WO2009015968A1 - Surface-modified, pyrogenically produced silicic acids - Google Patents

Surface-modified, pyrogenically produced silicic acids Download PDF

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Publication number
WO2009015968A1
WO2009015968A1 PCT/EP2008/058413 EP2008058413W WO2009015968A1 WO 2009015968 A1 WO2009015968 A1 WO 2009015968A1 EP 2008058413 W EP2008058413 W EP 2008058413W WO 2009015968 A1 WO2009015968 A1 WO 2009015968A1
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Prior art keywords
modified
alkyl
pyrogenic silica
aryl
pyrogenically produced
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PCT/EP2008/058413
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German (de)
French (fr)
Inventor
Jürgen Meyer
Mario Scholz
Kai Schumacher
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Evonik Degussa Gmbh
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Publication of WO2009015968A1 publication Critical patent/WO2009015968A1/en

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • 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
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C01P2006/11—Powder tap 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
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the invention relates to surface-modified, pyrogenic silicas, a process for their preparation and their use.
  • Adhesives Besides the thickening effect, the incorporability into the liquid system is also of great importance.
  • the invention relates to a surface-modified, pyrogenically prepared silica, which is characterized in that their incorporation into liquid systems is improved without affecting the thickening effect.
  • Another object of the invention is a process for the preparation of surface-modified pyrogenic silica, which is characterized in that one has the pyrogenic silica, which is in the form of aggregates of primary particles and has a BET surface area of 90 ⁇ 15 m 2 / g , where the Aggregates have an average area of 10,000 - 20,000 nm, an average equivalent circle diameter (ECD) of 90 - 130 nm and a mean circumference of 1000 - 1400 nm surface-modified in a known manner.
  • ECD average equivalent circle diameter
  • the pyrogenic silica used as starting material is known from EP 1 681 265 A2.
  • the surface modification can be carried out by spraying the silicic acids optionally with water and then with the surface modifier.
  • the spraying can also be done in reverse order.
  • the water used may be acidified with an acid, for example hydrochloric acid, to a pH of 7 to 1. If several surface modifiers are used, they may be applied together, but separately, sequentially or as a mixture.
  • the surface modifier (s) may be dissolved in suitable solvents. After the spraying is finished, mixing can be continued for 5 to 30 minutes.
  • the mixture is then thermally treated at a temperature of 20 to 400 0 C over a period of 0.1 to 6 h.
  • the thermal treatment can be carried out under protective gas, such as nitrogen.
  • An alternative method of surface modification of the silicic acids can be carried out by treating the silicas with the surface modifier in vapor form and then thermally treating the mixture at a temperature of 50 to 800 ° C. for a period of 0.1 to 6 hours.
  • the thermal treatment can be carried out under protective gas, such as nitrogen.
  • the temperature treatment can also be carried out in several stages at different temperatures.
  • Surface modifier can be made with single, dual or ultrasonic nozzles.
  • the surface modification can be carried out continuously or batchwise in heatable mixers and dryers with sprayers.
  • Suitable devices may be, for example: plowshare mixers, plate, fluidized bed or fluid bed dryers.
  • At least one compound selected from the group consisting of the following compounds can be used.
  • R alkyl, such as, for example, methyl, ethyl, n-propyl, i-propyl, butyl
  • R ' alkyl, such as, for example, methyl, ethyl, n-propyl, i-propyl, butyl
  • R ' alkyl, such as methyl, ethyl, n-propyl, i-propyl, butyl
  • R ' methyl, aryl (for example -C 6 H 5 , substituted
  • R ' methyl, aryl (for example -C 6 H 5 , substituted
  • R ' methyl, aryl (for example -C 6 H 5 , substituted
  • R ' methyl, aryl (eg -C 6 H 5 , substituted
  • Phenyl radicals -C 4 F 9 , -OCF 2 -CHF-CF 3 , -C 6 F 13 , -O-CF 2 -CHF 2
  • R alkyl, vinyl, aryl
  • R ' alkyl, vinyl, aryl
  • Cyclic polysiloxanes of the type D 3, D 4, D 5, where D 3, D 4 and D 5 cyclic polysiloxanes with 3.4 or 5 units of the type -O-Si (CH 3 ) 2 - is understood.
  • octamethylcyclotetrasiloxane D 4
  • Phenyl and substituted phenyl radicals (CH 2 ) n -NH 2 , H
  • Phenyl and substituted phenyl radicals (CH 2 ) n -NH 2 , H
  • Phenyl and substituted phenyl radicals (CH 2 ) n -NH 2 , H
  • Phenyl and substituted phenyl radicals (CH 2 ) n -NH 2 , H
  • silanes can be used as surface modifiers:
  • Hexamethyldisilazane, dimethylpolysiloxane, octyltrimethoxysilane, octyltriethoxysilane and polydimethylsiloxane can be used with particular preference.
  • polydimethylsiloxanes In particular, one can use polydimethylsiloxanes.
  • inventive surface-modified, pyrogenically prepared silica can be used as a filler for resins.
  • Another object of the invention are resins which contain the surface-modified, pyrogenically prepared silica according to the invention.
