Method of Preparing Hydrophobic Silica Directly

(19) TZZ_Z¥_T

(11) EP 1 807 347 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C01B 33/12 (2006.01) C09C 1/30 (2006.01) 22.01.2014 Bulletin 2014/04 G03G 9/09 (2006.01)

(21) Application number: 05813927.0 (86) International application number: PCT/US2005/037728 (22) Date of filing: 20.10.2005 (87) International publication number: WO 2006/045012 (27.04.2006 Gazette 2006/17)

(54) METHOD OF PREPARING HYDROPHOBIC SILICA DIRECTLY FROM AN AQUEOUS COLLOIDAL SILICA DISPERSION VERFAHREN ZUR HERTSTELLUNG VON HYDROPHOBEN SILICIUMDIOXID DIREKT AUS EINER WÄSSRIGEN DISPERSION VON KOLLOIDALEM SILICIUMDIOXID PROCEDE DE PREPARATION DE SILICE HYDROPHOBE DIRECTEMENT A PARTIR D’UNE DISPERSION DE SILICE COLLOIDALE AQUEUSE

(84) Designated Contracting States: (74) Representative: Grünecker, Kinkeldey, AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Stockmair & Schwanhäusser HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI Leopoldstrasse 4 SK TR 80802 München (DE)

(30) Priority: 20.10.2004 US 620589 P (56) References cited: EP-A1- 0 475 132 EP-A1- 0 609 870 (43) Date of publication of application: EP-A2- 0 928 818 WO-A1-2004/035473 18.07.2007 Bulletin 2007/29 US-A- 3 850 971 US-A- 4 344 800 US-A- 5 226 930 US-A- 5 226 930 (73) Proprietor: CABOT CORPORATION US-A- 5 900 315 US-A- 5 989 768 Boston, Massachusetts 02210-2019 (US) US-A- 6 051 672

(72) Inventor: ADAMS, Curtis, E. Watertown, Massachusetts 02472 (US)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 807 347 B1

Printed by Jouve, 75001 PARIS (FR) EP 1 807 347 B1

Description

FIELD OF THE INVENTION

5 [0001] This invention pertains to a method of preparing hydrophobic silica particles, as well as to methods of preparing compositions comprising hydrophobic silica particles.

BACKGROUND OF THE INVENTION

10 [0002] Hydrophobic silica particles possess physical properties that are useful in a number of applications requiring a high degree of dispersibility, including use in toner compositions, as antiblocking agents, as adhesion modifiers, and as polymer fillers. Untreated silica particles are hydrophilic due to the presence of silanol groups (Si- OH) on the surface of the untreated silica particles. By treating hydrophilic silica particles, the hydrophilic nature of the silica particles can be reduced, thereby imparting varying degrees of hydrophobicity to the particles. 15 [0003] Many different methods are known for treating the surface of silica particles. Some methods involve coating the particles with a silicone-type composition or other hydrophobic composition. Other methods involve reacting the surface silanol groups with a treating agent to effectively replace the hydrophilic silanol groups with other, hydrophobic, chemical groups. However, many treating agents are difficult to disperse in water, or tend to hydrolyze in water prior to replacing the surface silanol groups. Thus, the direct treatment of an aqueous dispersion of silica is often inefficient or 20 difficult to achieve. As a result, these types of treatments are often acid-catalyzed reactions as disclosed in EP-A-928 818, or require the use of organic solvents. According to WO 2004/035473 A1, surface treatment is conducted with alkoxysilanes or epoxysilanes. [0004] Thus, a need still exists for simple and economical methods of preparing hydrophobic silica particles, especially methods that can be used to prepare hydrophobic silica directly from an aqueous dispersion of silica. The present 25 invention provides such a method. These and other advantages of the invention will be apparent from the description of the invention provided herein.

BRIEF SUMMARY OF THE INVENTION

30 [0005] The invention provides a method of preparing hydrophobic silica particles comprising (a) providing an aqueous colloidal silica dispersion comprising about 5-70 wt. % of hydrophilic silica particles, wherein the hydrophilic silica particles have an average overall particle size of about 10-1000 nm, (b) combining the dispersion with about 3-75mmole/m 2 (based on the BET surface area of the hydrophilic silica particles) of a silyl amine treating agent to provide a reaction mixture, wherein the reaction mixture has a pH of about 7 or more and comprises no more than about 20 wt.% of an 35 organic solvent, and (c) drying the dispersion to provide hydrophobic silica particles. The invention further provides a method of preparing a toner composition and a method of preparing a polymer composition, which methods comprise (a) preparing hydrophobic silica particles in accordance with the method of the invention and (b) combining the hydrophobic silica particles with toner particles or a polymer, as appropriate.

40 DETAILED DESCRIPTION OF THE INVENTION

[0006] The invention provides a method of preparing hydrophobic silica particles comprising (a) providing an aqueous colloidal silica dispersion comprising about 5-70 wt. % of hydrophilic silica particles, wherein the hydrophilic silica particles have an average overall particle size of about 10-1000 nm, (b) combining the dispersion with about 3-75mmole/m 2 45 (based on the BET surface area of the hydrophilic silica particles) of a silyl amine treating agent to provide a reaction mixture; wherein the reaction mixture has a pH of about 7 or more and comprises no more than about 50 wt.% of an organic solvent, and (c) drying the dispersion to provide hydrophobic silica particles. [0007] The term "silyl amine treating agent" as used in the context of the present invention refers to an organosilicon compound (or a mixture of organosilicon compounds) comprising a Si-N bond that is capable of reacting with silanol 50 groups on the surface of the silica particles. Any suitable silyl amine treating agent can be used. The silyl amine treating agentcan be water- miscibleor water- immiscible. Suitable compounds include those of the general formula (R 3Si)nNR’(3-n) wherein n=1-3; each R is independently selected from the group consisting of hydrogen, a 1C-C18 alkyl or branched alkyl, a C3-C18 haloalkyl, vinyl, a C 6-C14 aromatic group, a C 2-C18 alkenyl group, a C3-C18 epoxyalkyl group, and linear or branched CmH2mX, wherein m is 1-18; each R’ is independently hydrogen, C1-C18 alkyl or branched alkyl, or when 55 n=1, a C2-C6 cyclic alkylene; X is NR"2, SH, OH, OC(O)CR"=CR"2, CO2R", or CN; and wherein R" is independently hydrogen, a C 1-C18 alkyl or branched alkyl, a C 2-C18 unsaturated group, a C 1-C18 acyl or C 3-C18 unsaturated acyl group, a C2-C6 cyclic alkylene or a C6-C18 aromatic group. The treating agent may also be a bisaminodisilane or a disilane of the general formula R’ 2N-SiR2-(Z-SiR2)p-NR’2 where Z is C 1-C18 linear or branched alkylene, O, NR’ or S and p is 0-100.

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Preferably, each R’ is H or CH3. It also is preferred that each R is a C1-C18 alkyl or branched alkyl. The silyl amine treating agent can comprise one or more of the above organosilicon compounds. Preferred silyl amine treating agents include but are not limited to vinyldimethylsilylamine, octyldimethylsilylamine, phenyldiinethylsilylamine, bis(dimethyl- aminodimethylsilyl)-ethane, hexamethyldisilazane, bis(trifluoropropyl)tetramethyl-disilazane (F-HMDZ), and mixtures 5 thereof. [0008] The silyl amine treating agent also can comprise, in addition to or instead of the above compounds, one or more cyclic silazanes having the general formula

wherein R1 and R2 are independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryl, and aryloxy; R3 is selected from the group consisting of hydrogen, (CH2)nCH3, wherein n is an integer between 0 and 3, C 20 (O)(CH2)nCH3, wherein n is an integer between 0 and 3, C (O)NH2, C(O)NH(CH2)nCH3, wherein n is an integer between 0 and 3, and C(O)N[(CH2)nCH3](CH2)mCH3, wherein n and m are integers between 0 and 3; and R 4 is [(CH2)a(CHX)b, (CYZ)c], wherein X, Y and Z are independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryl, and aryloxy, and a, b, and c are integers of 0 to 6 satisfying the condition that (a+b+c) equals an integer of 2 to 6. Suitable cyclic silazanes, and methods of preparing cyclic silazanes, are described in U.S. Patent 5,989,768. 25 [0009] Without wishing to be bound by any particular theory, it is believed that the silylating agent reacts with the silanol groups on the surface of the silica particles according to the following general reaction:

Si-OH + (R3Si)nNR’(3-n) → Si-O-SiR3 + (R3Si)(n-1)NHR’(3-n)

