US20050032965A1 - Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution, and the uses thereof, in particular for reinforcing polymers - Google Patents

Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution, and the uses thereof, in particular for reinforcing polymers Download PDF

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US20050032965A1
US20050032965A1 US10/486,573 US48657304A US2005032965A1 US 20050032965 A1 US20050032965 A1 US 20050032965A1 US 48657304 A US48657304 A US 48657304A US 2005032965 A1 US2005032965 A1 US 2005032965A1
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silica
surface area
specific surface
ctab
reaction mixture
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Remi Valero
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Rhodia Chimie SAS
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/14—Pore volume
    • 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
    • C01P2006/16—Pore diameter
    • 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
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • C01P2006/80—Compositional purity
    • 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
    • C01P2006/90—Other properties not specified above
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a novel process for preparing silica, to silicas having a particular particle size distribution and/or a particular pore distribution, especially in the form of powder, of approximately spherical beads or of granules, and to their applications, such as the reinforcement of polymers.
  • the invention firstly provides a novel process for preparing silica, of the type comprising the reaction of a silicate with an acidifying agent whereby a silica suspension is obtained, followed by the separation and the drying of this suspension, characterized in that the reaction of the silicate with the acidifying agent is carried out according to the following successive steps:
  • the acidifying agent and the silicate are chosen in a manner well known per se.
  • acidifying agent a strong mineral acid, such as sulphuric acid, nitric acid or hydrochloric acid, or an organic acid, such as acetic acid, formic acid or carbonic acid, will in general be used.
  • a strong mineral acid such as sulphuric acid, nitric acid or hydrochloric acid
  • an organic acid such as acetic acid, formic acid or carbonic acid
  • the acidifying agent may be dilute or concentrated; its normality may be between 0.4 and 36N, for example between 0.6 and 1.5N.
  • the acidifying agent is sulphuric acid
  • its concentration may be between 40 and 180 g/l, for example between 60 and 130 g/l.
  • silicate it is possible to use any standard form of silicates such as metasilicates, disilicates and, advantageously, an alkali metal silicate, especially sodium or potassium silicate.
  • the silicate may have a concentration (expressed as SiO 2 content) of between 40 and 3-30 g/l, for example between 60 and 300 g/l, in particular between 60 and 260 g/l.
  • sulphuric acid will generally be employed as the acidifying agent, and sodium silicate as silicate.
  • sodium silicate is used, this is generally present with an SiO 2 /Na 2 O weight ratio of between 2.5 and 4, for example between 3.2 and 3.8.
  • the reaction between the silicate and the acidifying agent takes place in a very specific manner according to the following steps.
  • an aqueous stock having a pH of between 2 and 5 is formed.
  • the stock formed has a pH of between 2.5 and 5, especially between 3 and 4.5; this pH is, for example, between 3.5 and 4.5.
  • This initial stock may be obtained by addition of acidifying agent to water so as to obtain a pH value of the stock between 2 and 5, preferably between 2.5 and 5, especially between 3 and 4.5, and for example between 3.5 and 4.5.
  • It may also be prepared by addition of acidifying agent to a stock containing preformed silica particles at a pH of less than 7, so as to obtain a pH value between 2 and 5, preferably between 2.5 and 5, especially between 3 and 4.5 and for example between 3.5 and 4.5.
  • the stock formed in step (i) may optionally include an electrolyte. However, it is preferable for no electrolyte to be added during the preparation process, in particular in step (i).
  • electrolyte is understood here in its normally accepted meaning, that is to say it means any ionic or molecular substance which, when it is in solution, decomposes or dissociates to form ions or charged particles.
  • electrolyte mention may be made of a salt of the group of alkali-metal and alkaline-earth metal salts, especially the salt of the metal of the initial silicate and of the acidifying agent, for example sodium chloride in the case of the reaction of a sodium silicate with hydrochloric acid or, preferably, sodium sulphate in the case of the reaction of a sodium silicate with sulphuric acid.
  • the second step (step (ii)) consists of a simultaneous addition of acidifying agent and of silicate in such a way (in particular with such flow rates) that the pH of the reaction mixture is maintained between 2 and 5, preferably between 2.5 and 5, especially between 3 and 4.5, for example between 3.5 and 4.5.
  • a step (iii) the addition of the acidifying agent is stopped, while continuing to add silicate into the reaction mixture so as to obtain a pH value of the reaction mixture of between 7 and 10, preferably between 7.5 and 9.5.
  • this maturing step may, for example, last 2 to 45 minutes, in particular from 5 to 25 minutes, and preferably includes neither addition of acidifying agent nor addition of silicate.
  • step (iii) and the optional maturing step acidifying agent and silicate are again simultaneously added in such a manner (in particular with such flow rates) that the pH of the reaction mixture is maintained between 7 and 10, preferably between 7.5 and 9.5.
  • step (iv) is advantageously carried out in such a way that the pH value of the reaction mixture is always equal (to within ⁇ 0.2) to that achieved after the preceding step.
  • step (ii) and step (iv) for example between, on the one hand, the optional maturing step following step (iii) and, on the other hand, step (iv), to add acidifying agent to the reaction mixture, the pH of the reaction mixture after this addition of acidifying agent being, however, between 7 and 9.5, preferably between 7.5 and 9.5.
  • a step (v) the addition of the silicate is stopped, while continuing to add acidifying agent into the reaction mixture so as to obtain a pH value of the reaction mixture of less than 6, preferably between 3 and 5.5, in particular between 3 and 5, for example between 3 and 4.5.
  • this step (v) may then be advantageous, after this step (v) and therefore just after stopping the addition of acidifying agent, for the reaction mixture to undergo a maturing step, especially at the pH obtained after step (v), and in general with stirring; this maturing step may last, for example, from 2 to 45 minutes, in particular from 5 to 20 minutes, and preferably includes no addition of acidifying agent nor addition of silicate.
  • the reaction vessel in which the entire reaction between the silicate and the acidifying agent takes place is usually fitted with suitable stirring equipment and with suitable heating equipment.
  • the entire reaction between the silicate and the acidifying agent is generally carried out between 70 and 95° C., in particular between 75 and 90° C.
  • the entire reaction between the silicate and the acidifying agent is carried out at a constant temperature, usually between 70 and 95° C., in particular between 75 and 90° C.
  • the temperature at the end of the reaction is higher than the temperature at the start of the reaction: thus, the temperature at the start of the reaction is preferably maintained (for example during steps (i) to (iii)) at between 70 and 85° C., and then the temperature is increased, preferably up to a value between 85 and 95° C., at which value it is maintained (for example during steps (iv) and (v)) until the end of the reaction.
  • the separation used in the preparation-process according to the invention usually comprises filtration followed, if necessary, by washing.
  • the filtration is carried out using any suitable method, for example by means of a filter press, a band filter or a vacuum filter.
  • the silica suspension thus recovered (the filter cake) is then dried.
  • This drying may be carried out using any means known per se.
  • the drying is spray drying.
  • any suitable type of spray dryer may be used, especially a turbine, nozzle, liquid-pressure or two-fluid type spray dryer.
  • a turbine spray dryer is used, and when the filtration is carried out by means of a vacuum filter, a turbine spray dryer is used.
  • the filter cake is not always under conditions allowing spray drying, especially because of its high viscosity.
  • the cake is then subjected to a disintegration operation.
  • This operation may be carried out mechanically, by passing the cake through a colloidal-type mill or a ball mill.