  • the invention has the following advantages: Easier incorporation into liquid systems without compromising the thickening effect.
  • the cup is inserted into the aluminum insert of the holding device of the dissolver (Getzmann Dispermat).
  • the measured time is transferred to a school grading system (grade 1 - grade 5).
  • Grade 1 corresponds to a very good (fast) training.
  • Grade 5 corresponds to a very poor (slow) incorporation. Determination of the thickening effect in an epoxy resin
  • the cup is closed with the hole cover to prevent the silicic acid from dusting away.
  • the disc is immersed to 10mm above the bottom of the cup. It is dispersed at a speed of 3000 rpm for 3 minutes. Meanwhile, it is deaerated under vacuum.
  • the dispersed sample is transferred to a 250ml glass bottle.
  • the sample is stored for 90 minutes in a water bath at 25 ° C.
  • the spindle of the Brookfield Rheometer is immersed to the specified mark. It is measured as follows:
  • the readings are the viscosities [Pa * s] at the respective rpm. Incorporation behavior and thickening effect - results
  • inventive silica shows a significantly better incorporation behavior. That is, it is incorporated faster than the comparative silicic acid, although both the

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Surface-modified, pyrogenically produced silicic acid is manufactured by modifying, in a known manner, the surface of the pyrogenically produced silicic acid which is provided in the form of aggregates of primary particles and has a BET surface area of 90 ± 15 m2/g, the aggregates having a mean area of 10,000 to 20,000 nm2, a mean equivalent circle diameter (ECD) of 90 to 130 nm, and a mean circumference of 1,000 to 1,400 nm. Said surface-modified, pyrogenically produced silicic acid can be used as a filler for thickening liquid systems.

Description

Oberflächenmodifizierte, pyrogen hergestellte Kieselsäuren Surface-modified, pyrogenic silicas
Die Erfindung betrifft oberflächenmodifizierte, pyrogen hergestellte Kieselsäuren, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung.The invention relates to surface-modified, pyrogenic silicas, a process for their preparation and their use.
Es ist bekannt, aus pyrogen hergestellten Kieselsäuren durch Oberflächenmodifizierung oberflächenmodifizierte pyrogene Kieselsäuren herzustellen. So hergestellte Kieselsäuren finden in vielen Anwendungsbereichen Verwendung, zum Beispiel zur Rheologiesteuerung von flüssigen Systemen, in Harzen sowie für die Anwendung inIt is known to produce surface-modified fumed silicas from fumed silicas by surface modification. Silicas produced in this way are used in many fields of application, for example for the rheology control of liquid systems, in resins and for use in
Klebstoffen. Neben der Verdickungswirkung kommt dabei auch der Einarbeitbarkeit in das flüssige System eine große Bedeutung zu.Adhesives. Besides the thickening effect, the incorporability into the liquid system is also of great importance.
Die bekannten oberflächenmodifizierten pyrogenen Kieselsäuren weisen den Nachteil auf, dass ihreThe known surface-modified fumed silicas have the disadvantage that their
Einarbeitbarkeit in flüssige Systeme unbefriedigend ist.Incorporation into liquid systems is unsatisfactory.
Es bestand somit die Aufgabe oberflächenmodifizierte pyrogene Kieselsäuren herzustellen, die eine verbesserte Einarbeitbarkeit in flüssige Systeme besitzen, ohne andere wichtige Eigenschaften, wie die Verdickungswirkung zu beeinträchtigen .It was therefore the object to produce surface-modified fumed silicas which have improved incorporability into liquid systems, without affecting other important properties, such as the thickening effect.
Gegenstand der Erfindung ist eine oberflächenmodifizierte, pyrogen hergestellte Kieselsäure, welche dadurch gekennzeichnet ist, dass ihre Einarbeitbarkeit in flüssige Systeme ohne Beeinträchtigung der Verdickungswirkung verbessert ist.The invention relates to a surface-modified, pyrogenically prepared silica, which is characterized in that their incorporation into liquid systems is improved without affecting the thickening effect.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung der oberflächenmodifizierten pyrogen hergestellten Kieselsäure, welches dadurch gekennzeichnet ist, dass man die pyrogen hergestellte Kieselsäure, die in Form von Aggregaten von Primärpartikeln vorliegt und eine BET-Oberflache von 90 ± 15 m2/g besitzt, wobei die Aggregate eine mittlere Fläche von 10000 - 20000 nm , einen mittleren, äquivalenten Kreisdurchmesser (ECD = Equivalent Circle Diameter) von 90 - 130 nm und einen mittleren Umfang von 1000 - 1400 nm aufweisen, auf bekannte Weise oberflächenmodifiziert.Another object of the invention is a process for the preparation of surface-modified pyrogenic silica, which is characterized in that one has the pyrogenic silica, which is in the form of aggregates of primary particles and has a BET surface area of 90 ± 15 m 2 / g , where the Aggregates have an average area of 10,000 - 20,000 nm, an average equivalent circle diameter (ECD) of 90 - 130 nm and a mean circumference of 1000 - 1400 nm surface-modified in a known manner.
Die als Edukt eingesetzte pyrogen hergestellte Kieselsäure ist bekannt aus der EP 1 681 265 A2.The pyrogenic silica used as starting material is known from EP 1 681 265 A2.