30 If n is greater than 1, the silyl amine treating agent is capable of transferring more than one silyl group per molecule of treating agent. [0010] The amount of silyl amine treating agent used in the inventive method is based on the BET surface area of the silica particles used. The amount of the silyl amine treating agent is, therefore, expressed in terms of mmole of treating agent per square meter (m2) of surface area of the hydrophilic silica particles used (based on the BET surface area of 35 the silica particles), which is abbreviated for the purposes of this invention as "mmole/m2." According to the method of the invention, about 3 mmole/m2 or more (e.g., about 5 mmole/m2 or more) of the silyl amine treating agent should be used. However, more of the treating agent can be used to ensure more complete contact and treatment of the silica particles with the treating agent. Thus, about 9 mmole/m2 or more (e.g., about 12 mmole/m2 or more) or even about 30 mmole/m2 or more (e.g., about 36 mmole/m2 or more) of the treating agent can be used. Although there is no theoretical 40 limit on the amount of treating agent used, it is advisable to limit the amount of the treating agent in order to reduce the amount of organic impurities present in the treated silica particles, and to avoid costly waste of the treating agent. Thus, the amount of treating agent used will typically be about 75m mole/m2 or less (e.g., about 50 mmole/m2 or less), such as about 36 mmole/m2 or less (e.g., about 20 mmole/m2 or less), or even about 9 mmole/m2 or less (e.g., about 7 mmole/m2 or less). Preferably, the amount of silyl amine treating agent used is within the range of about 3-75 mmole/m2 (e.g., about 45 3-36 mmole/m2), such as about 6-36 mmole/m2 (e.g., about 6-18 mmole/m2 or about 9-18 mmole/m2). The concentration of silica in the dispersion also plays a role in the amount of treating agent needed. Lower concentrations call for larger amounts of treating agent, within the bounds described above. [0011] The hydrophobicity of the silica particles prepared by the method of the invention depends, at least in part, upon the nature of the silyl amine treating agent used (e.g., the type of organosilicon functional groups provided by the 50 silyl amine treating agent) and the degree of silylation of the surface silanol groups (e.g., the percentage of silanol groups that have reacted with the silyl amine treating agent). For example, treating agents comprising larger alkyl groups with more carbon atoms can provide a greater hydrophobic effect than smaller alkyl groups with fewer carbon atoms. Also, the degree of hydrophobicity of the silica particles increases with an increasing degree of silylation (i.e., an increasing percentage of silylated silanol groups). The extent to which the surface silanol groups are silylated depends, at least in 55 part, on the type and amount of silyl amine treating agent used, the reaction time, the reaction temperature, and the reactivity of the particular silyl amine treating agent used. Due to steric crowding by the organosilicon functional group attached by the treating agent, not all of the surface silanol groups are available to react with a treating agent molecule. For example, when the organosilicon group is a trimethylsilyl group, the steric limit of available surface silanol groups

3 EP 1 807 347 B1

is approximately 2.7 silanol groups per square nanometer of silica surface area (e.g., about 2.7 groups/nm2 or about 4.5 mequiv/m2). Hydrophobic silica particles prepared by the method of the invention preferably, but not necessarily, have a majority (e.g., about 50% or more, about 75% or more, or even about 85% or more), or substantially all (e.g., about 95% or more or even 99% or more) of the available silica surface silanol groups silylated. However, the preparation 5 of hydrophobic silica particles having less than a majority (e.g., about 25% or more, or 35% or more) of the available silica surface silanol groups silylated also is contemplated. [0012] The carbon content of the hydrophobic silica particles also can be used as an indicator of the level of treatment of the hydrophobic silica particles and, thus, as an indicator of the degree of hydrophobicity. Carbon content of the treated particles can be determined using commercially available carbon analyzers. The hydrophobic silica particles 10 prepared in accordance with the invention desirably have a carbon content, after refluxing and extraction in a suitable washing solvent (e.g., acetone) for 30 minutes, of about 0.01 % or more per square meter of silica surface area (%/m 2), preferably about 0.013%/m2 or more, or even about 0.016%/m 2 or more (e.g., about 0.02%/m2 or more). [0013] The aqueous colloidal silica dispersion can comprise any suitable type of silica particles, provided that the silica particles have an average overall particle size of about 10-1000 nm. The term "overall particle size" as used herein refers 15 to the size of an independent particle when dispersed in an aqueous dispersing medium (e.g., water). The overall particle size is separate and distinct from the primary particle size, the aggregate particle size, and the agglomerate particle size. Thus, the overall particle size of a given silica particle might be the same or different from its primary particle size, aggregate particle size, or agglomerate particle size. The average overall particle size, as defined herein, is the average overall particle size by volume as measured using dynamic light scattering (DLS). DLS can be performed using com- 20 mercially available equipment (e.g., Microtrac® UPA 150 manufactured by Leeds and Northrup Co.). The silica particles can have an average overall particle size of about 20-800 nm (about 30-700 nm), such as about 40-600 nm (about 50-500 nm), or even about 60-400 nm (e.g., about 70-300 nm). Preferably, the silica particles have an average overall particle size of about 100 nm or more, such as about 100-350 nm (e.g., about 120-300 nm). [0014] Suitable silica particles include wet- process type silica particles (e.g., condensation- polymerized silica particles 25 suchas silica gels andsilica sols) made from any starting material including, butnot limited to, chlorosilanes,alkoxysilane s, and sodium silicate. The colloidal silica dispersion also can comprise silica fume, mineral silica, or silica of a biological origin (e.g., diatomite), as well as fumed or pyrogenic silica, which is typically produced by the vapor phase hydrolysis of a silica precursor, such as silicon tetrachloride, dichlorodimethylsilane, or octamethyl- cyclotetrasiloxane, ina hydrogen/ oxygen flame (or as the by- product of such a process). In this process, submicron sized molten spheres of silica, known 30 as primary particles, are formed. These particles collide and fuse to form three dimensional, branched, chain-like aggregates that are typically less than 1000 nm in spherical diameter. The aggregates can become loosely associated with one another to form agglomerates, which can easily exceed 1000 nm in spherical diameter. If dispersed with sufficient force (e.g., using high-shear mixers) the agglomerates can be broken down into aggregate particles. [0015] The silica particles can have any suitable surface area. Fumed or pyrogenic silicas typically have surface areas 35 of about 35-400 m2/g, such as about 50-200 m 2/g. Wet-process silicas generally have lower surface areas. Preferably, the silica particles have a surface area of less than about 50 m2/g, and more preferably less than about 35 m2/g. The surface area of the silica particles can be measured by any suitable method known in the art. Typically, the surface area of the silica particles is determined by the method of S. Brunauer, P.H. Emmet, and I. Teller, J. Am. Chemical Society, 60, 309 (1938), which is commonly referred to as the BET method. 40 [0016] The term "colloidal dispersion" as used herein refers to a dispersion of colloidal particles (e.g., particles having an average overall particle size of about 1000 nm or less). The colloidal stability of such a dispersion prevents any substantial portion of the particles from irreversibly agglomerating. Agglomeration of particles can be detected by an increase in the average overall particle size. In this regard, the colloidal dispersion can be stabilized or non- stabilized. The term "stabilized" as used herein refers to the addition of a stabilizing ingredient, for example, an acid, base, or other 45 stabilizing agent known in the art in an amount sufficient to increase the stability of the dispersion. Methods of stabilizing colloidal dispersions are known in the art. Whether stabilized or not, the colloidal dispersion used in conjunction with the invention preferably has a degree of colloidal stability such that the average overall particle size of the colloidal particle as measured by DLS does not change over a period of 3 weeks or more (e.g., 4 weeks or more, or even 5 weeks or more), more preferably 6 weeks or more (e.g., 7 weeks or more, or even 8 weeks or more), most preferably 10 weeks 50 or more (e.g., 12 weeks or more, or even 16 weeks or more). Aqueous colloidal silica dispersions are commercially available, generally at a slightly basic pH (e.g., about 9-10), but are also available as neutral and acidic dispersions. [0017] The amount of silica in the aqueous colloidal silica dispersion is about 5-70 wt.% based on the total weight of the dispersion. Typically, the amount of silica in the dispersion will be about 20 wt.% or more (e.g., about 25 wt.% or more) or even about 35 wt. % or more (e.g., about 40 wt.% or more). Thus, the amount of silica in the dispersion can be 55 about 10-65 wt.% (e.g., about 15-60 wt%.) or about 20-50 wt.% (e.g., about 25-45 wt.%). [0018] The aqueous colloidal silica dispersion and the silyl amine treating agent can be combined to provide a reaction mixture by any suitable method. Preferably, the silyl amine treating agent and the aqueous colloidal silica dispersion are combined with mixing or agitation to facilitate contact between the silica particles and the silyl amine treating agent.