  • the disintegration is generally carried out in the presence of an aluminium compound, in particular sodium aluminate, and optionally in the presence of an acidifying agent, as described above (in the latter case, the aluminium compound and the acidifying agent are generally added simultaneously).
  • the disintegration operation makes it possible in particular to lower the viscosity of the suspension to be subsequently dried.
  • the silica that can then be obtained is usually in the form of approximately spherical beads.
  • the silica that can then be obtained is generally in the form of a powder.
  • the silica that can then be obtained may be in the form of a powder.
  • the product dried (especially by a turbine spray dryer) or milled as indicated above, may optionally be subjected to an agglomeration step which consists, for example, of direct compression, wet granulation (that is to say with the use of a binder such as water, a silica suspension, etc.), extrusion or, preferably, dry compacting.
  • agglomeration step which consists, for example, of direct compression, wet granulation (that is to say with the use of a binder such as water, a silica suspension, etc.), extrusion or, preferably, dry compacting.
  • de-aeration an operation also called predensification or degassing
  • the silica that can then be obtained by this agglomeration step is generally in the form of granules.
  • the silica powders like the silica beads, obtained by the process according to the invention thus offer the advantage inter alia of obtaining granules in a simple, effective and economic manner, especially by conventional forming operations, such as for example granulation or compacting, without these operations causing any degradation liable to mask, or even destroy, the good intrinsic properties that these powders or these beads have, as may be the case in the prior art when processing conventional powders.
  • the preparation process according to the invention makes it possible in particular to obtain silicas more of the precipitative-silica type which, on the one hand, are highly structured and non-friable and, on the other hand, generally have a high dispersibility in polymers, give the latter a very satisfactory compromise of properties, in particular as regards their dynamic and mechanical properties (especially a good reinforcing effect and very good abrasion resistance), without impairing their Theological properties.
  • the silicas obtained preferably have a particular particle size distribution and/or pore distribution.
  • the silicas that can be obtained by the process of the invention constitute one of the aspects of the present invention.
  • Further objects of the invention consist of novel silicas, more of the precipitated-silica type, which are highly structured and possess a specific particle size distribution and/or a particular pore distribution; furthermore, they generally have good dispersibility in polymers, give the latter a very satisfactory compromise of properties, in particular as regards their dynamic properties (especially a reduction in the strain energy dissipation (low Payne effect), low hysteresis losses at high temperature (especially a reduction in tan ⁇ at 60° C.) without impairing their rheological properties (and therefore without impairing their processability/formability (for example, a lower green viscosity for the same specific surface area)) and possess good mechanical properties, in particular a good reinforcing effect, especially in terms of moduli, and very good abrasion resistance, hence improved wear resistance in the case of finished articles based on the said polymers.
  • dynamic properties especially a reduction in the strain energy dissipation (low Payne effect), low hysteresis losses at high temperature
  • the BET specific surface area is determined using the Brunauer-Emmet-Teller method described in “The Journal of the American Chemical Society”, Vol. 60, page 309, February 1938 and corresponding to the International Standard ISO 5794/1 (Appendix D).
  • the CTAB specific surface area is the external surface area determined according to the NF T 45007 (November 1987) (5.12) standard.
  • the DOP oil uptake is determined according to the NF T 30-022 (March 1953) standard using dioctyl phthalate.
  • the pH is measured according to the ISO 787/9 standard (the pH of a 5% suspension in water).
  • the XDC particle size analysis method using centrifugal sedimentation, by which, on the one hand, the size distribution widths of silica objects and, on the other hand, the XDC mode illustrating its size of objects were measured, is described below.
  • the apparatus register record the values of the 16 wt %, 50 wt % (or median) and 84 wt % let-through diameters and the value of the mode (the derivative of the cumulative particle size curve gives a frequency curve the abscissa of the maximum of which (abscissa of the main population) is called the mode).
  • the size distribution width L d of objects corresponds to the (d84 ⁇ d16)/d50 ratio in which dn is the size for which n % of particles (by weight) have a size smaller than that size (the distribution width L d is therefore calculated from the cumulative particle size curve taken in its entirety).
  • the size distribution width L′ d of objects smaller than 500 nm, measured by XDC particle size analysis, after ultrasonic disintegration (in water), corresponds to the (d84 ⁇ d16)/d50 ratio in which dn is the size for which n % of particles (by weight), with respect to the particles smaller in size than 500 nm, have a size smaller than that size (the distribution width L′ d is therefore calculated from the cumulative particle size curve truncated above 500 nm).
  • each specimen is prepared as follows: each specimen is predried for 2 hours in an oven at 200° C. and then placed in a test container within 5 minutes following its removal from the oven and vacuum-degassed, for example using a rotary vane pump; the pore diameters (AUTOPORE III 9420 Micromeritics porosimeter) are calculated by the Washburn equation with a contact angle ⁇ of 140° and a surface tension ⁇ of 484 dynes/cm (or N/m).
  • V (d5 ⁇ d50) represents the pore volume formed by the pores of diameters between d5 and d50 and V (d 5 ⁇ d100) represents the pore volume formed by the pores of diameters between d5 and d100, dn here being the pore diameter for which n % of the total surface area of all the pores is formed by the pores of diameter greater than that diameter (the total surface area of the pores (S 0 ) may be determined from the mercury intrusion curve).
  • the dispersibility (and disintegratability) of the silicas according to the invention may be quantified by means of specific disintegration tests.
  • the cohesion of the agglomerates is assessed by a particle size measurement (using laser diffraction) carried out on a suspension of silica ultrasonically disintegrated beforehand; in this way, the disintegratability of the silica (the break-up of objects from 0.1 to a few tens of microns) is measured.
  • the ultrasonic disintegration is carried out using a Bioblock Vibracell sonifier (600-W) fitted with a 19 mm diameter probe.
  • the particle size measurement is carried out by laser diffraction on a SYMPATEC particle size analyser.
  • the value of the median diameter ⁇ 50S (or Sympatec median diameter) that is obtained is smaller the higher the disintegratability of the silica. It is also possible to determine the (10 ⁇ volume of suspension (in ml) introduced)/(optical density of the suspension detected by the particle size analyser) ratio may also be determined (this optical density is around 20). This ratio is indicative of the content of particles of a size of less than 0.1 ⁇ m, which particles are not detected by the particle size analyser. This ratio is called the ultrasonic Sympatec disintegration factor (F DS ).
  • F DS ultrasonic Sympatec disintegration factor
  • the cohesion of the agglomerates is assessed by a particle size measurement (using laser diffraction) carried out on a suspension of silica ultrasonically disintegrated beforehand; in this way, the disintegrability of the silica (break-up of objects from 0.1 to a few tens of microns) is measured.
  • the ultrasonic disintegration is carried out using a Bioblock VIBRACELL sonifier (600 W), used at 80% of maximum power, fitted with a 19 mm diameter probe.
  • the particle size measurement is carried out by laser diffraction on a Malvern Mastersizer 2000 particle size analyser.
  • silica 1 gram is weighed in a pillbox (height: 6 cm and diameter: 4 cm) and deionized water is added to bring the weight to 50 grams: an aqueous suspension containing 2% silica, which is homogenized for 2 minutes by magnetic stirring, is thus produced. Ultrasonic disintegration is then carried out for 420 seconds. Next, the particle size measurement is taken after all of the homogenized suspension has been introduced into the container of the particle size analyser.