Die Oberflächenmodifizierung kann man durchführen, indem man die Kieselsäuren gegebenfalls mit Wasser und anschließend mit dem Oberflächenmodifizierungsmittel besprüht. Die Besprühung kann auch in umgekehrter Reihenfolge erfolgen. Das eingesetzte Wasser kann mit einer Säure, zum Beispiel Salzsäure, bis zu einem pH-Wert von 7 bis 1 angesäuert sein. Falls mehrere Oberflächenmodifizierungsmittel eingesetzt werden, können diese gemeinsam, aber getrennt, nacheinander oder als Gemisch aufgebracht werden.The surface modification can be carried out by spraying the silicic acids optionally with water and then with the surface modifier. The spraying can also be done in reverse order. The water used may be acidified with an acid, for example hydrochloric acid, to a pH of 7 to 1. If several surface modifiers are used, they may be applied together, but separately, sequentially or as a mixture.
Die oder das Oberflächenmodifizierungsmittel können in geeigneten Lösungsmitteln gelöst sein. Nachdem das Sprühen beendet ist, kann noch 5 bis 30 min nachgemischt werden.The surface modifier (s) may be dissolved in suitable solvents. After the spraying is finished, mixing can be continued for 5 to 30 minutes.
Das Gemisch wird anschließend bei einer Temperatur von 20 bis 400 0C über einen Zeitraum von 0,1 bis 6 h thermisch behandelt. Die thermische Behandlung kann unter Schutzgas, wie zum Beispiel Stickstoff, erfolgen. Eine alternative Methode der Oberflächenmodifizierung der Kieselsäuren kann man durchführen, indem man die Kieselsäuren mit dem Oberflächenmodifizierungmittel in Dampfform behandelt und das Gemisch anschließend bei einer Temperatur von 50 bis 800 0C über einen Zeitraum von 0,1 bis 6 h thermisch behandelt. Die thermische Behandlung kann unter Schutzgas, wie zum Beispiel Stickstoff, erfolgen . Die Temperaturbehandlung kann auch mehrstufig bei unterschiedlichen Temperaturen erfolgen.The mixture is then thermally treated at a temperature of 20 to 400 0 C over a period of 0.1 to 6 h. The thermal treatment can be carried out under protective gas, such as nitrogen. An alternative method of surface modification of the silicic acids can be carried out by treating the silicas with the surface modifier in vapor form and then thermally treating the mixture at a temperature of 50 to 800 ° C. for a period of 0.1 to 6 hours. The thermal treatment can be carried out under protective gas, such as nitrogen. The temperature treatment can also be carried out in several stages at different temperatures.
Die Aufbringung des oder derThe application of the
Oberflächenmodifizierungsmittel kann mit Einstoff-, Zweistoff- oder Ultraschalldüsen erfolgen.Surface modifier can be made with single, dual or ultrasonic nozzles.
Die Oberflächenmodifizierung kann man in beheizbaren Mischern und Trocknern mit Sprüheinrichtungen kontinuierlich oder ansatzweise durchführen. Geeignete Vorrichtungen können zum Beispiel sein: Pflugscharmischer, Teller-, Wirbelschicht- oder Fließbetttrockner.The surface modification can be carried out continuously or batchwise in heatable mixers and dryers with sprayers. Suitable devices may be, for example: plowshare mixers, plate, fluidized bed or fluid bed dryers.
Als Oberflächenmodifizierungsmittel kann mindestens eine Verbindung aus der Gruppe der folgenden Verbindungen eingesetzt werden.As the surface modifier, at least one compound selected from the group consisting of the following compounds can be used.