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Mixing or agitation is especially important if the silyl amine treating agent is water- immiscible, in which case the reaction mixture will comprise an aqueous phase comprising the untreated colloidal silica particles, and a non-aqueous phase comprising the silyl amine treating agent. Mixing or agitation can be accomplished by any method, such as by using a mixing or agitating device. Examples of suitable devices include paddle stirrers, radial flow or axial flow impellers, 5 homogenizers, ball mills, jet mills, and similar devices. [0019] The reaction mixture can be maintained at any temperature that allows the silyl amine treating agent to react with aqueous colloidal silica dispersion (e.g., react with the silanol groups on the surface of the s ilica particles). G enerally, the reaction mixture is maintained at a temperature of about 5-100° C, such as about 15-80° C, or about 20-50° C, for about 5 minutes or longer (e.g., about 30 minutes or longer), or even about 60 minutes or longer (e.g., about 120 minutes 10 or longer, or about 180 minutes or longer). Longer reaction times (e.g., 5 hours or more, 10 hours or more, or even 20 hours or more) may be required depending on the particular reaction conditions (e.g., temperature and concentration of reagents) used. [0020] The reaction mixture can be contained in an open or closed reactor. While the treatment can be done in air, oxygen is preferably excluded from the reaction atmosphere, in which case the reaction can be conducted under an 15 atmosphere consisting essentially of nitrogen, argon, carbon dioxide, or a mixture thereof. [0021] Without wishing to be bound by any particular theory, it is believed that ammonia or an amine can be produced as a by-product of the reaction between the silyl amine treating agent and the silanol groups on the silica particles, and that ammonia- or amine-catalyzed hydrolysis of the silica surface can occur as a result. This side reaction can be minimized by controlling the amount of the silyl amine treating agent used. Also, this side reaction can be controlled by 20 passing carbon dioxide gas through the reaction mixture. The carbon dioxide can reduce the levels of liberated ammonia or amines by converting them into ammonium bicarbonate or amine bicarbonate salts, which are unable to react with the silica surface at an appreciable rate. The ammonium bicarbonate or amine bicarbonate salts can be removed from the mixture during or after the completion of the reaction by known methods. Alternatively, to the extent it may be advantageous to do so in any given application, additional ammonia can be added to the reaction mixture to increase 25 the amount of ammonia in solution. [0022] In orderto facilitate thereaction between the silyl amine treatingagent and the aqueous colloidalsilica dispersion, the reaction mixture should have a pH of about 7 or more (e.g., about 8 or more), such as about 9 or more (e.g., about 10 or more). Preferably the pH is about 7-11 (e.g., about 9-11). The pH of the dispersion may be altered by the addition of acids, bases, or buffers. These include materials that may react in situ to release acidic or basic substances. For 30 example, trimethylchlorosilane may be added to the reaction mixture to lower the pH by the evolution hydrochloric acid. Likewise, a buffering salt such as ammonium bicarbonate may be added to maintain the pH at a different level. [0023] The reaction mixture comprises no more than about 50 wt.% of an organic solvent, and preferably comprises no more than about 20 wt. % of an organic solvent. More preferably, the reaction mixture comprises no more than about 15 wt.% (e.g., no more than about 10 wt. %) or no more than about 5 wt. % (e.g., no more than about 1 wt. %) of an organic 35 solvent. Desirably, the reaction mixture is free of an organic solvent. According to one aspect of the invention, the reaction mixture consists essentially of the aqueous colloidal silica dispersion and the silyl amine treating agent, along with any reaction by-products that might be present. Within these guidelines, however, a small amount of an organic solvent can be used. Suitable organic solvents include water-immiscible and water-miscible organic solvents, preferably in which the silyl treating amine agent is at least partially soluble. Non-limiting examples of suitable water-immiscible organic 40 solvents include dichloromethane, dichloroethane, tetrachloroethane, benzene, toluene, heptane, octane, cyclohexane, and similar solvents. Non- limiting examples of water- miscible organic solvents include alcohols (e.g., methanol, ethanol, isopropanol, etc.), tetrahydrofuran, acetone, and similar solvents. [0024] The hydrophobic silica particles can be isolated and dried from the reaction mixture. The terms "dry" and "dried" as used herein with reference to the hydrophobic silica particles means substantially or completely free of the liquid 45 components of the reaction mixture, including water and other liquid-phase solvents, reactants, by-products, and any other liquid component that might be present. Similarly, the term "drying" as used herein refers to the process of removing the liquid components of the reaction mixture from the hydrophobic s ilica particles. [0025] The hydrophobic silica particles can be isolated from the reaction mixture prior to drying, or the hydrophobic silica particles can be dried directly from the reaction mixture. Any suitable method can be used to isolate the hydrophobic 50 silica particles from the reaction mixture. Suitable methods include filtration and centrifugation. [0026] The hydrophobic silica particles can be dried after isolation from the reaction mixture, or directly from the reaction mixture, by evaporating the volatile components of the reaction mixture from the hydrophobic silica particles. Evaporation of the volatile components of the reaction mixture can be accomplished using heat and/or reduced atmos- pheric pressure. When heat is used, the hydrophobic silica particles can be heated to any suitable drying temperature, 55 for example, using an oven or other similar device. The drying temperature chosen will depend, at least in part, on the specific components of the reaction mixture that require evaporation. Typically, the drying temperature will be about 40° C or higher (e.g., about 50° C or higher) such as about 70° C or higher (e.g., about 80° C or higher) or even about 120° C or higher (e.g., about 130° C or higher). Thus, the drying temperatures fall generally within the range of about 40-250°

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C (e.g., about 50-200° C), such as about 60-200° C (e.g., about 70-175° C), or about 80-150° C (e.g., about 90-130° C). [0027] The hydrophobic silica particles can be dried at any pressure that will provide a useful rate of evaporation. When drying temperatures of about 120° C and higher (e.g., about 120-150° C) are used, drying pressures of about 125 kPa or less (e.g:, about 75-125 kPa) are suitable. At drying temperatures lower than about 120° C (e.g., about 40-120° 5 C), drying pressures of about 100 kPa or less (e.g., about 75 kPa or less) are useful. Of course, reduced pressure (e.g., pressures of about 100 kPa or less, 75 kPa or less, or even 50 kPa or less) can be used as a sole method for evaporating the volatile components of the reaction mixture. [0028] The hydrophobic silica particles also can be dried by other methods. For example, spray drying can be used to dry the hydrophobic silica particles. Spray drying involves spraying the reaction mixture, or some portion thereof, 10 comprising the hydrophobic silica particles as a fine mist into a drying chamber, wherein the fine mist is contacted with hot air causing the evaporation of volatile components of the reaction mixture. Alternatively, the hydrophobic silica particles can be dried by lyophilization, wherein the liquid components of the reaction mixture are converted to a solid phase (i.e., frozen) and then to a gas phase by the application of a vacuum. For example, the reaction mixture comprising the hydrophobic silica particles can be brought to a suitable temperature (e.g., about-20° C or less, or about -10° C or 15 less, or even -5° C or less) to freeze the liquid components of the reaction mixture, and a vacuum can be applied to evaporate those components of the reaction mixture to provide dry hydrophobic silica particles. [0029] The hydrophobic silica particles can be neutralized prior to drying by addition of an acid, such as a mineral acid

(e.g., HCl or HNO3), an organic acid, or gas-acid (e.g., CO2) to the silica before or after isolation from the reaction medium. The neutralization of the hydrophobic silica prior to drying desirably enables the production of a dry powder 20 product that has a neutral pH (as measured when dispersed in a solution). [0030] The hydrophobic silica particles can be washed prior to or after isolation and/or drying from the reaction mixture. Washing the hydrophobic silica particles can be performed using a suitable washing solvent, such as water, a water- miscible organic solvent, a water-immiscible solvent, or a mixture thereof. The washing solvent can be added to the reaction mixture and the resulting mixture suitably mixed, followed by filtration, centrifugation, or drying to isolate the 25 washed hydrophobic silica particles. Alternatively, the hydrophobic silica particles can be isolated from the reaction mixture prior to washing. The washed hydrophobic s ilica particles can be further washed with additional washing steps followed by additional filtration, centrifugation, and/or drying steps. [0031] The hydrophobic silica particles have an overall particle size that is dependent, at least in part, on the overall particle size of the silica used in the initial dispersion. Preferably, the average overall particle size of the hydrophobic 30 silica particles is about five times or less, more preferably about two times or less, the average overall particle size of the silica used in the initial dispersion. When even smaller particles are desired, the average overall particle size of the hydrophobic silica particles is desirably about 175% or less, such as about 150% or less or even 125% or less, of the average overall particle size of the silica particles used in the initial dispersion. The average overall particle size of the hydrophobic silica particles can be determined by the method described in Example 1. The particle size of the hydrophobic 35 silica particles can be further reduced, if desired. Suitable processes for the reduction of the particle size of the hydrophob ic silica particles include but are not limited to wet or dry grinding, hammer milling, and jet milling. [0032] The hydrophobic silica particles can be used for many different applications including but not limited to toners compositions, antiblocking agents, adhesion modifiers, polymer additives (e.g., for elastomers and rubbers, such as silicone rubbers), abrasion-resistant coatings and films, delustering coatings and films, reological control agents (e.g., 40 for epoxies or liquid polymers), and mechanical/ optical control agents (e.g., for composites and plastics). The hydrophobic silica particles are especially useful in toner compositions. In that regard, the invention provides a method for preparing a toner composition, as well as a method of preparing a polymer composition, which methods comprise preparing hydrophobic silica particles according to the methods described herein and (b) combining the hydrophobic silica particles with toner particles or a polymer to provide a toner composition or polymer composition, respectively. 45 [0033] Thus, the method of preparing a toner composition comprises (a) providing an aqueous colloidal silica dispersion comprising about 5-70 wt. % of hydrophilic silica particles, wherein the hydrophilic silica particles have an average overall particle size of about 10-1000 nm, (b) combining the dispersion with about 3-75 mmole/m2 (based on the BET surface area of the hydrophilic silica particles) of a silyl amine treating agent to provide a reaction mixture, wherein the reaction mixture has a pH of about 7 or more and comprises no more than about 50 wt.% of an organic solvent, (c) drying the 50 dispersion to provide hydrophobic silica particles and (d) combining the hydrophobic silica particles with toner particles to provide a toner composition. Any suitable toner particles can be used in accordance with this method. The method of preparing toner compositions may further comprise the addition of other components such as binders, resins, colorants, or other metal oxide particles. The other aspects of the method for preparing a toner composition according to the invention are as described with respect to the method of preparing hydrophobic silica particles of the invention. 55 [0034] Similarly, the method of preparing a polymer composition comprises (a) providing an aqueous colloidal silica dispersion comprising about 5-70 wt.% of hydrophilic silica particles, wherein the hydrophilic silica particles have an average overall particle size of about 10-1000 nm, (b) combining the dispersion with about 3-75m mole/m2 (based on the BET surface area of the hydrophilic silica particles) of a silyl amine treating agent to provide a reaction mixture,