  • the value of the median diameter ⁇ 50M (or Malvern median diameter) that is obtained is smaller the higher the disintegratability of the silica. It is also possible to determine the (10 ⁇ blue laser obscuration value)/(red laser obscuration value) ratio. This ratio is indicative of the content of particles smaller in size than 0.1 ⁇ m. This ratio is called the Malvern ultrasonic disintegration factor (F DM ).
  • a disintegration rate may be measured by means of another ultrasonic disintegration test, at 100% power of a 600 watt probe, operating in pulsed mode (i.e.: on for 1 second/off for 1 second) so as to prevent the ultrasonic probe from heating up excessively during the measurement.
  • This known test forming the subject matter for example of Application WO 99/28376 (see also Applications WO 99/28380, WO 00/73372 and WO 00/73373), allows the variation in the volume-average size of the particle agglomerates to be continuously measured during sonification, according to the indications given below.
  • the set-up used consists of a laser particle size analyser (of the MASTERSIZER S type sold by Malvern Instruments: He—Ne laser source emitting in the red at a wavelength of 632.8 nm) and of its preparation station (Malvern Small Sample Unit MSX1), between which a continuous flux stream treatment cell (Bioblock M72410) fitted with an ultrasonic probe (600 watt VIBRACELL-type 12.7 mm sonifier sold by Bioblock) was inserted. A small quantity (150 mg) of silica to be analysed is introduced with 160 ml of water into the preparation station, the rate of circulation being set at its maximum.
  • At least three consecutive measurements are carried out in order to determine, using the known Fraunhofer calculation method (Malvern 3$$D calculation matrix), the initial volume-average diameter of the agglomerates, denoted d v [0].
  • Sonification pulsesed mode: on for 1 s/off for 1 s
  • 100% power i.e. 100% of the maximum position of the tip amplitude
  • the variation in the volume-average diameter d v [t] as a function of time t is monitored for about 8 minutes, a measurement being taken approximately every 10 seconds.
  • the aforementioned Application WO 99/28376 describes in detail a measurement device that can be used for carrying out this ultrasonic disintegration test.
  • This device consists of a closed circuit in which a stream of particle agglomerates in suspension in a liquid can circulate.
  • This device essentially comprises a specimen preparation station, a laser particle size analyser and a treatment cell. Setting to atmospheric pressure, within the specimen preparation station and the actual treatment cell, makes it possible for the air bubbles that form during sonification (i.e. the action of the ultrasonic probe) to be continuously removed.
  • the specimen preparation station (Malvern Small Sample Unit MSX1) is designed to receive the silica specimen to be tested (in suspension in the liquid) and to make it circulate around the circuit at the preset speed (potentiometer ⁇ maximum speed about 3 l/min) in the form of a stream of liquid suspension.
  • This preparation station simply consists of a receiving container which contains the suspension to be analysed and through which the said suspension flows. It is equipped with a variable-speed stirring motor so as to prevent any sedimentation of the particle agglomerates of the suspension, a centrifuge mini-pump is designed to circulate the suspension in the circuit; the inlet of the preparation station is connected to the open air via an opening intended to receive the charge specimen to be tested and/or the liquid used for the suspension.
  • a laser particle size analyser (MASTERSIZER S) whose function is to continuously measure, at regular time intervals, the volume-average size d v of the agglomerates, as the stream passes, by a measurement cell to which the recording means and the automatic calculation means of the particle size analyser are coupled.
  • laser particle size analysers make use, in a known manner, of the principle of light diffraction by solid objects in suspension in a medium whose refractive index is different from that of the solid. According to the Fraunhofer theory, there is a relationship between the size of the object and the angle of diffraction of the light (the smaller the object the larger the angle of diffraction).
  • a treatment cell fitted with an ultrasonic probe is inserted between the preparation station and the laser particle size analyser, the said cell being able to operate in continuous or pulsed mode and intended to continuously break up the particle agglomerates as the stream passes.
  • This stream is thermostatically controlled by means of a cooling circuit placed, within the cell, in a jacket surrounding the probe, the temperature being controlled, for example, by a temperature probe immersed in the liquid within the preparation station.
  • the Sears number is determined using the method described by G. W. Sears in the article in Analytical Chemistry, Vol. 28, No. 12, December 1956 entitled “ Determination of specific surface area of colloidal silica by titration with sodium hydroxide”.
  • the Sears number is the volume of 0.1M sodium hydroxide solution needed to raise the pH of a 10 g/l silica suspension in a 200 g/l sodium chloride medium from 4 to 9.
  • the solution obtained is then homogenized by magnetic stirring, using a bar magnet having dimensions of 25 mm ⁇ 5 mm. A check is made that the pH of the suspension is less than 4, if necessary by adjusting it using a 1M hydrochloric acid solution.
  • a 0.1M sodium hydroxide solution is added at a rate of 2 ml/min by means of a Metrohm titrator pH meter (672 Titroprocessor, 655 Dosimat) precalibrated using pH 7 and pH 4 buffer solutions.
  • the titrator pH meter was programmed as follows: 1) Call up the “Get pH” program- and 2) Introduce the following parameters: pause (wait time before the start of titration): 3 s; reactant flow rate: 2 ml/min; anticipation (adaptation of the titration rate to the slope of the pH curve): 30; stop pH: 9.40; critical EP (sensitivity of detection of the equivalence point): 3; report (parameters for printing the titration report): 2, 3 and 5 (i.e. creation of a detailed report, list of measurement points and titration curve)).
  • the exact volumes V 1 and V 2 of sodium hydroxide solution added in order to obtain a pH of 4 and a pH of 9, respectively, are determined by interpolation.
  • the Sears number for 1.5 grams of dry silica is equal to ((V 2 ⁇ V 1 ) ⁇ 150)/(SC ⁇ M), where:
  • the number of silanols per nm 2 of surface area is determined by grafting methanol onto the surface of the silica.
  • 1 gram of raw silica is put into suspension in 10 ml of methanol, in a 110 ml autoclave (Top Industrie, reference 09990009).
  • a bar magnet is introduced and the autoclave, hermetically sealed and thermally insulated, is heated to 200° C. (40 bar) on a magnetic stirrer, heating for 4 hours.
  • the autoclave is then cooled in a cold water bath.
  • the grafted silica is recovered by settling and the residual methanol is evaporated in a stream of nitrogen.
  • the grafted silica is vacuum dried for 12 hours at 130° C.
  • the carbon content is determined by an elemental analyser (NCS 2500 analyser from CE Instruments) on the raw silica and on the grafted silica. This quantitative determination is carried out on the grafted silica within the three days following the end of drying—this is because the humidity of the air or heat may cause hydrolysis of the methanol grafting.
  • silica according to this variant of the invention possesses, for example:
  • This silica may have a ratio V (d5 ⁇ d50) /V (d5 ⁇ d100) of at least 0.73, in particular at least 0.74. This ratio may be at least 0.78, especially at least 0.80 or even at least 0.84.
  • This silica may have a pore distribution width ldp of greater than 1.05, for example greater than 1.25 or even greater than 1.40.
  • the silica according to this variant of the invention preferably possesses a size distribution width L d ((d84 ⁇ d16)/d50) of objects measured by XDC particle size analysis after ultrasonic disintegration, of at least 0.91, in particular at least 0.94, for example at least 1.0.
  • This silica may have a ratio V (d5 ⁇ d50) /V (d5 ⁇ d100) of at least 0.73, in particular at least 0.74. This ratio may be at least 0.78, especially at least 0.80 or even at least 0.84.