a) Organosilane des Types (RO)3Si(CnH2n+1) und (RO)3Si(CnH2n-!) R = Alkyl, wie zum Beispiel Methyl-, Ethyl-, n-Propyl-, i-Propyl-, Butyl- n = 1 - 20 b) Organosilane des Types R' x (RO) ySi (CnH2n+1) unda) organosilanes of the type (RO) 3 Si (C n H 2n + 1 ) and (RO) 3 Si (C n H 2n - ! ) R = alkyl, such as, for example, methyl, ethyl, n-propyl, i-propyl-, butyl-n = 1 - 20 b) organosilanes of the type R ' x (RO) y Si (C n H 2n + 1 ) and
R1X(ROySi(CnH2n-!)R 1 X (ROySi (C n H 2n - ! )
R = Alkyl, wie zum Beispiel Methyl-, Ethyl-, n-Propyl-, i-Propyl-, Butyl-R = alkyl, such as, for example, methyl, ethyl, n-propyl, i-propyl, butyl
R' = Alkyl, wie zum Beispiel Methyl-, Ethyl-, n-Propyl-, i-Propyl-, Butyl-R '= alkyl, such as, for example, methyl, ethyl, n-propyl, i-propyl, butyl
R'=Cycloalkyl n = 1 - 20 x+y = 3 x = 1,2 y 1,2 c) Halogenorganosilane des Types X3Si (CnH2n+1) und X3Si (CnH2n-i) X = Cl, Br n = 1 - 20 d) Halogenorganosilane des Types X2 (R' ) Si (CnH2n+1) und X2 (R') Si (CnH2n-!) X = Cl, Br R' = Alkyl, wie zum Beispiel Methyl-, Ethyl-, n-Propyl-, i-Propyl-, Butyl- R'=Cycloalkyl n = 1 - 20 e) Halogenorganosilane des Types X (R' ) 2Si (CnH2n+1) und
Figure imgf000005_0001
R '= cycloalkyl n = 1 - 20 x + y = 3 x = 1.2 y 1.2 c) halogenorganosilanes of the type X 3 Si (C n H 2n + 1 ) and X 3 Si (C n H 2n -i ) X = Cl, Br n = 1 - 20 d) halogenorganosilanes of the type X 2 (R ') Si (C n H 2n + 1 ) and X 2 (R') Si (C n H 2n - ! ) X = Cl , Br R '= alkyl, such as, for example, methyl, ethyl, n-propyl, i-propyl, butyl R' = cycloalkyl n = 1-20 e) halogenorganosilanes of the type X (R ') 2 Si (C n H 2n + 1 ) and
Figure imgf000005_0001
X = Cl, BrX = Cl, Br
R' = Alkyl, wie zum Beispiel Methyl-, Ethyl-, n-Propyl- , i-Propyl-, Butyl- R'=Cycloalkyl n = 1 - 20 f) Organosilane des Types (RO) 3Si (CH2) m-R'R '= alkyl, such as methyl, ethyl, n-propyl, i-propyl, butyl R' = cycloalkyl n = 1-20 f) organosilanes of the type (RO) 3 Si (CH 2 ) m -R '
R = Alkyl, wie Methyl-, Ethyl-, Propyl- m = 0, 1 - 20R = alkyl, such as methyl, ethyl, propyl m = 0, 1-20
R' = Methyl-, Aryl (zum Beispiel -C6H5, substituierteR '= methyl, aryl (for example -C 6 H 5 , substituted
Phenylreste)phenyl)
-C4F9, OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 -C 4 F 9 , OCF 2 -CHF-CF 3 , -C 6 F 13 , -O-CF 2 -CHF 2
-NH2, -N3, -SCN, -CH=CH2, -NH-CH2-CH2-NH2, -N- (CH2-CH2-NH2) 2 -NH 2 , -N 3 , -SCN, -CH = CH 2 , -NH-CH 2 -CH 2 -NH 2 , -N- (CH 2 -CH 2 -NH 2 ) 2
-0OC(CH3)C = CH2 -OOC (CH 3 ) C = CH 2
-OCH2-CH(O)CH2 -OCH 2 -CH (O) CH 2
-NH-CO-N-CO- (CH2)s-NH-CO-N-CO- (CH 2 ) s
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3 -Sx- (CH2) 3Si (OR)3 -NH-COO-CH 3 , -NH-COO-CH 2 -CH 3 , -NH- (CH 2 ) 3 Si (OR) 3 -S x - (CH 2 ) 3 Si (OR) 3
-SHSH
-NR'R' 'R' ' ' (R' = Alkyl, Aryl; R' ' = H, Alkyl, Aryl; R' ' ' = H, Alkyl, Aryl, Benzyl, C2H4NR' ' ' ' R' ' ' ' ' mit R' ' ' ' = H, Alkyl und R' ' ' ' ' = H, Alkyl) g) Organosilane des Typs (R" ) x (RO) ySi (CH2) m-R'-NR'R '' R '''(R' = alkyl, aryl, R '' = H, alkyl, aryl, R '''= H, alkyl, aryl, benzyl, C 2 H 4 NR'''' R '''''withR''''= H, alkyl and R''''' = H, alkyl) g) organosilanes of the type (R ") x (RO) y Si (CH 2 ) m -R '
R" = Alkyl x+y = 3 = Cycloalkyl x = 1,2 Y = 1,2 m = 0, 1 bis 20R "= alkyl x + y = 3 = cycloalkyl x = 1.2 Y = 1.2 m = 0, 1 to 20
R' = Methyl-, Aryl (zum Beispiel -C6H5 , substituierteR '= methyl, aryl (for example -C 6 H 5 , substituted
Phenylreste)phenyl)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 -C 4 F 9 , -OCF 2 -CHF-CF 3 , -C 6 F 13 , -O-CF 2 -CHF 2