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wherein the reaction mixture has a pH of about 7 or more and comprises no more than about 50 wt.% of an organic solvent, (c) drying the dispersion to provide hydrophobic silica particles and (d) combining the hydrophobic silica particles with a polymer to provide a polymer composition. The method of preparing a polymer composition can be used with any suitable polymer to provide any type of polymer composition, such as an epoxy, coating composition, film forming 5 composition, or plastic composition. [0035] The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.

EXAMPLES 10 [0036] In each of the following examples, reactions were conducted in a 500 mL 3- necked flask fitted with an overhead agitator and 0.6 cm (0.25 inch) thermocouple, unless otherwise noted. The carbon content of the hydrophobic silica particles was used as a measure of the extent of silylation of surface silanol groups. Carbon content was measured using a model C- 200 Carbon Analyzer instrument (LECO Corp.). Particle sizes were determined by dynamic light scat- 15 tering using a Microtrac® UPA 150 instrument (Leeds and Northrup Co.). The following hydrophilic colloidal silica dispersions used in the examples: MP 1040 (Nissan Chemical), PL 13 (Fuso Chemical), and Snowtex® ZL (Nissan Chem- ical).

EXAMPLE 1 20 [0037] The following example illustrates the preparation of hydrophobic silica particles by treating a hydroph ilic colloidal silica dispersion with a treating agent, in accordance with the invention. [0038] Hydrophobic silica particle samples 1A- 3A were prepared from the commercially available hydrophilic colloidal silica dispersions indicated in Table 1. Hexamethyldisilazane [HMDZ] was added directly to each of the hydrophilic 25 colloidal silica dispersions in a 2 liter 3- necked flask fitted with an overhead agitator and 0.6 cm (0.25 inch) thermocouple, and the mixtures were stirred rapidly at room temperature (19-21°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for the duration of the reaction time, which was between 20 and 24 hours. Table 1 provides the specific reaction times and the amount of silica dispersion and HMDZ used in preparing each sample. Intermediate samples were removed from each reaction mixture at various 30 times, dried on a moisture balance at 160°C, and tested for carbon content. These results are provided in Table 3. [0039] After allowing the dispersions to react for the time specified in Table 1, each dispersion was poured into a Pyrex dish and dried in a forced-air oven at 128-135° C. The final products were tested for carbon content and BET surface area. The particle size of the silica dispersions was measured by dynamic light scattering before and after treatment. The after-treatment silica particles were ground in a mortar and dispersed in tetrahydrofuran by ultrasound for 5-10 35 minutes prior to measuring the particle size. The results of the testing are provided in Tables 1 and 2.

Table 1 Hydrophilic Silica Dispersion Reaction Time Carbon Content Sample HMDZ (g) (hours) (%) BET (m2/g) 40 Type Amount (g) MP 1040, 40% 1A 999 35 21.5 0.67 31 solids MP 2040, 27% 45 1B 798 17 24 0.22 17 solids 1C PL 13, 36% solids 1087 21 23 0.29 18

50 Table 2 Average Particle Size (by volume) Before Average Particle Size (by volume) After Treatment Sample Treatment (nm) (nm) 1A 141 148 55 1B 233 257 1C 212 288

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Table 3 Sample Reaction Time (hours) /Percent (%) Carbon

5 1A 2.75/0.04 4.75/0.21 20.5/0.59 1B 4/0.09 6.25/0.19 22.75/0.23 1C 2.5/0.18 5.75/0.22 21.5/0.29

10 [0040] The percent carbon content measurements provided in Table 1 indicate that the silica particles in each of samples 1A-1C contained sufficient hydrophobic groups to render the silica particles hydrophobic. The percent carbon content measurements of the intermediate samples in Table 3 show that the level of treatment increases with reaction time. The similar average particle size of the hydrophobic (post-treatment) silica particles as compared to the particle size of the silica particles before treatment (Table 2) shows that no significant agglomeration of the colloidal particles 15 occurred during or after treatment. These results demonstrate that hydrophobic silica particles can be prepared directly from commercially available dispersions in accordance with the invention..

EXAMPLE 2

20 [0041] The following example illustrates the preparation of hydrophobic silica particles by treating a hydroph ilic colloidal silica dispersion with HMDZ and subsequently isolating and washing the hydrophobic silica particles, in accordance with the invention. [0042] Hydrophobic silica particle samples 2A and 2B were prepared from the commercially available hydrophilic colloidal silica dispersions indicated in Table 4. HMDZ was added directly to each hydrophilic colloidal silica dispersion 25 in a 100 mL round bottomed flask fitted with a magnetic stir bar, and the mixtures were stirred rapidly at room temperature (19-21° C) at a rate such that the vortex of the dispersion extended at least to the top of the stir bar. Stirring at this rate was continued for the duration of the reaction time specified in Table 4. Table 4 provides the amount of silica dispersion and HMDZ used in preparing each sample. [0043] After allowing the dispersions to react for the specified time, each dispersion was poured into a glass dish and 30 dried in a forced air oven at 128-135° C, and the final products were tested for carbon content. A sample of each dried product was washed by refluxing in toluene for 30 minutes, isolating the silica particles by filtration, and washing again with fresh toluene. The washed samples were dried under vacuum at 60-70° C for 18 hours, and subsequently tested for carbon content. The results are presented in Table 4.

35 Table 4

Hydrophilic Silica Dispersion Reaction Carbon Content (%) Sample HMDZ (g) Temp. (°C) Type Amount (g) Time (hours) Before Wash After Wash MP-1040, 40 2A 50 g 3.5 g 20-23 20 0.90 0.57 40% solids MP-1040, 2B 50 g 1.8 g 20-23 20 0.65 0.61 40% solids

45 [0044] The reduced carbon content in the washed samples is the result of removing non- volatile treatment by- products from the surface of the silica particles. These results show that washing the samples can decrease the level of organic impurities in the samples without significantly affecting the hydrophobic nature of the silica particles. [0045] The results further show that washing sample 2A reduced the carbon content of the sample by about 34%, whereas washing sample 2B reduced the carbon content of the sample by only about 7%. This illustrates that a greater 50 excess of HMDZ was used in preparing sample 2A. By reducing the amount of HMDZ used, the level of organic impurities in the hydrophobic silica product can be reduced.

EXAMPLE 3

55 [0046] The following example illustrates the effect of reaction time and temperature on the preparation of hydrophobic silica particles in accordance with the invention. [0047] Hydrophobic silica particle samples 3A- 3C were prepared from the commercially available hydrophilic colloidal

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silica dispersions indicated in Table 5. HMDZ was added directly to each hydrophilic colloidal silica dispersion, and the mixtures were stirred rapidly at room temperature (19-21°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for the duration of the reaction time specified in Table 5. Table 5 provides the amount of silica dispersion and HMDZ used in preparing each sample. Intermediate 5 samples were removed from the reaction at various times, dried on a moisture balance at 160°C, and analyzed for carbon content. These results are provided in Table 6. [0048] After allowing the dispersions to react for the specified time, each dispersion was poured into a glass dish and dried in a forced air oven at 128-135 °C, and the final products were tested for carbon content. A sample of each dried product was washed by refluxing in acetone for 30-60 minutes, isolating the silica particles by filtration, and washing 10 again with fresh acetone. The washed samples were dried under vacuum at 60-70 °C for 18 hours, and subsequently tested for carbon content. The results are presented in Table 5.