  • This silica may have a ratio V (d5 ⁇ d50) /V (d5 ⁇ d100) of at least 0.78, especially at least 0.80 or even at least 0.84.
  • the pore volume provided by the coarsest pores usually represents the largest proportion of the structure.
  • the silicas may have both an object size distribution width L d of at least one 1.04 and an object size (smaller than 500 nm) distribution width L′ d of at least 0.95.
  • the size distribution width L d of objects of the silicas according to the invention may in certain cases be at least 1.10, in particular at least 1.20; it may be at least 1.30, for example at least 1.50 or even at least 1.60.
  • the object size (smaller than 500 nm) distribution L′ d of the silicas according to the invention may be, for example, at least 1.0, in particular at least 1.10 and especially at least 1.20.
  • the silicas according to the invention possess a particular surface chemistry such that they have a (Sears number ⁇ 1000)/(BET specific surface area (S BET )) ratio of less than 60, preferably less than 55, for example less than 50.
  • the silicas according to the invention generally have a high, and therefore a typical object size which may be such that the mode of their particle size distribution measured by XDC particle size analysis after ultrasonic disintegration (in water) satisfies the condition: XDC mode (nm) ⁇ (5320/S CTMB (m 2 /g))+8, or even the condition: XDC mode (in nm) ⁇ (5320/S CTAB (m 2 /g))+10.
  • the silicas according to the invention may possess, for example, a pore volume (V 80 ) formed by the pores having diameters between 3.7 and 80 nm of at least 1.35 cm 3 /g, in particular at least 1.40 cm 3 /g or even at least 1.50 cm 3 /g.
  • V 80 pore volume formed by the pores having diameters between 3.7 and 80 nm of at least 1.35 cm 3 /g, in particular at least 1.40 cm 3 /g or even at least 1.50 cm 3 /g.
  • the silicas according to the invention preferably have a satisfactory dispersibility in polymers.
  • ⁇ 50S Their median diameter ( ⁇ 50S ), after ultrasonic disintegration, is in general less than 8.5 ⁇ m; it may be less than 6.0 ⁇ m, for example less than 5.5 ⁇ m.
  • ⁇ 50M median diameter after ultrasonic disintegration, is in general less than 8.5 ⁇ m, it may be less than 6.0 ⁇ m, for example less than 5.5 ⁇ m.
  • ⁇ a rate of disintegration, denoted by ⁇ , measured in the test referred to previously as ultrasonic disintegration in pulsed mode, at 100% power of a 600 watt probe, of at least 0.0035 ⁇ m ⁇ 1 .min ⁇ 1 , in particular at least 0.0037 ⁇ m ⁇ 1 .min ⁇ 1 .
  • the silicas according to the invention may have an ultrasonic disintegration factor (F DS ) of greater than 3 ml, in particular greater than 3.5 ml, especially greater than 4.5 ml.
  • F DS ultrasonic disintegration factor
  • F DM ultrasonic disintegration factor
  • the silicas according to the present invention may have a weight-average particle size, measured by XDC particle size analysis after ultrasonic disintegration, d w , of between 20 and 300 nm, especially between 30 and 300 nm, for example between 40 and 160 nm.
  • the silicas according to the present invention also have at least one, or even all, of the following three characteristics:
  • the silicas according to the invention generally have:
  • Their CTAB specific surface area may be between 90 and 230 m 2 /g, especially between 95 and 200 m 2 /g, for example between 120 and 190 m 2 /g.
  • their BET specific surface area may be between 110 and 270 m 2 /g, especially between 115 and 250 m 2 /g, for example between 135 and 235 m 2 /g.
  • the silicas according to the invention generally have:
  • Their CTAB specific surface area may be between 115 and 260 m 2 /g, especially between 145 and 260 m 2 /g.
  • their BET specific surface area may be between 120 and 280 m 2 /g, especially between 150 and 280 m 2 /g.
  • the silicas according to the present invention may have a certain microporosity; thus, the silicas according to the invention usually are such that (S BET ⁇ S CTAB ) ⁇ 5 m 2 /g, in particular ⁇ 15 m 2 /g, for example ⁇ 25 m 2 /g.
  • the silicas according to the invention are generally such that (S BET ⁇ S CTAB ) ⁇ 50 m 2 /g, preferably ⁇ 40 m 2 /g.
  • the pH of the silicas according to the invention is usually between 6.3 and 7.8, especially between 6.6 and 7.5.
  • DOP oil uptake that varies, usually, between 220 and 330 ml/100 g, for example between 240 and 300 ml/100 g.
  • They may be in the form of approximately spherical beads with a mean size of at least 80 ⁇ M.
  • This mean size of the beads may be at least 100 ⁇ m, for example at least 150 ⁇ m; it is in general at most 300 ⁇ m and preferably lies between 100 and 270 ⁇ m.
  • This mean size is determined according to the NF X 11507 (December 1970) standard by dry screening and determination of the diameter corresponding to a cumulative oversize of 50%.
  • the silicas according to the invention may also be in the form of powder having a mean size of at least 15 ⁇ m; for example, it is between 15 and 60 ⁇ m (especially between 20 and 45 ⁇ m) or between 30 and 150 ⁇ m (especially between 45 and 120 ⁇ m).
  • They may also be in the form of granules having a size of at least 1 mm, in particular between 1 and 10 mm, along the axis of their largest dimension (length).
  • the silicas according to the invention are preferably prepared by the preparation process according to the invention and described above.
  • silicas according to the invention or those prepared by the process according to the invention find particularly useful application in the reinforcement of natural or synthetic polymers.
  • the polymer compositions in which they are used, especially as reinforcing filler, are in general based on one or more polymers or copolymers, in particular one or more elastomers, especially thermoplastic elastomers, preferably having at least one glass transition temperature between ⁇ 150 and +300° C., for example between ⁇ 150 and +20° C.
  • diene polymers in particular diene elastomers.
  • polymers or copolymers derived from aliphatic or aromatic monomers comprising at least one unsaturated group such as especially ethylene, propylene, butadiene, isoprene and styrene), polybutyl acrylate, or blends thereof; mention may also be made of silicone elastomers, functionalized elastomers (for example those functionalized by functional groups capable of reacting with the surface of the silica) and halogenated polymers.
  • silicone elastomers for example those functionalized by functional groups capable of reacting with the surface of the silica
  • halogenated polymers for example, polyamides may be mentioned.
  • the polymer (or copolymer) may be a bulk polymer (or copolymer), a polymer (or copolymer) latex or a solution of a polymer (or copolymer) in water or in any other suitable dispersing liquid.
  • diene elastomers mention may be made, for example, of polybutadienes (BR), polyisoprenes (IR), butadiene copolymers, isoprene copolymers, or blends thereof, and in particular styrene-butadiene copolymers (SBR, especially emulsion styrene-butadiene copolymers ESBR or solution styrene-butadiene copolymers SSBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), styrene-butadiene-isoprene copolymers (SBIR) and ethylene-propylene-diene terpolymers (EPDM).
  • BR polybutadienes
  • IR polyisoprenes
  • IR butadiene copolymers
  • isoprene copolymers or blends thereof
  • SBR
  • NR natural rubber
  • the polymer compositions may be sulphur-vulcanized (vulcanisates are then obtained) or crosslinked, especially by peroxides.
  • the polymer compositions furthermore include at least one coupling (silica/polymer) agent and/or at least one covering agent; they may also include inter alia an antioxidant.