-NH2, -N3, -SCN, -CH=CH2, -NH-CH2-CH2-NH2, -N- (CH2-CH2-NH2) 2 -NH 2 , -N 3 , -SCN, -CH = CH 2 , -NH-CH 2 -CH 2 -NH 2 , -N- (CH 2 -CH 2 -NH 2 ) 2
-OOC (CH3)C = CH2 -OCH2-CH(O)CH2 -NH-CO-N-CO- (CH2) 5 -NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3 -OOC (CH 3 ) C = CH 2 -OCH 2 -CH (O) CH 2 -NH-CO-N-CO- (CH 2 ) 5 -NH-COO-CH 3 , -NH-COO-CH 2 -CH 3 , -NH- (CH 2 ) 3 Si (OR) 3
-Sx- (CH2) 3Si (OR)3 -S x - (CH 2 ) 3 Si (OR) 3
-SHSH
- NR'R' 'R' ' ' (R' = Alkyl, Aryl; R' ' = H,NR'R '' R '' '(R' = alkyl, aryl, R '' = H,
Alkyl, Aryl; R' ' ' = H, Alkyl, Aryl, Benzyl, C2H4NR' ' ' ' R' ' ' ' ' mit R' ' ' ' = H, Alkyl und R' ' ' ' ' = H, Alkyl)Alkyl, aryl; R '"= H, alkyl, aryl, benzyl, C 2 H 4 NR""R''''' with R '''' = H, alkyl and R '''''= H, alkyl)
h) Halogenorganosilane des Types X3Si (CH2) m-R' X = Cl, Br m = 0,1 - 20h) halogenorganosilanes of the type X 3 Si (CH 2 ) m -R'X = Cl, Br m = 0.1-20
R' = Methyl-, Aryl (zum Beispiel -C6H5, substituierteR '= methyl, aryl (for example -C 6 H 5 , substituted
Phenylreste)phenyl)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 -NH2, -N3, -SCN, -CH=CH2,-C 4 F 9 , -OCF 2 -CHF-CF 3 , -C 6 F 13 , -O-CF 2 -CHF 2 -NH 2 , -N 3 , -SCN, -CH = CH 2 ,
-NH-CH2-CH2-NH2 -N- (CH2-CH2-NH2) 2 -0OC(CH3)C = CH2 -OCH2-CH(O)CH2 -NH-CO-N-CO- (CH2) 5 -NH-CH 2 -CH 2 -NH 2 -N- (CH 2 -CH 2 -NH 2 ) 2 -OOC (CH 3 ) C =CH 2 -OCH 2 -CH (O) CH 2 -NH-CO- N-CO- (CH 2 ) 5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3 -NH-COO-CH 3 , -NH-COO-CH 2 -CH 3 , -NH- (CH 2 ) 3 Si (OR) 3
-Sx- (CH2) 3Si(OR)3 -SH i) Halogenorganosilane des Types (R) X2Si (CH2) m-R' X = Cl, Br-S x - (CH 2 ) 3 Si (OR) 3 -SH i) Halogenorganosilanes of the type (R) X 2 Si (CH 2 ) m -R 'X = Cl, Br
R = Alkyl, wie Methyl,- Ethyl-, Propyl- m = 0,1 - 20R = alkyl, such as methyl, ethyl, propyl, m = 0.1-20
R' = Methyl-, Aryl (z.B. -C6H5, substituierteR '= methyl, aryl (eg -C 6 H 5 , substituted
Phenylreste) -C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 Phenyl radicals) -C 4 F 9 , -OCF 2 -CHF-CF 3 , -C 6 F 13 , -O-CF 2 -CHF 2
-NH2, -N3, -SCN, -CH=CH2, -NH-CH2-CH2-NH2, -N- (CH2-CH2-NH2) 2 -0OC(CH3)C = CH2 -OCH2-CH(O)CH2 -NH-CO-N-CO- (CH2) 5 -NH 2 , -N 3 , -SCN, -CH = CH 2 , -NH-CH 2 -CH 2 -NH 2 , -N- (CH 2 -CH 2 -NH 2 ) 2 -OOC (CH 3 ) C = CH 2 -OCH 2 -CH (O) CH 2 -NH-CO-N-CO- (CH 2 ) 5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR)3, wobei R = Methyl-, Ethyl-, Propyl-, Butyl- sein kann -Sx- (CH2) 3Si (OR) 3, wobei R = Methyl-, Ethyl-, Propyl-, Butyl- sein kann-NH-COO-CH 3 , -NH-COO-CH 2 -CH 3 , -NH- (CH 2 ) 3 Si (OR) 3 , where R = methyl, ethyl, propyl, butyl- S x - (CH 2 ) 3 Si (OR) 3 , where R = methyl, ethyl, propyl, butyl
-SH j) Halogenorganosilane des Types (R)2X Si (CH2) m-R' X = Cl, Br R = Alkyl m = 0,1 - 20 R' = Methyl-, Aryl (z.B. -C6H5, substituierteSH j) Halogenorganosilanes of the type (R) 2 X Si (CH 2 ) m -R'X = Cl, Br R = alkyl m = 0.1-20 R '= methyl, aryl (eg -C 6 H 5 , substituted
Phenylreste)phenyl)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 -C 4 F 9 , -OCF 2 -CHF-CF 3 , -C 6 F 13 , -O-CF 2 -CHF 2
-NH2, -N3, -SCN, -CH=CH2, -NH-CH2-CH2-NH2,-NH 2 , -N 3 , -SCN, -CH = CH 2 , -NH-CH 2 -CH 2 -NH 2 ,
-N- (CH2-CH2-NH2) 2 -OOC (CH3)C = CH2 -N- (CH 2 -CH 2 -NH 2 ) 2 -OOC (CH 3 ) C = CH 2
-OCH2-CH(O)CH2 -OCH 2 -CH (O) CH 2
-NH-CO-N-CO- (CH2) 5 -NH-CO-N-CO- (CH 2 ) 5
-NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3 -NH-COO-CH 3 , -NH-COO-CH 2 -CH 3 , -NH- (CH 2 ) 3 Si (OR) 3
-Sx- (CH2) 3Si (OR)3 -SH k) Silazane des Types R1R2Si-N-SiR2R'-S x - (CH 2 ) 3 Si (OR) 3 -SH k) silazanes of the type R 1 R 2 Si-N-SiR 2 R '
HH
R = Alkyl, Vinyl, Aryl R' = Alkyl, Vinyl, ArylR = alkyl, vinyl, aryl R '= alkyl, vinyl, aryl