Table 5

Hydrophilic Silica Dispersion Reaction Carbon Content (%) 15 Sample HMDZ (g) Temp (°C) Type Amount (g) Time (hours) Before Wash After Wash Snowtex® 3A ZL, 40% 200 g 7 20-23 23 0.62 0.54 solids 20 Snowtex® 3B ZL, 40% 200 g 7 42-48 8.5 0.99 0.62 solids Snowtex® 25 3C ZL, 40% 100 g 1.8 45 8.5 0.42 0.39 solids

30 Table 6 Sample Reaction Time (hours)/Percent (%) Carbon 3A 0.83/0.07 3/0.39 4.75/0.32 7/0.46 3B 1/0.38 2.5/0.64 4/0.85 8.5/0.99 35 3C 1/0.12 2.5/0.26 4/0.33 8.5/0.42

[0049] Comparison of the carbon content of samples 3A and 3B shows that a higher degree of treatment can be achieved in a shorter amount of time using increased reaction temperatures. At the increased reaction temperature and 40 reduced reaction time, the concentration of treating agent can be reduced while maintaining an acceptable level of treatment (sample 3C).

EXAMPLE 4

45 [0050] The following example illustrates the effect of using water-miscible organic solvents in combination with the method of the invention. [0051] Hydrophobic silica particle samples 4A and 4B were prepared from a commercially available hydrophilic colloidal silica dispersion (Snowtex® ZL, 40% solids) by adding 3.5 g HMDZ and 16.8 wt. % isopropanol (IPA) (4A) or 16.8 wt.% tetrahydrofuran (THF) (4B) directly to 100 g of the hydrophilic colloidal silica dispersion, and stirring rapidly at room 50 temperature (19-21°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for the duration of the reaction time, which was 22 hours. [0052] After allowing the dispersion to react for the specified time, the dispersion was poured into a glass dish and dried in a forced air oven at 128-135 °C. The carbon content of the final products is shown in Table 7.

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Table 7

Hydrophilic Silica Co-Solvent ReactionTime Carbon Sample Dispersion HMDZ (g) Type, Temp (°C) (hours) Content (%) 5 Type Amount (g) Amount (g) Snowtex® 4A ZL, 40% 100 3.5 IPA, 20 23-26 22 0.23 solids

10 Snowtex® 4B ZL, 40% 200 7 THF, 40 20-23 22 0.44 solids

[0053] Samples 4A and 4B were prepared in the same manner as sample 3A (Example 3), except that the reaction 15 mixture used to prepare samples 4A and 4B included a cosolvent. A comparison of the carbon content of sample 4A with the carbon content of sample 3A demonstrates that the inclusion of 16.8 wt. % isopropanol as a cosolvent resulted in a significant decrease in the treatment level. Inclusion of 16.8 wt.% tetrahydrofuran as a cosolvent in sample 4B resulted in a higher carbon content as compared to sample 4A, containing the isopropanol, but still resulted in a decrease in carbon content over sample 3A, which contained no organic cosolvent. 20 EXAMPLE 5

[0054] The following example illustrates the effect of pH on the preparation of hydrophobic silica particles in accordance with the invention. 25 [0055] Hydrophobic silica particle samples 5A and 5B were prepared from the commercially available hydrophilic silica dispersions indicated in Table 8. HMDZ was added directly to each hydrophilic colloidal s ilica dispersion, and the pH of sample 5A was adjusted to about 7.5 by addition of 10 wt. % hydrochloric acid (the pH of sample 5B was not adjusted). The mixtures were stirred rapidly at room temperature (19-21°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for duration of the reaction time specified in 30 Table 8. The amounts of the silica dispersions and HMDZ used are provided in Table 8. [0056] After allowing the dispersions to react for the time specified in Table 8, the pH value of each dispersion was tested. Then, each dispersion was poured into a glass dish and dried in a forced air oven at 128-135 °C, and the final products were tested for carbon content. The pH values of the dispersions at the end of the reaction times and the carbon content of the final products are provided in Table 8. 35 Table 8

Hydrophilic Silica Dispersion Reaction Time Carbon Content Sample HMDZ (g) Temp (°C) pH Type Amount (g) (hours) (%) 40 Snowtex® ZL, 5A 200 g 7 23 8.5 7.5 0.23 40% solids Snowtex® ZL, 5B 200 g 7 20-23 7 10.8 0.46 40% solids 45

[0057] Comparison of the carbon content of sample 5A (lower pH) with sample 5B (higher pH) indicates that the method of preparing hydrophobic silica particles of the invention is more effective at higher pH values.

EXAMPLE 6 50

[0058] The following example illustrates the effect of excess ammonia on the preparation of hydrophobic silica particles in accordance with the invention. [0059] Hydrophobic silica particle sample 6 was prepared from a commercially available hydrophilic colloidal silica dispersion (MP-1040, 40% solids) by adding 0.64 g of aqueous ammonia (28%) to 50.5 g of the hydrophilic colloidal 55 silica dispersion in a 100 mL 3-necked flask fitted with a magnetic stir bar and thermometer, followed by the addition of 3.5 g of HMDZ. The mixture was stirred at room temperature (19-21°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for the duration of the reaction time,

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which was 20 hours. [0060] After allowing the dispersion to react for the specified time, the dispersion was poured into a glass dish and dried in a forced air oven at 128-135 °C. The final product had a carbon content of 0.28%. [0061] Comparison of the carbon content of sample 6 with that of sample 2A (Example 2), which was prepared in a 5 similar manner without the addition of ammonia, indicates that the method of the invention can be conducted in the presence of excess ammonia, but results in a lower level of treatment under a given set of conditions.

EXAMPLE 7

10 [0062] The following example illustrates the effect of pH-adjusting additives on the preparation of hydrophobic silica particles in accordance with the invention. [0063] Hydrophobic silica particle samples 7A-7D were prepared from the commercially available hydrophilic silica

dispersions indicated in Table 9. HMDZ and either ammonium bicarbonate (NH 4HCO3) or trimethylchlorosilane (TMCS) as a pH-adjusting additive were added directly to each hydrophilic colloidal silica dispersion (except for sample 7D, 15 which did not contain a pH adjusting additive). The mixtures were stirred rapidly at room temperature (20-23°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for the time specified in Table 9. The amounts of the silica dispersions, pH-adjusting additives, and HMDZ used are provided in Table 9. [0064] After allowing the dispersions to react for the specified time, the pH of the dispersions was measured, as 20 provided in Table 9. The dispersions were then poured into a glass dish and dried in a forced air oven at 128-135°C. The carbon content of the final products is provided in Table 9.

Table 9 Hydrophilic Silica Dispersion pH-Adjusting Carbon 25 Sample HMDZ (g) Additive, pH Reaction Time Content (%) Type Amount (g) Amount Snowtex® ZL, TMCS, 0.245 7A 100 1.8 10.2 24 0.41 40% solids mL 30 Snowtex® ZL, NH HCO , 7B 100 1.8 4 3 9.7 24 0.36 40% solids 0.608 g Snowtex® ZL, NH HCO , 7C 100 1.8 4 3 9.9 24 0.41 40% solids 0.304 g 35 Snowtex® ZL, 7D 200 3.5 none 10.7 23.5 0.43 40% solids

[0065] These results show that the treatment process is effective in the presence of additives that moderately lower

40 the pH of the reaction mixture. However, significantly lower pH values tend to reduce the treatment level (Example 5).

EXAMPLE 8

[0066] The following example illustrates the preparation of hydrophobic silica particles by treating a hydroph ilic colloidal

45 dispersion of silica with a treating agent and subsequently isolating and washing the silica, in accordance with the invention. [0067] Hydrophobic silica particle samples 8A and 8B were prepared from the commercially available hydrophilic colloidal silica dispersions indicated in Table 10. bis (trifluoropropyl)tetramethyl-disilazane (F-HMDZ) was added directly to the hydrophilic colloidal silica dispersion in a 250 ml 3-necked round flask fitted with an overhead agitator, cooling

50 water condenser, and thermocouple. The mixture was stirred at 460 RPM and heated to 100°C. Stirring continued at 100°C for the duration of the reaction time, which is specified in Table 10. Table 10 also provides the amount of the silica dispersion and F-HMDZ used in preparing each sample. [0068] After allowing the dispersions to react for the specified time, each dispersion was filtered and twice washed with DI water. The wet samples were then poured into a glass dish and dried in a forced-air oven at 130°C. The final

55 products were tested for carbon content. A sample of each dried product was extracted with toluene for 3 hours and then dried under vacuum at 90-100° C for 18 hours and subsequently tested for carbon content. The results are presented in Table 10.

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Table 10 Hydrophilic Silica F-HMDZ (g) Carbon Content (%) Dispersion Reaction 5 Sample Temp. (°C) time (hours) Before After Type Amount (g) Extraction Extraction 8A MP-1040 50 3.5 100 2 2.81 0.694 40% solids 10 8B MP-1040 100 3.5 100 2 1.65 0.786 40% solids

[0069] The reduced carbon content in the toluene extracted samples is the result of removing non- volatile treatment 15 by-products and unreacted F-HMDZ from the surface of the silica particles. These results demonstrate that washing the samples can decrease the level of organic impurities in the samples without significantly affecting the hydrophobic nature of the silica particles.