  • the coupling agent may be pregrafted onto the polymer.
  • silica according to the invention may allow the quantity of coupling agent to be employed in reinforced polymer compositions to be substantially reduced, for example by around 20%, while maintaining a substantially identical compromise of properties.
  • the coupling agent may optionally be combined with a suitable “coupling activator”, that is to say a compound which, when mixed with this coupling agent, increases the effectiveness of the latter.
  • the proportion by weight of silica in the polymer composition may vary over quite a wide range. Usually it represents from 20 to 80%, for example 30 to 70%, of the quantity of polymer(s).
  • the silica according to the invention may advantageously constitute all of the inorganic reinforcing filler, and even all of the reinforcing filler, of the polymer composition.
  • At least one other reinforcing filler such as in particular a commercial highly dispersible silica such as, for example, Z1165 MP or Z1115 MP, a treated precipitated silica (for example one “doped” using a cation such as aluminium), or another inorganic reinforcing filler such as, for example, alumina, or even an organic reinforcing filler, especially carbon black (optionally covered with an inorganic layer, for example with silica), may optionally be combined with this silica according to the invention.
  • the silica according to the invention therefore preferably constitutes at least 50%, or even at least 80%, by weight of all of the reinforcing filler.
  • a coupling (silica/polymer) agent polymer compositions based, for example, on natural rubber (NR), polyisoprene (IR), polybutadiene (BR), styrene-butadiene copolymer (SBR) and butadiene-acryonitrile copolymer (NBR).
  • NR natural rubber
  • IR polyisoprene
  • BR polybutadiene
  • SBR styrene-butadiene copolymer
  • NBR butadiene-acryonitrile copolymer
  • a coupling (silica/polymer) agent polymer compositions based, for example, on natural rubber (NR), polyisoprene (IR), polybutadiene (BR), styrene-butadiene copolymer (SBR), polychloroprene, butadiene-acrylonitrile copolymer (NBR), hydrogenated or carboxylated nitrile rubber, isobutylene-isoprene copolymer (IIR), halogenated (especially brominated or chlorinated) butyl rubber, ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), chlorinated polyethylene, chlorosulphonated polyethylene, epichlorohydrin rubber, silicones, fluorocarbon rubber and polyacrylates.
  • NR natural rubber
  • IR polyisoprene
  • BR polybutadiene
  • SBR styrene-butadiene copolymer
  • the silicas according to the invention or those prepared by the process according to the invention may also be employed as a catalyst support, as an absorbent for active materials (in particular a support for liquids, for example those used in food, such as vitamins (vitamin E), choline chloride), as a viscosity-modifying, texturing or anti-clumping agent, as an element for battery separators, or as an additive for dentrifices or for paper.
  • active materials in particular a support for liquids, for example those used in food, such as vitamins (vitamin E), choline chloride
  • a viscosity-modifying, texturing or anti-clumping agent as an element for battery separators, or as an additive for dentrifices or for paper.
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.52) having a concentration of 230 g/l at a rate of 76 g/min and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.
  • the stirring rate was increased to 450 rpm.
  • reaction mixture is taken to a pH of 4 by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 10 minutes at pH 4.
  • 250 ml of flocculant FA 10 polyoxyethylene having a molar mass of 5 ⁇ 10 6 g
  • the slurry was filtered and washed under vacuum (16.7% solids content). After dilution (13% solids content), the cake obtained was mechanically broken up. The resulting slurry was spray dried by means of a turbine spray dryer.
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.55) having a concentration of 235 g/l at a rate of 50 g/min and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.
  • reaction mixture is taken to a pH of 4 over 5 minutes by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 10 minutes at pH 4.
  • the slurry was filtered and washed under vacuum (5.5% cake solids content). After dilution (12% solids content), the cake obtained was mechanically broken up. The resulting slurry was spray dried by means of a turbine spray dryer.
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.55) having a concentration of 230 g/l at a rate of 50 g/min and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.
  • a new simultaneous addition was carried out for 60 minutes with a sodium silicate flow rate of 50 g/min (the same sodium silicate as in the case of the first simultaneous addition) and a flow rate of sulphuric acid, with a concentration of 80 g/l, set so as to maintain the pH of the reaction mixture at a value of 8.
  • reaction mixture is taken to a pH of 4 over 4 minutes by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 10 minutes at pH 4.
  • the slurry was filtered and washed under vacuum (13.7% cake solids content). After dilution (11.2% solids content), the cake obtained was mechanically broken up. The resulting slurry was spray dried by means of a turbine spray dryer.
  • the characteristics of the silica P3 were then the following:
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.5) having a concentration of 230 g/l at a rate of 76 g/min and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 8.9.
  • a sol of scarcely aggregated particles was obtained.
  • the sol was withdrawn and rapidly cooled using a copper coil through which cold water circulates. The reactor was rapidly cleaned.
  • a new simultaneous addition was carried out for 60 minutes with a sodium silicate flow rate of 76 g/min (the same sodium silicate as in the case of the first simultaneous addition) and a flow rate of sulphuric acid, with a concentration of 80 g/l, set so as to maintain the pH of the reaction mixture at a value of 8.
  • the stirring rate was increased when the mixture became very viscous.
  • reaction mixture is taken to a pH of 4 over 5 minutes by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 10 minutes at pH 4.
  • the slurry was filtered and washed under vacuum (15% cake solids content). After dilution, the cake obtained was mechanically broken up. The resulting slurry was spray dried by means of a turbine spray dryer.
  • the characteristics of the silica P4 were then the following:
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.48) having a concentration of 230 g/l at a rate of 75 g/min and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.2.
  • the pH was brought to pH 8 by introducing sulphuric acid having a concentration of 80 g/l.
  • sulphuric acid having a concentration of 80 g/l.
  • a new simultaneous addition carried out over 50 minutes, of sodium silicate at a rate of 76 g/min (the same sodium silicate as in the first simultaneous addition) and of sulphuric acid, with a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 8.
  • reaction mixture is taken to a pH of 4 by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 10 minutes at pH 4.
  • the slurry was filtered and washed under vacuum (19.6% cake solids content). After dilution (10% solids content), the cake obtained was mechanically broken up. The resulting slurry was spray dried by means of a turbine spray dryer.
  • Silica Z1165 MP had the following characteristics:
  • compositions in parts by weight Composition R1 Composition C1 Composition C2 SBR (1) 100 100 100 Silica Z1165MP 50 0 0 Silica of 0 50 50 Example 4 Silane Si69 (2) 4 4 6.25 Diphenylguanidine 1.45 1.45 1.45 Stearic acid 1.1 1.1 1.1 Zinc oxide 1.82 1.82 1.82 Antioxidant (3) 1.45 1.45 1.45 Sulphenamide (4) 1.3 1.3 1.3 Sulphur 1.1 1.1 1.1 (1) Solution-synthesized styrene-butadiene copolymer (BUNA VSL 5525-0 type) not oil-extended; (2) Filler/polymer coupling agent (sold by Degussa); (3) N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine; (4) N-cyclohexyl-2-benzothiazyl sulphenamide (CBS).
  • BUNA VSL 5525-0 type Solution-synthesized st
  • Composition C1 contained a quantity of coupling agent identical to that of reference composition R1.
  • Composition C2 contained an optimized quantity of coupling agent with regard to the specific surface area of the silica used (Example 4).