1) Cyclische Polysiloxane des Types D 3, D 4, D 5, wobei unter D 3, D 4 und D 5 cyclische Polysiloxane mit 3,4 oder 5 Einheiten des Typs -O-Si (CH3) 2- verstanden wird. Z.B. Octamethylcyclotetrasiloxan = D 41) Cyclic polysiloxanes of the type D 3, D 4, D 5, where D 3, D 4 and D 5 cyclic polysiloxanes with 3.4 or 5 units of the type -O-Si (CH 3 ) 2 - is understood. For example, octamethylcyclotetrasiloxane = D 4
Figure imgf000007_0001
(m) Polysiloxane beziehungsweise Silikonöle des Types
Figure imgf000007_0001
(m) polysiloxanes or silicone oils of the type
Y-O-Y-O-
Figure imgf000008_0001
3) Si (CH3) 2 (CnH2n+1) n=l-20
Figure imgf000008_0001
3 ) Si (CH 3 ) 2 (C n H 2n + 1 ) n = 1-20
R = Alkyl, wie CnH2n+I, wobei n = 1 bis 20 ist, Aryl, wieR = alkyl, such as C n H 2n + I , where n = 1 to 20, aryl, as
Phenyl - und substituierte Phenylreste, (CH2) n-NH2, HPhenyl and substituted phenyl radicals, (CH 2 ) n -NH 2 , H
R' = Alkyl, wie CnH2n+I, wobei n = 1 bis 20 ist, Aryl, wieR '= alkyl, such as C n H 2n + I , where n = 1 to 20, aryl, as
Phenyl - und substituierte Phenylreste, (CH2) n-NH2, HPhenyl and substituted phenyl radicals, (CH 2 ) n -NH 2 , H
R" = Alkyl, wie CnH2n+1, wobei n = 1 bis 20 ist, Aryl, wieR "= alkyl, such as C n H 2n + 1 , where n = 1 to 20, aryl, as
Phenyl - und substituierte Phenylreste, (CH2) n-NH2, HPhenyl and substituted phenyl radicals, (CH 2 ) n -NH 2 , H
R'" = Alkyl, wie CnH2n+1, wobei n = 1 bis 20 ist, Aryl, wieR '"= alkyl, such as C n H 2n + 1 , where n = 1 to 20, aryl, as
Phenyl - und substituierte Phenylreste, (CH2) n-NH2, HPhenyl and substituted phenyl radicals, (CH 2 ) n -NH 2 , H
Bevorzugt können als Oberflächenmodifizierungsmittel folgende Silane eingesetzt werden:The following silanes can be used as surface modifiers:
Octyltrimethoxysilan, Octyltriethoxysilan,Octyltrimethoxysilane, octyltriethoxysilane,
Hexamethyldisilazan, 3-Methacryloxypropyl-trimethoxysilan,Hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane,
3-Methacryloxypropyltriethoxysilan,3-methacryloxypropyltriethoxysilane,
Hexadecyltrimethoxysilan, Hexadecyltriethoxysilan, Dimethylpolysiloxan, Glycidyloxypropyltrimethoxysilan, Glycidyloxypropyltriethoxysilan,Hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dimethylpolysiloxane, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane,
Nonafluorohexyltrimethoxysilan, Tridecaflourooctyltri- methoxysilan, Tridecaflourooctyltriethoxysilan, Aminopropyl-triethoxysilan, Hexamethyldisilazan sowie Polydimethylsiloxan .Nonafluorohexyltrimethoxysilane, Tridecaflourooctyltri- methoxysilane, Tridecaflourooctyltriethoxysilane, aminopropyltriethoxysilane, hexamethyldisilazane and polydimethylsiloxane.
Besonders bevorzugt können Hexamethyldisilazan, Dimethylpolysiloxan, Octyltrimethoxysilan, Octyltriethoxysilan sowie Polydimethylsiloxan eingesetzt werden .Hexamethyldisilazane, dimethylpolysiloxane, octyltrimethoxysilane, octyltriethoxysilane and polydimethylsiloxane can be used with particular preference.
Insbesondere kann man Polydimethylsiloxane einsetzen. Die erfindungsgemaße oberflachenmodifizierte, pyrogen hergestellte Kieselsaure kann als Füllstoff für Harze verwendet werden.In particular, one can use polydimethylsiloxanes. The inventive surface-modified, pyrogenically prepared silica can be used as a filler for resins.
Ein weiterer Gegenstand der Erfindung sind Harze, die die erfindungsgemaße oberflachenmodifizierte, pyrogen hergestellte Kieselsaure enthalten.Another object of the invention are resins which contain the surface-modified, pyrogenically prepared silica according to the invention.