EXAMPLE 9 20 [0070] The following example illustrates the effect of homogenization and spray drying on the preparation of hydrophobic silica in accordance with the invention. [0071] Hydrophobic silica particles (samples 9A and 9B) were prepared from commercially available hydrophilic colloidal silica dispersions listed in Table 11. The colloidal silica dispersions were added to a reactor and diluted with 25 deionized water to provide the silica concentrations indicated in Table 11. HMDZ was added to the diluted dispersions in the indicated amounts. Sample 9A was recycled at 50° C through an in- line homogenizer to facilitate vigorous mixing of the dispersion with the HMDZ. Sample 9B also was recycled at 50° C, but was not homogenized. Both samples were spray dried. The carbon content of the dried samples is provided in Table 11.

30 Table 11

Hydrophilic Silica Dispersion Carbon Content Sample HMDZ (kg) Homogenized Type Amount (kg) Diluted Conc. (%) MP-1040, 40% 35 9A 40 21 3.2 yes 0.98 solids MP-1040, 40% 9B 41 21 3.5 no 0.84 solids

40 [0072] Comparison of the carbon content of sample 9A with that of sample 9B shows that the use of homogenization results in an increased treatment level. Spray drying produced a fine powder directly in the drying step.

EXAMPLE 10

45 [0073] The following example illustrates the effect of neutralization of hydrophobic silica prepared in accordance with the invention. [0074] Hydrophobic silica particles were prepared from a commercially available hydrophilic colloidal silica dispersion (Snowtex XL), which was diluted to 32 wt.% silica with deionized water. 2.9 kg of HMDZ was added to the diluted dispersion. The mixture was heated to 50° C and recycled through an in-line homogenizer for 24 hours to facilitate 50 vigorous mixing of the silica dispersion with the HMDZ. One half of the treated particle dispersion was spray dried after treatment (sample 10A). The second half of the dispersion was neutralized by adding dilute aqueous HCl to the solution prior to spray drying (sample 10). The dried particles were re- dispersed in a mixture of isopropyl alcohol and water, and the pH of the particles was measured using a pH probe. [0075] Sample 10A had a carbon content of about 1.16 and a pH of about 10.6, whereas sample 10B had a carbon 55 content of about 0.97 and a pH of about 7.7. These results show that neutralization of the treated silica solution prior to drying results in a product with a neutral pH, although with a slight loss in treatment level.

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COMPARATIVE EXAMPLE 11

[0076] The following example illustrates the treatment of a colloidal silica dispersion with hexamethyldisiloxane (HMDS) and ammonia instead of a silyl amine treating agent, not in accordance with the invention. 5 [0077] A hydrophobic colloidal silica dispersion (sample 11) was prepared from a commercially available hydrophilic silica dispersion (Snowtex® ZL, 40% solids) by adding 1.5 g of aqueous ammonia (10%) and 7 g of HMDS to 200 g of the hydrophilic silica dispersion. The mixture was stirred at room temperature (22-23°C) at a rate such that the vortex of the dispersion extended at least to the top of the agitator blade. Stirring at this rate was continued for 24 hours. [0078] After allowing the dispersion to react for the specified time, the dispersion was poured into a glass dish and 10 dried in a forced air oven at 128-135 °C. The final product had a carbon content of 0.03%. [0079] Sample 11 was prepared in the same manner as sample 3A (Example 3), except that the HMDZ used in sample 3A was replaced with an equivalent amount of HMDS and ammonia. A comparison of the carbon content of sample 8 (0.03%) with that of sample 3A (0.54% after washing) indicates that hexamethyldisiloxane and ammonia are not effective at treating colloidal silica in accordance with the invention. 15 [0080] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open- ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to 20 each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification 25 should be construed as indicating any non-claimed element as essential to the practice of the invention.

Claims

30 1. A method of preparing hydrophobic silica particles comprising

(a) providing an aqueous colloidal silica dispersion comprising 5-70 wt. % of hydrophilic silica particles, wherein the hydrophilic silica particles have an average overall particle size of 10-1000 nm, (b) combining the dispersion with 3-75m mole/m2 (based on the BET surface area of the hydrophilic silica 35 particles) of a silyl amine treating agent to provide a reaction mixture, wherein the reaction mixture has a pH of 7 or more and comprises no more than 50 wt. % of an organic solvent, and (c) drying the dispersion to provide hydrophobic silica particles.

2. The method of claim 1, wherein the dispersion comprises 15-60 wt. % silica particles. 40 3. The method of claim 2, wherein the dispersion comprises 20-50 wt. % silica particles.

4. The method of claim 1, wherein the reaction mixture is maintained at a temperature of 5-100° C for 5 minutes or longer.

45 5. The method of claim 4, wherein the reaction mixture is maintained at a temperature of 15-50° C for 5 minutes or longer.

6. The method of claim 1, wherein the silyl amine treating agent is water-immiscible.

7. The method of claim 1, wherein the silyl amine treating agent has the general formula (R3Si)nNR’(3-n) wherein 50 n is 1-3; each R is independently selected from the group consisting of hydrogen, a C 1-C18 alkyl or branched alkyl, a C 3-C18 haloalkyl, vinyl, a C 6-C14 aromatic group, a C 2-C18 alkenyl group, a C 3-C18 epoxyalkyl group, and linear or branched CmH2mX, wherein m is 1-18; each R’ is independently hydrogen, C1-C18 alkyl or branched alkyl, or when n=1, a C 2-C6 cyclic alkylene; 55 X is NR"2, SH, OH, OC(O)CR"=CR"2, CO2R"2, or CN; and R" is independently hydrogen, a C 1-C18 alkyl or branched alkyl, a C 2-C18 unsaturated group, a C 1-C18 acyl or C 3-C18 unsaturated acyl group, a C2-C6 cyclic alkylene or a C6-C18 aromatic group.

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8. The method of claim 7, wherein each R’ is hydrogen.

9. The method of claim 1, wherein the silyl amine treating agent is a bisaminodisilane.

5 10. The method of claim 1, wherein the silyl amine treating agent is bis (trifluoropropyl)tetramethyl-disilazane (F-HMDZ).

11. The method of claim 1, wherein the silyl amine treating agent is hexamethyldisilazane.

12. The method of claim 1, wherein the silyl amine treating agent is a silazane having the formula 10

20 wherein R1 and R2 are independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryl, and aryloxy; R3 is selected from the group consisting of hydrogen, (CH2)nCH3, wherein n is an integer between 0 and 3, C(O) (CH2)nCH3, wherein n is an integer between 0 and 3, C(O) NH2, C(O)NH(CH2)nCH3, wherein n is an integer between 0 and 3, and C(O)N[(CH2)nCH3](CH2)mCH3, wherein n and m are integers between 0 and 3; and 25 R4 is [(CH 2)a(CHX)b,(CYZ)c], wherein X, Y and Z are independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryl, and aryloxy, and a, b, and c are integers of 0 to 6 satisfying the condition that (a+b+c) equals an integer of 2 to 6.

13. The method of claim 1, wherein the dispersion is dried at 40-250° C. 30 14. The method of claim 13, wherein the dispersion is dried at 80-150 C.

15. The method of claim 1, wherein the dispersion is dried by lyophilization.

35 16. The method of claim 1, wherein the dispersion is dried at a pressure of 100 kPa or less.

17. The method of claim 1, wherein the dispersion is spray-dried.

18. The method of claim 1, wherein the dispersion is washed prior to drying. 40 19. The method of claim 1, further comprising isolating the hydrophobic silica particles by filtration or centrifugation.

20. The method of claim 1, further comprising reducing the overall particle size of the hydrophobic silica particles.

45 21. The method of claim 20, wherein the overall particle size of the hydrophobic silica particles is reduced by grinding, hammer milling, or jet milling.

22. The method of claim 1, wherein the hydrophilic silica particles are fumed silica particles.

50 23. The method of claim 1, wherein the hydrophilic silica particles have an average overall particle size of 100 nm or more.

24. The method of claim 1, wherein the hydrophobic silica particles have an average overall particle size that is five times or less the average overall particle size of the hydrophilic silica particles.

55 25. The method of claim 1, wherein the silica particles have a surface area of 50 m2/g or less.

26. The method of claim 25, wherein the silica particles have a surface area of 35 m2/g or less.

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27. The method of claim 1, wherein the silica dispersion is combined with 8-36 mmole/m2 (based on the BET surface area of the silica) of the silyl amine treating agent.

28. The method of claim 27, wherein the silica dispersion is combined with 9-18 mmole/m2 (based on the BET surface 5 area of the silica) of the silyl amine treating agent.

29. The method of claim 1, wherein the reaction mixture comprises no more than 20 wt. % of an organic solvent.

30. The method of claim 29, wherein the reaction mixture is free of an organic solvent. 10 31. The method of claim 1, wherein the reaction mixture consists essentially of the colloidal silica dispersionand the silyl amine treating agent.

32. The method of claim 1, wherein the pH is 7-11. 15 33. The method of claim 32, wherein the pH is 9-11.

34. The method of claim 1, wherein the hydrophobic silica particles are neutralized prior to drying.

20 35. The method of claim 1, wherein the aqueous colloidal dispersion of silica is stab ilized.

36. A method of preparing a toner composition comprising

(a) preparing hydrophobic silica particles by the method of claim 1, and 25 (b) combining the hydrophobic silica particles with toner particles to provide a toner composition.