  • compositions were prepared by thermomechanically working the elastomers in an internal mixer (of the Brabender type) having a volume of 75 cm 3 , in two steps, with a mean blade speed of 50 revolutions/minute until a temperature of 120° C. was obtained, these steps being followed by a finishing step carried out on an external mixer.
  • the vulcanization temperature was chosen to be 170° C.
  • the vulcanization conditions for the compositions were tailored to the vulcanization rates of the corresponding compounds.
  • compositions are given below, the measurements having been carried out (on the vulcanized compositions) according to the following standards and/or methods:
  • a Monsanto 100 S rheometer was used especially for the measurement of the minimum torque (C min ) and the maximum torque (C max ).
  • Ts2 corresponded to the time over which it was possible to monitor the mixture; the polymer mixture cured after Ts2 (start of vulcanization).
  • T90 corresponded to the time it took for the mixture to undergo 90% vulcanization.
  • the x % moduli corresponded to the stress measured at a tensile strain of x %.
  • TABLE 2 Vulcanization Composition R1 Composition C1 Composition C2 Cmin (in ⁇ lb) 10 21 14 Ts2 (min) 3.1 2.1 3.1 T90 (min) 29.4 42.0 36.4 C max (in ⁇ lb) 91 97.5 103 Mechanical 10% modulus 0.95 1.3 1.05 (MPa) 100% modulus 3.6 4.0 4.6 (MPa) 200% modulus 9.5 9.8 12.2 (MPa)
  • compositions C1 and C2 containing a silica according to the invention exhibit a useful compromise of properties compared with that of reference composition R1.
  • composition C1 led to a more pronounced reinforcement in terms of moduli than reference composition R1.
  • composition C2 results in a vulcanization rate comparable to that of reference composition R1; in addition, composition C2 has moduli (in particular, 100% and 200% moduli) very much higher than those obtained with reference composition R1.
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.53) having a concentration of 230 g/l at a rate of 50 g/min and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.2.
  • the pH was brought to pH 8 by introducing sulphuric acid having a concentration of 80 g/l.
  • sulphuric acid having a concentration of 80 g/l.
  • a new simultaneous addition carried out over 50 minutes, of sodium silicate at a rate of 50 g/min (the same sodium silicate as in the first simultaneous addition) and of sulphuric acid, with a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 8.
  • reaction mixture is taken to a pH of 4 by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 10 minutes at pH 4.
  • the slurry was filtered and washed under vacuum (16.8% cake solids content). After dilution (10% solids content), the cake obtained was mechanically broken up. The resulting slurry was spray dried by means of a turbine spray dryer.
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.52) having a concentration of 230 g/l at a rate of 190 l/hour and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.
  • reaction mixture is taken to a pH of 5.2 by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 5 minutes at pH 5.2.
  • the slurry was filtered and washed in a filter press (22% cake solids content).
  • the cake obtained was broken up by adding a quantity of sodium aluminate corresponding to an Al/SiO 2 weight ratio of 0.3%.
  • the resulting slurry was spray dried by means of a nozzle spray drier.
  • a sodium silicate solution (having an SiO 2 /Na 2 O weight ratio of 3.52) having a concentration of 230 g/l at a rate of 190 l/hour and sulphuric acid, having a concentration of 80 g/l, at a rate set so as to maintain the pH of the reaction mixture at a value of 4.
  • reaction mixture is taken to a pH of 5.2 by sulphuric acid having a concentration of 80 g/l.
  • the mixture is matured for 5 minutes at pH 5.2.
  • the slurry was filtered and washed in a vacuum filter (18% cake solids content).
  • the cake obtained was broken up mechanically using industrial water (10% of water added with respect to the cake) by adding a quantity of sodium aluminate corresponding to an Al/SiO 2 weight ratio of 0.3%.
  • the resulting slurry was spray dried by means of a turbine spray drier.
  • composition C3 the other containing silica prepared in Example 8 and a coupling agent (composition C3).
  • Composition R2 Composition C3 BR (1) 70 70 SBR (2) 15 15 NBR (3) 15 15 Silica Z1165MP 50 0 Silica of 0 50
  • Example 8 SILQUEST A1891 (4) 1 1 Liquid paraffin (5) 10 10 Stearic acid 1.5 1.5 Zinc oxide 3 3 Polyethylene 3 3 glycol (6) TBBS (7) 1 1 TBzTD (8) 0.6 0.6 Sulphur 1.5 1.5 (1) Polybutadiene (KOSYN KBR01 type); (2) Solution-synthesized styrene-butadiene copolymer (BUNA VSL 5025 type) not oil-extended; (3) Butadiene-acrylonitrile copolymer (KRYNAC 34-50 type); (4) ⁇ -Mercaptopropyltriethoxysilane filler/polymer coupling agent (sold by Crompton); (5) PLASTOL 352
  • compositions were prepared by thermomechanically working the elastomers in an internal mixer (Banbury type) having a volume of 1200 cm 3 .
  • the initial temperature and the speed of the rotors were set so as to achieve drop temperatures of the compounds of about 120° C. This step was followed by a finishing step carried out on an external mixer at temperatures below 110° C. This phase allowed the vulcanization system to be introduced.
  • the vulcanization temperature was chosen to be 160° C.
  • the vulcanization conditions for the compositions were tailored to the vulcanization rates of the corresponding mixtures.
  • compositions are given below, the measurements having been carried out according to the following standards and/or methods:
  • a Monsanto 100 S rheometer was used especially for the measurement of the minimum torque (C min ) and the maximum torque (C max ).
  • Ts2 corresponded to the time over which it was possible to monitor the mixture; the polymer mixture cured after Ts2 (start of vulcanization).
  • T90 corresponded to the time it took for the mixture to undergo 90% vulcanization.
  • the x % moduli corresponded to the stress measured at a tensile strain of x %.
  • Abrasion resistance DIN 53516 standard; the measured value is the abrasion loss: the lower the loss, the better the abrasion resistance.
  • Tensile strength 11.9 12.8 (MPa) Elongation at break 377 418 (%) Tear strength 68 73 (No. 10 notch) (kN/m) Shore A hardness 68 70 (pts) Abrasion loss (mm 3 ) 36 29
  • composition C3 containing a silica according to the invention exhibits a particularly beneficial compromise of properties compared with that of reference composition R2.
  • composition C3 While still having a vulcanization rate comparable to that of reference composition R2 and moduli similar to those of reference composition R2, composition C3 possesses a tensile strength, an elongation at break, a tear strength and a Shore hardness that are superior to those of reference composition R2. Above all, composition C3 has an abrasion resistance very much higher than reference composition R2: the abrasion loss is thus reduced by almost 20%.
  • composition C4 silica prepared in Example 9 and a coupling agent
  • composition C5 silica prepared in Example 9 and a coupling agent
  • Composition R3 Composition C4 Composition C5 SBR (1) 103 103 103 BR (2) 25 25 25 Silica Z1165MP 80 0 0 Silica of 0 80 0
  • Example 8 Silica of 0 0 80
  • Example 9 TESPT (3) 6.4 8.0 7.7 Stearic acid 2.0 2.0 2.0 Zinc oxide 2.5 2.5 2.5 Antioxidant (4) 1.9 1.9 1.9 DPG (5) 1.5 1.8 1.8 CBS (6) 2.0 2.0 2.0 2.0 2.0 Sulphur 1.1 1.1 1.1 (1)
  • Solution-synthesized styrene-butadiene copolymer (BUNA VSL 5025-1 type), oil-extended (37.5% by weight); (2) Polybutadiene (BUNA CB24 type sold by Bayer); (3) Filler/polymer coupling agent: bis(3-(triethoxys
  • Each of the three compositions was prepared in three successive phases.