Die Erfindung weist die folgenden Vorteile auf: Leichtere Einarbeitbarkeit in flussige Systeme, ohne die Verdickungswirkung zu beeinträchtigen.The invention has the following advantages: Easier incorporation into liquid systems without compromising the thickening effect.
BeispieleExamples
Herstellung des VergleichskieselsaureProduction of the comparison silicic acid
2 kg AEROSIL® 90 wurden in einem Mischer vorgelegt und unter Mischen mit 0,3 kg Rhodorsil Ol 47 V 100 (Polydimethylsiloxan) mittels einer Zweistoffduse besprüht. Nach beendetem Sprühen wurde noch 15 Minuten nachgemischt. Das Reaktionsgemisch wurde anschließend unter einer Stickstoffatmosphare getempert.2 kg of AEROSIL® 90 were introduced into a mixer and sprayed with a mixture of 0.3 kg Rhodorsil Ol 47 V 100 (polydimethylsiloxane) by means of a two-component nozzle. After spraying was continued for 15 minutes. The reaction mixture was then annealed under a nitrogen atmosphere.
Herstellung der erfindungsgemaßen Kieselsauren - BeispielPreparation of the Silicas According to the Invention - Example
2 kg der Kieselsaure 1 (Tabelle 4 aus EP 1681265) wurden in einem Mischer vorgelegt und unter Mischen mit 0,3 kg Rhodorsil Ol 47 V 100 (Polydimethylsiloxan) mittels einer Zweistoffduse besprüht. Nach beendetem Sprühen wurde noch 15 Minuten nachgemischt, und das Reaktionsgemisch anschließend unter einer Stickstoffatmosphare getempert. Physikalisch-chemische Daten2 kg of silica 1 (Table 4 from EP 1681265) were placed in a mixer and sprayed by mixing with 0.3 kg of Rhodorsil Ol 47 V 100 (polydimethylsiloxane) by means of a Zweistoffduse. After spraying was continued for 15 minutes, and the reaction mixture then annealed under a nitrogen atmosphere. Physicochemical data
Figure imgf000010_0001
Figure imgf000010_0001
Ermittlung des EinarbeitungsverhaltensDetermination of the training behavior
Zur Ermittlung des Einarbeitungsverhaltens wurde die Zeit gemessen, die notwendig ist, bis die Kieselsaure in einem Harz homogenisiert ist.To determine the incorporation behavior, the time was measured, which is necessary until the silica is homogenized in a resin.
Dazu werden in einem 350 ml Becher 100 g Palatal A 410 eingewogen und im Wasserbad auf 25°C temperiert.For this purpose, 100 g of Palatal A 410 are weighed into a 350 ml beaker and heated to 25 ° C. in a water bath.
Der Becher wird in den Aluminiumeinsatz der Haltevorrichtung des Dissolvers (Getzmann Dispermat) eingesetzt .The cup is inserted into the aluminum insert of the holding device of the dissolver (Getzmann Dispermat).
Der Ruhrer (Scheibendurchmesser 30 mm) wird auf Solltiefe t= 10mm über Becherboden eingetaucht und mit der Geschwindigkeit n=500 min"1 eingeschaltet .The Ruhrer (disc diameter 30 mm) is immersed above the cup base at a t = 10mm depth and switched on at the speed n = 500 min "1 .
3 g Kieselsaure werden gleichmaßig auf die Harzoberflache gegeben und die Stoppuhr gestartet.3 g of silicic acid are added evenly to the resin surface and the stopwatch is started.
Es wird die Zeit gemessen, die notwendig ist, bis die Kieselsaure homogenisiert ist.It measures the time necessary for the silicic acid to homogenize.
Die gemessene Zeit wird in ein Schulnotensystem (Note 1 - Note 5) übertragen . Note 1 entspricht einer sehr guten (schnellen) Einarbeitung. Note 5 entspricht einer sehr schlechten (langsamen) Einarbeitung. Ermittlung der Verdickungswirkung in einem EpoxidharzThe measured time is transferred to a school grading system (grade 1 - grade 5). Grade 1 corresponds to a very good (fast) training. Grade 5 corresponds to a very poor (slow) incorporation. Determination of the thickening effect in an epoxy resin
201,92g (92,15%) Renlam Ml und 8,08g (3,85%) Kieselsäure werden in einem 350 ml PE-Becher eingewogen.201.92 g (92.15%) of Renlam Ml and 8.08 g (3.85%) of silica are weighed in a 350 ml PE beaker.
Die Dissolverscheibe (Scheibendurchmesser : d = 50mm) wird bis zur Bechermitte eingetaucht und die Probe bei 1000 Upm homogenisiert .The dissolver disc (disc diameter: d = 50 mm) is immersed to the center of the cup and the sample homogenized at 1000 rpm.
Dabei ist der Becher mit dem Lochdeckel verschlossen, um ein Wegstauben der Kieselsäure zu verhindern.The cup is closed with the hole cover to prevent the silicic acid from dusting away.