37. A method of preparing a polymer composition comprising

(a) preparing hydrophobic silica particles by the method of claim 1, and 30 (b) combining the hydrophobic silica particles with a polymer to provide a polymer composition.

38. The method of claim 37, wherein the polymer composition is an epoxy, a coating composition, a film- forming composition, or a plastic composition.

35 Patentansprüche

1. Verfahren zur Herstellung von hydrophoben Siliciumdioxidteilchen, umfassend

40 (a) Bereitstellen einer wässrigen kolloidalen Siliciumdioxid-Dispersion, umfassend 5-70 Gew.% hydrophile Si- liciumdioxidteilchen mit einer durchschnittlichen Gesamtteilchengröße von 10-1000 nm, (b) Kombinieren der Dispersion mit 3-75 mmol/m2 (bezogen auf die BET-Oberfläche der hydrophilen Silicium- dioxidteilchen) eines Silylamin-Behandlungsmittels, um ein Reaktionsgemisch bereitzustellen, wobei das Re- aktionsgemisch einen pH von 7 oder mehr aufweist und nicht mehr als 50 Gew. % eines organischen Lösungs- 45 mittels umfasst, und (c) Trocknen der Dispersion, um hydrophobe Siliciumdioxidteilchen bereitzustellen.

2. Das Verfahren nach Anspruch 1, wobei die Dispersion 15-60 Gew.% Siliciumdioxidteilchen umfaßt.

50 3. Das Verfahren nach Anspruch 2, wobei die Dispersion 20-50 Gew.% Siliciumdioxidteilchen umfaßt.

4. Das Verfahren nach Anspruch 1, wobei das Reaktionsgemisch bei einer Temperatur von 5-100°C für 5 Minuten oder länger gehalten wird.

55 5. Das Verfahren nach Anspruch 4, wobei das Reaktionsgemisch bei einer Temperatur von 15-50°C für 5 Minuten oder länger gehalten wird.

6. Das Verfahren nach Anspruch 1, wobei das Silylamin-Behandlungsmittel nicht mit Wasser mischbar ist.

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7. Das Verfahren nach Anspruch 1, wobei das Silylamin-Behandlungsmittel die allgemeine Formel (R3Si)nNR’(3-n) hat, wobei n 1-3 ist; jedes R unabhängig voneinander ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, einem C 1-C18-Alkyl 5 oder verzweigten Alkyl, einem C3-C18-Halogenalkyl, Vinyl, einer aromatischen C6-C14-Gruppe, einer C2-C18-Alke- nylgruppe, einer C3-C18-Epoxyalkylgruppe, und linearem oder verzweigtem CmH2mX, wobei m 1-18 ist; jedes R’ unabhängig voneinander Wasserstoff, C 1-C18-Alkyl oder verzweigtes Alkyl, oder, wenn n = 1, ein cyclisches C2-C6-Alkylen ist; - X NR"2, SH, OH, OC(O)CR"=CR"2, CO2R"2 oder CN ist; und 10 R" unabhängig voneinander Wasserstoff, ein C 1-C18-Alkyl oder verzweigtes Alkyl, eine ungesättigte C 2-C18-Gruppe, eine C1-C18-Acyl- oder ungesättigte C3-C18-Acylgruppe, eine cyclische C2-C6-Alkylen- oder eine aromatische C6-C18-Gruppe ist.

8. Das Verfahren nach Anspruch 7, wobei jedes R’ Wasserstoff ist. 15 9. Das Verfahren nach Anspruch 1, wobei das Silylamin-Behandlungsmittel ein Bisaminodisilan ist.

10. Das Verfahren nach Anspruch 1, wobei das Silylamin-Behandlungsmittel Bis(trifluorpropyl)tetramethyldisilazan (F- HMDZ) ist. 20 11. Das Verfahren nach Anspruch 1, wobei das Silylamin-Behandlungsmittel Hexamethyldisilazan ist.

12. Das Verfahren nach Anspruch 1, wobei das Silylamin-Behandlungsmittel ein Silazan mit der Formel ist

wobei R1 und R2 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, Halogen, 35 Alkyl, Alkoxy, Aryl und Aryloxy;

R3 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, (CH2)nCH3, wobei n eine ganze Zahl zwischen 0 und 3 ist, C(O)(CH2)nCH3, wobei n eine ganze Zahl zwischen 0 und 3 ist, C(O)NH2, C(O)NH(CH2)nCH3, wobei n eine ganze Zahl zwischen 0 und 3 ist, und C(O)N[(CH2)nCH3](CH2)mCH3, wobei n und m ganze Zahlen zwischen 0 und 3 sind; und 40 R4 [(CH 2)a(CHX)b,(CYZ)c]ist, wobei X, Yund Z unabhängig voneinander ausgewählt sind aus derGruppe, bestehend aus Wasserstoff, Halogen, Alkyl, Alkoxy, Aryl und Aryloxy, und a, b und c ganze Zahlen von 0 bis 6 sind, die die Bedingung erfüllen, dass (a+b+c) gleich einer ganzen Zahl von 2 bis 6 ist.

13. Das Verfahren nach Anspruch 1, bei dem die Dispersion bei 40-250°C getrocknet wird. 45 14. Das Verfahren nach Anspruch 13, wobei die Dispersion bei 80-150°C getrocknet wird.

15. Das Verfahren nach Anspruch 1, wobei die Dispersion durch Gefriertrocknung getrocknet wird.

50 16. Das Verfahren nach Anspruch 1, wobei die Dispersion bei einem Druck von 100 kPa oder weniger getrocknet wird.

17. Das Verfahren nach Anspruch 1, wobei die Dispersion sprühgetrocknet wird.

18. Das Verfahren nach Anspruch 1, wobei die Dispersion vor dem Trocknen gewaschen wird. 55 19. Das Verfahren nach Anspruch 1, ferner-umfassend das Isolieren der hydrophoben Siliciumdioxidteilchen durch Filtration oder Zentrifugation.

16 EP 1 807 347 B1

20. Das Verfahren nach Anspruch 1, ferner umfassend das Reduzieren der Gesamtteilchengröße der hydrophoben Siliciumdioxidteilchen.

21. Das Verfahren nach Anspruch 20, wobei die Gesamtteilchengröße der hydrophoben Siliciumdioxidteilchen durch 5 Mahlen, Hammermahlen, oder Strahlmahlen reduziert wird.

22. Das Verfahren nach Anspruch 1, wobei die hydrophilen Siliciumdioxidteilchen pyrogene Kieselsäureteilchen sind.

23. Das Verfahren nach Anspruch 1, wobei die hydrophilen Siliciumdioxidteilchen eine durchschnittliche Gesamtteil- 10 chengröße von 100 nm oder mehr aufweisen.

24. Das Verfahren nach Anspruch 1, wobei die hydrophoben Siliciumdioxidteilchen eine durchschnittliche Gesamtteil- chengröße haben, die das fünffache oder weniger der durchschnittlichen Gesamtteilchengröße der hydrophilen Siliciumdioxidteilchen ist. 15 25. Das Verfahren nach Anspruch 1, wobei die Siliciumdioxidteilchen eine Oberfläche von 50 m2/g oder weniger aufweisen.

26. Das Verfahren nach Anspruch 25, wobei die Siliciumdioxidteilchen eine Oberfläche von 352 /gm oder weniger 20 aufweisen.

27. Das Verfahren nach Anspruch 1, wobei die Siliciumdioxid-Dispersion mit 8-36 mmol/m2 (bezogen auf die BET- Oberfläche des Siliciumdioxids) des Silylamin-Behandlungsmittels kombiniert wird.

25 28. Das Verfahren nach Anspruch 27, wobei die Siliciumdioxid-Dispersion mit 9-18m mol/m2 (bezogen auf die BET- Oberfläche des Siliciumdioxids) des Silylamin-Behandlungsmittels kombiniert wird.

29. Das Verfahren nach Anspruch 1, wobei das Reaktionsgemisch nicht mehr als 20 Gew.% eines organischen Lö- sungsmittels umfasst. 30 30. Das Verfahren nach Anspruch 29, wobei das Reaktionsgemisch frei von einem organischen Lösungsmittel ist.

31. Das Verfahren nach Anspruch 1, wobei das Reaktionsgemisch im Wesentlichen aus der kolloidalen Siliciumdioxid- Dispersion und dem Silylamin-Behandlungsmittel besteht. 35 32. Das Verfahren nach Anspruch 1, wobei der pH 7-11 ist.

33. Das Verfahren nach Anspruch 32, wobei der pH 9-11 ist.

40 34. Das Verfahren nach Anspruch 1, wobei die hydrophoben Siliciumdioxidteilchen vor dem Trocknen neutralisiert werden.