  • the first two phases carried out in an internal mixer, allowed thermomechanical working at high temperature until a maximum temperature of about 150° C. was obtained. They were followed by a third mechanical working phase carried out on cylinders at temperatures below 110° C. The latter phase allowed the vulcanization system to be introduced.
  • the mixer employed for the first two phases was an internal mixer of the Brabender type, with a capacity of 70 cm 3 .
  • the initial temperature and the speed of the rotors were set each time so as to achieve drop temperatures of the compound close to 150° C.
  • the first step made it possible to incorporate the elastomers (at to), the silica (divided introduction, 2 ⁇ 3 then 1 ⁇ 3) with the coupling agent (at t 0 +2 min), then with the DPG (at t 0 +4 min) and finally the stearic acid (at t 0 +6 min).
  • a second step in this mixer made it possible, by a thermomechanical treatment, to improve the dispersion of the silica and of its coupling agent in the elastomeric matrix.
  • the zinc oxide and the antioxidant were incorporated (at t′ 0 +1 min).
  • the third phase made it possible to introduce the vulcanization system (sulphur and CBS). It was carried out on a cylinder mixer preheated to 50° C. The duration of this phase was between 5 and 20 minutes.
  • each final compound was calendered in the form of sheets 2-3 mm in thickness.
  • the vulcanization temperature was chosen to be 160° C.
  • the vulcanization conditions for the compositions were tailored to the vulcanization rates of the corresponding compounds.
  • compositions are given below, the measurements having been carried out according to the standards and/or methods indicated in Example 10.
  • compositions C4 and C5 each containing a silica according to the invention exhibit a particularly beneficial compromise of properties compared with that of reference composition R3.
  • compositions C4 and C5 While still having a vulcanization rate comparable to that of reference composition R3, compositions C4 and C5 possess moduli and a Shore hardness higher than those of reference composition R3. Above all, compositions C4 and C5 exhibit a much higher abrasion resistance than reference composition R3: the abrasion loss is thus reduced by about 20%. Finally, compositions C4 and C5 possess a lower tan ⁇ at 60° C. than reference composition R3, it also proving to be particularly beneficial in the case of the properties of finished articles based on these compositions C4 or C5.

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FR3123655B1 (fr) 2021-06-07 2023-04-28 Michelin & Cie Bande transporteuse comprenant une composition à base d’élastomère fortement saturé
FR3123919B1 (fr) 2021-06-15 2023-04-28 Michelin & Cie Composition de caoutchouc a base de copolymere contenant des unites ethylene et des unites dieniques, et de polyethylene
FR3123920B1 (fr) 2021-06-15 2023-04-28 Michelin & Cie Composition de caoutchouc a base de copolymere contenant des unites ethylene et des unites dieniques, et de polyethylene
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FR3124512B1 (fr) 2021-06-25 2024-10-04 Michelin & Cie Composition de caoutchouc
FR3124798B1 (fr) 2021-06-30 2024-09-06 Michelin & Cie Composition de caoutchouc
FR3127224B1 (fr) 2021-09-23 2023-09-29 Michelin & Cie Produit renforcé comprenant une composition de caoutchouc à base d’un composé polyphénolique, une guanidine et au moins un composé péroxyde
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FR3129676B1 (fr) 2021-11-26 2023-10-20 Michelin & Cie Mélange de caoutchouc comprenant un accélérateur de vulcanisation rapide
FR3130281B1 (fr) 2021-12-10 2025-07-25 Michelin & Cie Composition de caoutchouc antivibratoire
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FR3130810A1 (fr) 2021-12-16 2023-06-23 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
FR3131318B1 (fr) 2021-12-23 2023-11-17 Michelin & Cie Polymère portant des groupes pendants fonctionnels particuliers époxy.
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FR3133857B1 (fr) 2022-03-23 2024-03-08 Michelin & Cie Composition élastomérique aux propriétés améliorées
FR3135722B1 (fr) 2022-05-17 2024-04-19 Michelin & Cie Composition de caoutchouc a base d’un elastomere fortement sature et d’un plastifiant liquide
FR3135723B1 (fr) 2022-05-17 2024-04-19 Michelin & Cie Composition de caoutchouc a base d’un elastomere fortement sature et d’un plastifiant liquide polaire
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FR3136768B1 (fr) 2022-06-20 2024-05-31 Michelin & Cie Composition de caoutchouc diénique comportant une microsilice.
FR3136776B1 (fr) 2022-06-20 2024-05-31 Michelin & Cie Composition de caoutchouc diénique comprenant une polynitrone.
FR3136770B1 (fr) 2022-06-21 2024-05-10 Michelin & Cie Composition de caoutchouc comprenant un élastomère diénique fortement saturé
FR3136775B1 (fr) 2022-06-21 2024-05-10 Michelin & Cie Composition de caoutchouc comprenant un élastomère diénique fortement saturé
FR3136773B1 (fr) 2022-06-21 2024-05-10 Michelin & Cie Composition de caoutchouc comprenant un élastomère diénique fortement saturé
FR3136771B1 (fr) 2022-06-21 2024-05-10 Michelin & Cie Composition de caoutchouc comprenant un élastomère diénique fortement saturé
FR3137391B1 (fr) 2022-06-30 2024-06-21 Michelin & Cie Composition de caoutchouc comprenant un estolide comme plastifiant biosourcé
FR3137388B1 (fr) 2022-06-30 2024-06-21 Michelin & Cie Composition de caoutchouc comprenant un plastifiant biosourcé de la famille des estolides
FR3137389B1 (fr) 2022-06-30 2024-06-14 Michelin & Cie Composition de caoutchouc comprenant un ester d'acide gras comme plastifiant
FR3137390B1 (fr) 2022-06-30 2024-06-21 Michelin & Cie Composition de caoutchouc comprenant un plastifiant biosourcé
FR3138351B1 (fr) 2022-07-29 2025-04-25 Michelin & Cie Pneumatique à armature de carcasse radiale
FR3138352B1 (fr) 2022-07-29 2025-04-25 Michelin & Cie Pneumatique à armature de carcasse radiale
FR3138350B1 (fr) 2022-07-29 2025-04-18 Michelin & Cie Pneumatique à armature de carcasse radiale
FR3140374A1 (fr) 2022-10-04 2024-04-05 Compagnie Generale Des Etablissements Michelin Pneumatique
FR3140373A1 (fr) 2022-10-04 2024-04-05 Compagnie Generale Des Etablissements Michelin PNEUMATIQUE POURVU D'UN FLANC EXTERNE A BASE D'UNE COMPOSITION COMPRENANT du noir de carbone de pyrolyse
FR3141181B1 (fr) 2022-10-20 2024-10-04 Michelin & Cie Bandage plein de galet de roulement comprenant une composition de caoutchouc
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FR3143035B1 (fr) 2022-12-08 2024-11-29 Michelin & Cie Composition de caoutchouc