Sobald die Kieselsäure vollständig eingearbeitet ist, wird die Scheibe bis 10mm über Becherboden eingetaucht. Es wird bei einer Geschwindigkeit von 3000 Upm 3 Minuten lang dispergiert. Währenddessen wird unter Vakuum entlüftet.Once the silica is fully incorporated, the disc is immersed to 10mm above the bottom of the cup. It is dispersed at a speed of 3000 rpm for 3 minutes. Meanwhile, it is deaerated under vacuum.
Die dispergierte Probe wird in eine 250ml Glasflasche umgefüllt . Es erfolgt eine Lagerung der Probe von 90 Minuten im Wasserbad bei 25°C.The dispersed sample is transferred to a 250ml glass bottle. The sample is stored for 90 minutes in a water bath at 25 ° C.
Nach 90 Minuten wird die Probe 1 Minute lang mit dem Spatel aufgerührt. Anschließend wird mittels Brookfield DV III die Viskosität der Probe bestimmt.After 90 minutes the sample is stirred for 1 minute with the spatula. Subsequently, the viscosity of the sample is determined by means of Brookfield DV III.
Dazu wird die Spindel des Brookfield Rheometers bis zur vorgegeben Markierung eingetaucht. Es wird wie folgt gemessen :For this purpose, the spindle of the Brookfield Rheometer is immersed to the specified mark. It is measured as follows:
5 Upm - Wert ablesen nach 60 Sekunden5 rpm - Read value after 60 seconds
50 Upm - Wert ablesen nach 30 Sekunden.50 rpm - Read value after 30 seconds.
Die abgelesenen Werte sind die Viskositäten [Pa*s] bei den jeweiligen Upm. Einarbeitungsverhalten und Verdickungswirkung - ErgebnisseThe readings are the viscosities [Pa * s] at the respective rpm. Incorporation behavior and thickening effect - results
Figure imgf000012_0001
Figure imgf000012_0001
Es ist deutlich zu erkennen, dass die erfindungsgemaße Kieselsaure ein deutlich besseres Einarbeitungsverhalten zeigt. Das heißt, sie wird schneller eingearbeitet als die Vergleichskieselsaure, obwohl sowohl dieIt can be clearly seen that the inventive silica shows a significantly better incorporation behavior. That is, it is incorporated faster than the comparative silicic acid, although both the
Verdickungswirkung als auch die sonstigen physikalischchemischen Daten vergleichbar sind. Thickening effect and the other physico-chemical data are comparable.

Claims

Patentansprüche : Claims:
1. Oberflächenmodifizierte, pyrogen hergestellte Kieselsäure, dadurch gekennzeichnet, dass sie eine verbesserte Einarbeitbarkeit in flüssige Systeme besitzt.1. Surface-modified, pyrogenic silica, characterized in that it has an improved incorporation into liquid systems.
2. Verfahren zur Herstellung der oberflächenmodifizierten, pyrogen hergestellten Kieselsäure gemäß Anspruch 1, dadurch gekennzeichnet, dass man die pyrogen hergestellte Kieselsäure, die in Form von Aggregaten von Primärpartikeln vorliegt und eine BET-Oberflache von 90 ± 15 m2/g besitzt, wobei die Aggregate eine mittlere Fläche von 10000 - 20000 nm2, einen mittleren, äquivalenten Kreisdurchmesser (ECD = Equivalent Circle Diameter) von 90 - 130 nm und einen mittleren Umfang von 1000 - 1400 nm aufweisen, auf bekannte Weise oberflächenmodifiziert.2. A process for the preparation of surface-modified, pyrogenic silica according to claim 1, characterized in that one has the pyrogenic silica, which is in the form of aggregates of primary particles and has a BET surface area of 90 ± 15 m 2 / g, wherein the Aggregates have an average area of 10,000 - 20,000 nm 2 , a mean equivalent circle diameter (ECD) of 90 - 130 nm and a mean circumference of 1000 - 1400 nm surface-modified in a known manner.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass man die Kieselsäuren gegebenenfalls mit Wasser und anschließend mit dem Oberflächenmodifizierungsmittel besprüht.3. The method according to claim 2, characterized in that optionally spraying the silicas with water and then with the surface modifier.
4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass man die Kieselsäuren mit dem4. The method according to claim 2, characterized in that the silicas with the
Oberflächenmodifizierungsmittel in Dampfform behandelt und das Gemisch anschließend bei einer Temperatur von 50 bis 800 0C über einen Zeitraum von 0,1 bis 6 h thermisch behandelt.Treated surface modifier in vapor form and then the mixture thermally treated at a temperature of 50 to 800 0 C over a period of 0.1 to 6 h.
5. Verwendung der oberflächenmodifizierten, pyrogen hergestellten Kieselsäure zur Verdickung von flüssigen Systemen .5. Use of surface-modified, pyrogenic silica for thickening liquid systems.
6. Verwendung der oberflächenmodifizierten, pyrogen hergestellten Kieselsäure zur Verdickung von Harzen. 6. Use of the surface-modified, pyrogenic silica to thicken resins.
PCT/EP2008/058413 2007-07-30 2008-07-01 Surface-modified, pyrogenically produced silicic acids WO2009015968A1 (en)

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