 - LOD
Figure imgf000022_0001
100
% ignition loss = x 100
100 - LOD m0 x
100 m0 = weighed amount (g)
LOD = loss on drying (%) mi = weight of ignited sample (g)
The result is expressed to one decimal place. DBP number
Equipment for determining DBP number
Balance with top pan
Plastic beaker (250 ml)
Brabender plastograph with metering unit
Reagent
Dibutyl phthalate (tech.)
Method
1. Checking the cutoff point
-Switch on the plastograph without the metering pump. -Open the protective cover for the control panel
(under the display) -Press the "Func" key: the display alternates between the cutoff value "1000" and the alarm "Al H.A."; after 5 sec. the display returns to normal mode.
Calibration -Switch on the plastograph without the metering pump. -Switch on the kneader (press both start buttons simultaneously) . -With the "Cal" key pressed down, press the "Funk" key once; the display alternates between the current zero point and "Lo S.C.". -Press the "Cal" key again; after four seconds
(calibration) the instrument displays the current total range "10000" and "Fu S.C.". -Press the "Cal" key again; after four seconds
(calibration) the instrument displays the friction- corrected zero point "tare". -Press the "Cal" key again and wait for 5 sec. -If necessary carry out the "Cutoff point" and "Calibration process" steps once a day before measurements . 3. Measurement
12.5 g of the sample are weighed into a plastic beaker and poured into the mixing chamber. If instructed, a different weighed amount can also be used (e.g. 8, or 20 g) . The DBP metering unit is switched on. As soon as the filling process has been completed (display F) , the plastograph is ready for operation. Start the measurement by pressing the start buttons simultaneously.
- The metering unit delivers 4 ml DBP/min until the preset cutoff point (1000) is reached.
- The device switches off automatically.
- The consumption of DBP can then be read from the display of the metering unit.
Calculation
Metering unit display x 1.047 x 100
DBP (%) =
Weighed amount (g)
Always give the result with the weighed amount.

Claims

Claims :
1. Aerogel-type, structured silica, characterized in that it is surface-modified.
2. Process for the production of the aerogel-type, structured silica according to claim 1, characterized in that an aerogel-type, structured silica is prepared, optionally sprayed first with water or with acidified water and then with the silanizing agent, which can optionally be dissolved in a solvent, post-mixed and the mixture conditioned.
3. Use of the aerogel-type, structured silica according to claim 1 as a flatting agent in surface coatings.
PCT/EP2003/012382 2002-12-18 2003-11-06 Surface-modified, aerogel-type, structured silica Ceased WO2004054927A1 (en)

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