FR3144142A1 (fr) 2022-12-21 2024-06-28 Compagnie Generale Des Etablissements Michelin Compositions elastomeriques comprenant un noir de carbone de pyrolyse
FR3144147A1 (fr) 2022-12-21 2024-06-28 Compagnie Generale Des Etablissements Michelin Compositions elastomeriques comprenant un noir de carbone traité au silicium
FR3144145A1 (fr) 2022-12-21 2024-06-28 Compagnie Generale Des Etablissements Michelin Compositions elastomeriques comprenant un noir de carbone de pyrolyse
FR3144143A1 (fr) 2022-12-21 2024-06-28 Compagnie Generale Des Etablissements Michelin Compositions elastomeriques comprenant un noir de carbone traité au silicium
FR3144148A1 (fr) 2022-12-21 2024-06-28 Compagnie Generale Des Etablissements Michelin Compositions elastomeriques comprenant un noir de carbone de pyrolyse
FR3145756A1 (fr) 2023-02-09 2024-08-16 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc a base d’elastomere dienique fortement sature et d’un derive d’imidazole
FR3145755B1 (fr) 2023-02-09 2025-02-07 Michelin & Cie Composition de caoutchouc a base d’elastomere dienique fortement sature et d’une resine renforçante
FR3146144B1 (fr) 2023-02-24 2025-01-31 Michelin & Cie Compositions élastomériques aux propriétés améliorées
FR3146143B1 (fr) 2023-02-24 2025-01-31 Michelin & Cie Compositions élastomériques aux propriétés améliorées
CN120957875A (zh) 2023-03-28 2025-11-14 米其林集团总公司 包含特定增塑体系的橡胶组合物
FR3148030A1 (fr) 2023-04-24 2024-10-25 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
FR3148433B1 (fr) 2023-05-03 2025-03-21 Michelin & Cie Pneumatique à haute capacité de chargement à flancs résistants à l’ozone et à l’efflorescence
FR3148434A1 (fr) 2023-05-03 2024-11-08 Compagnie Generale Des Etablissements Michelin Pneumatique à haute capacité de chargement à flancs résistants à la déchirabilité
FR3149013A1 (fr) 2023-05-25 2024-11-29 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
FR3149014A1 (fr) 2023-05-25 2024-11-29 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
FR3149322B1 (fr) 2023-05-31 2025-05-02 Michelin & Cie Composition de caoutchouc comprenant un élastomère diénique fortement saturé
FR3149614B1 (fr) 2023-06-09 2025-05-02 Michelin & Cie Composition de caoutchouc antivibratoire
FR3149613B1 (fr) 2023-06-09 2025-05-02 Michelin & Cie Composition de caoutchouc antivibratoire
FR3154408A1 (fr) 2023-10-20 2025-04-25 Compagnie Generale Des Etablissements Michelin Compositions de caoutchouc comprenant un système de réticulation spécifique
FR3154406A1 (fr) 2023-10-20 2025-04-25 Compagnie Generale Des Etablissements Michelin Compositions de caoutchouc comprenant un système de réticulation spécifique
FR3154409A1 (fr) 2023-10-20 2025-04-25 Compagnie Generale Des Etablissements Michelin Compositions de caoutchouc comprenant un système de réticulation spécifique
FR3156448B1 (fr) 2023-12-12 2025-10-31 Michelin & Cie Composition de caoutchouc a base d’elastomere dienique fortement sature
FR3156798A1 (fr) 2023-12-19 2025-06-20 Compagnie Generale Des Etablissements Michelin Bandage pour bicyclette
FR3156797A1 (fr) 2023-12-19 2025-06-20 Compagnie Generale Des Etablissements Michelin Bandage pour bicyclette
FR3156796A1 (fr) 2023-12-19 2025-06-20 Compagnie Generale Des Etablissements Michelin Bandage pour bicyclette
FR3156799B1 (fr) 2023-12-19 2025-11-07 Michelin & Cie Bandage pour bicyclette
WO2025133223A1 (fr) 2023-12-22 2025-06-26 Rhodia Operations Procédé hydrothermal pour la préparation de silicate et de silice précipitée à partir de sable de fonderie usé
WO2025133233A1 (fr) 2023-12-22 2025-06-26 Rhodia Operations Procédé de préparation en four de silicate et de silice précipitée à partir de sable de fonderie usé, et silicate et silice précipitée pouvant être obtenus par ce procédé
CN118005023A (zh) * 2024-02-07 2024-05-10 金三江(肇庆)硅材料股份有限公司 二氧化硅的制备方法和牙膏
FR3159554A1 (fr) 2024-02-22 2025-08-29 Compagnie Generale Des Etablissements Michelin Pneumatique comprenant au moins une nappe de travail presentant un compromis de propriétés amélioré
FR3159971B1 (fr) 2024-03-05 2026-02-06 Michelin & Cie Composition de caoutchouc comprenant un elastomere dienique fortement sature
FR3161217B1 (fr) 2024-04-11 2026-03-27 Michelin & Cie Composition de caoutchouc comprenant une huile hydrocarbure à base d’une coupe issue de la pyrolyse
FR3161218B1 (fr) 2024-04-11 2026-03-27 Michelin & Cie Composition de caoutchouc comprenant une cire hydrocarbure à base d’une coupe issue de la pyrolyse
FR3163944A1 (fr) 2024-06-27 2026-01-02 Compagnie Generale Des Etablissements Michelin Produit renforcé à base d’au moins un élément de renfort métallique et d’une composition de caoutchouc.
FR3163946A1 (fr) 2024-06-28 2026-01-02 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe a base d'une composition comprenant un noir de carbone de pyrolyse et des nanotubes de carbone
FR3163945A1 (fr) 2024-06-28 2026-01-02 Compagnie Generale Des Etablissements Michelin Compositions élastomériques comprenant au moins un noir de carbone de pyrolyse et des nanotubes de carbone
FR3163942A1 (fr) 2024-07-01 2026-01-02 Compagnie Generale Des Etablissements Michelin Polymere greffe portant des groupes pendants fonctionnels imidazols
FR3165268A1 (fr) 2024-08-01 2026-02-06 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc a base d’elastomere dienique fortement sature
WO2026041441A1 (fr) 2024-08-19 2026-02-26 Rhodia Operations Amélioration de la dispersion de silice à l'aide d'une technologie de séchage par pulvérisation de vapeur surchauffée
FR3166634A1 (fr) 2024-09-24 2026-03-27 Compagnie Generale Des Etablissements Michelin Procédé de préparation d’un mélange caoutchouteux en phase liquide
FR3167155A1 (fr) 2024-10-03 2026-04-10 Compagnie Generale Des Etablissements Michelin Composition de caoutchouterie comprenant un antioxydant specifique

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BR0211703B1 (pt) 2012-02-22
EP1419106B1 (fr) 2016-10-12
JP4515761B2 (ja) 2010-08-04
EP1419106A1 (fr) 2004-05-19
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RU2270167C2 (ru) 2006-02-20
DK1419106T3 (en) 2017-01-30
EP2325141A1 (fr) 2011-05-25
CN100430317C (zh) 2008-11-05
EP2325141A9 (fr) 2012-05-23
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AU2002341047B8 (en) 2006-12-07
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CA2457769C (fr) 2011-04-26
RU2004107508A (ru) 2005-09-20
CN101412515A (zh) 2009-04-22
EP2325141B1 (fr) 2018-03-14
EP3078634A1 (fr) 2016-10-12
US20100221541A1 (en) 2010-09-02
CA2729228A1 (fr) 2003-02-27
CN1541186A (zh) 2004-10-27
PT1419106T (pt) 2016-12-27
US20110263784A1 (en) 2011-10-27
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KR100660366B1 (ko) 2006-12-21
US11241370B2 (en) 2022-02-08

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