35. Das Verfahren nach Anspruch 1, wobei die wässrige kolloidale Dispersion von Siliciumdioxid stabilisiert ist.

45 36. Verfahren zur Herstellung einer Tonerzusammensetzung, umfassend

(a) Herstellen von hydrophoben Siliciumdioxidteilchen nach dem Verfahren von Anspruch 1, und (b) Kombinieren der hydrophoben Siliciumdioxidteilchen mit Tonerteilchen, um eine Tonerzusammensetzung bereitzustellen. 50 37. Verfahren zur Herstellung einer Polymerzusammensetzung, umfassend

(a) Herstellen von hydrophoben Siliciumdioxidteilchen nach dem Verfahren von Anspruch 1, und (b) Kombinieren der hydrophoben Siliciumdioxidteilchen mit einem Polymer, um eine Polymerzusammenset- 55 zung bereitzustellen.

38. Das Verfahren nach Anspruch 37, wobei die Polymerzusammensetzung ein Epoxidharz, eine Beschichtungszu- sammensetzung, eine filmbildende Zusammensetzung oder eine Kunststoffzusammensetzung ist.

17 EP 1 807 347 B1

Revendications

1. Procédé pour préparer des particules de silice hydrophobe, comprenant les opérations consistant à :

5 (a) disposer d’une dispersion aqueuse de silice colloïdale comprenant 5 à 70 % en poids de particules de silice hydrophile, les particules de silice hydrophile ayant une granulométrie globale moyenne de 10 à 1000 nm, (b) combiner la dispersion avec 3 à 75 mmol/m2 (sur la base de la surface spécifique BET des particules de silice hydrophile) d’un agent de traitement de type silylamine pour former un mélange réactionnel, le mélange réactionnel ayant un pH de 7 ou plus et comprenant au plus 50 % en poids d’un solvant organique, et 10 (c) sécher la dispersion pour donner des particules de silice hydrophobe.

2. Procédé selon la revendication 1, dans lequel la dispersion comprend 15 à 60 % en poids de particules de silice.

3. Procédé selon la revendication 2, dans lequel la dispersion comprend 20 à 50 % en poids de particules de silice. 15 4. Procédé selon la revendication 1, dans lequel le mélange réactionnel est maintenu à une température de 5 à 100°C pendant 5 minutes ou plus.

5. Procédé selon la revendication 4, dans lequel le mélange réactionnel est maintenu à une température de 15 à 50°C 20 pendant 5 minutes ou plus.

6. Procédé selon la revendication 1, dans lequel l’agent de traitement de type silylamine n’est pas miscible avec l’eau.

7. Procédé selon la revendication 1, dans lequel l’agent de traitement de type silylamine est de formule générale 25 (R3Si)nNR’(3-n), dans laquelle n vaut de 1 à 3 ; chaque R est indépendamment choisi dans l’ensemble constitué par l’hydrogène, un alkyle ou alkyle ramifié en C 1 à C18, un halogénoalkyle en C3 à C18, vinyle, un groupe aromatique en C 6 à C14, un groupe alcényle en C2 à C18, un groupe époxyalkyle en C3 à C18, et CmH2mX linéaire ou ramifié où m vaut de 1 à 18 ; 30 chaque R’ est indépendamment l’hydrogène ou un alkyle ou alkyle ramifié en 1C à C18 ou, quand n vaut 1, un alkylène cyclique en C2 à C6 ; X est NR"2, SH, OH, OC(O)CR"-CR"2, CO2R"2, ou CN ; et R" est indépendamment l’hydrogène, un alkyle ou alkyle ramifié en C1 à C18, un groupe insaturé en C2 à C18, un acyle en C 1 à C 18 ou un groupe acyle insaturé en C 3 à C 18, un alkylène cyclique en C 2 à C 6 ou un groupe aromatique 35 en C6 à C18.

8. Procédé selon la revendication 7, dans lequel chaque R’ est l’hydrogène.

9. Procédé selon la revendication 1, dans lequel l’agent de traitement de type silylamine est un bisaminodisilane. 40 10. Procédé selon la revendication 1, dans lequel l’agent de traitement de type silylamine est le (trifluoropropyl)bis tétraméthyldisilazane (F-HMDZ).

11. Procédé selon la revendication 1, dans lequel l’agent de traitement de type silylamine est l’hexaméthyldisilazane. 45 12. Procédé selon la revendication 1, dans lequel l’agent de traitement de type silylamine est un silazane de formule

dans laquelle R1 et R2 sont indépendamment choisis dans l’ensemble constitué par l’hydrogène, un halogène,

18 EP 1 807 347 B1

alkyle, alcoxy, aryle, et aryloxy ; R3 est choisi dans l’ensemble constitué par l’hydrogène, (CH2)nCH3 où n est un entier compris entre 0 et 3, C(O) (CH2)nCH3 où n est un entier compris entre 0 et 3, C(O)NH2, C(O)NH(CH2)nCH3 où n est un entier compris entre 0 et 3, et C(O)N[(CH2)nCH3](CH2)mCH3 où n et m sont des entiers compris entre 0 et 3 ; et 5 R4 est [(CH 2)a(CHX)b(CYZ)c] où X, Y et Z sont indépendamment choisis dans l’ensemble constitué par l’hydrogène, les halogènes, alkyle, alcoxy, aryle, et aryloxy, et a, b et c sont des entiers de 0 à 6 satisfaisant à la condition selon laquelle (a+b+c) est égale à un entier de 2 à 6.

13. Procédé selon la revendication 1, dans lequel la dispersion est séchée à 40-250°C. 10 14. Procédé selon la revendication 13, dans lequel la dispersion est séchée à 80-150°C.

15. Procédé selon la revendication 1, dans lequel la dispersion est séchée par lyophilisation.

15 16. Procédé selon la revendication 1, dans lequel la dispersion est séchée sous une pression de 100 kPa ou moins.

17. Procédé selon la revendication 1, dans lequel la dispersion est séchée par pulvérisation.

18. Procédé selon la revendication 1, dans lequel la dispersion est lavée avant d’être séchée. 20 19. Procédé selon la revendication 1, comprenant en outre l’isolation des particules de silice hydrophobe par filtration ou centrifugation.

20. Procédé selon la revendication 1, comprenant en outre la réduction de la granulométrie globale des particules de 25 silice hydrophobe.

21. Procédé selon la revendication 20, dans lequel la granulométrie globale des particules de silice hydrophobe est réduite par concassage, broyage au marteau, ou broyage au jet.

30 22. Procédé selon la revendication 1, dans lequel les particules de silice hydrophile sont des particules de silice fumée.

23. Procédé selon la revendication 1, dans lequel les particules de silice hydrophile ont une granulométrie globale moyenne de 100 nm ou plus.

35 24. Procédé selon la revendication 1, dans lequel les particules de silice hydrophobe ont une granulométrie globale moyenne qui est de cinq fois ou moins la granulométrie globale moyenne des particules de silice hydrophile.

25. Procédé selon la revendication 1, dans lequel les particules de silice ont une surface spécifique de 50 m 2/g ou moins.

40 26. Procédé selon la revendication 25, dans lequel les particules de silice ont une surface spécifique de 35 m 2/g ou moins.

27. Procédé selon la revendication 1, dans lequel la dispersion de silice est combinée avec 8 à 36 mmol/m2 (sur la base de la surface spécifique BET de la silice) de l’agent de traitement de type silylamine.

45 28. Procédé selon la revendication 27, dans lequel la dispersion de silice est combinée avec 9 à 18m mol/m2 (sur la base de la surface spécifique BET de la silice) de l’agent de traitement de type silylamine.

29. Procédé selon la revendication 1, dans lequel le mélange réactionnel comprend au plus 20 % en poids d’un solvant organique. 50 30. Procédé selon la revendication 29, dans lequel le mélange réactionnel est exempt de solvant organique.

31. Procédé selon la revendication 1, dans lequel le mélange réactionnel est constitué essentiellement de la dispersion de silice colloïdale et de l’agent de traitement de type silylamine. 55 32. Procédé selon la revendication 1, dans lequel le pH est de 7 à 11.

33. Procédé selon la revendication 32, dans lequel le pH est de 9 à 11.

19 EP 1 807 347 B1

34. Procédé selon la revendication 1, dans lequel les particules de s ilice hydrophobe sont neutralisées avant le séchage.

35. Procédé selon la revendication 1, dans lequel la dispersion aqueuse colloïdale de silice est stabilisée.

5 36. Procédé pour préparer une composition de toner, comprenant les opérations consistant à :

(a) préparer des particules de silice hydrophobe- par le procédé de la revendication 1, et (b) combiner les particules de silice hydrophobe avec des particules de toner pour former une composition de toner. 10 37. Procédé pour préparer une composition de polymère, comprenant les opérations consistant à :

(a) préparer des particules de silice hydrophobe par le procédé de la revendication 1, et (b) combiner les particules de silice hydrophobe avec un polymère pour former une composition de polymère. 15 38. Procédé selon la revendication 37, dans lequel la composition de polymère est un époxy, une composition de revêtement, une composition filmogène, ou une composition plastique.

20 EP 1 807 347 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 928818 A [0003] • US 5989768 A [0008] • WO 2004035473 A1 [0003]

Non-patent literature cited in the description

• S. BRUNAUER ; P.H. EMMET ; I. TELLER. J. Am. Chemical Society, 1938, vol. 60, 309 [0015]