NOVEL PROCESS FOR THE PREPARATION OF PRECIPITATED SILICES, NOVEL PRECIPITED SILICES AND THEIR USES,

专利摘要:

公开号:FR3017610A1
申请号:FR1400415
申请日:2014-02-14
公开日:2015-08-21
发明作者:Cedric Boivin；Laurent Guy；Kilani Lamiri；Eric Perin
申请人:Rhodia Operations SAS；
IPC主号:

专利说明:

[0001] FIELD OF THE INVENTION The present invention relates to a new process for the preparation of precipitated silica, new precipitated silicas and their applications, such as the reinforcement of polymers. BACKGROUND OF THE INVENTION It is known to employ reinforcing white fillers in polymers, in particular elastomers, such as, for example, precipitated silica. The object of the present invention is to provide, in particular, an alternative filler for polymer compositions which advantageously provides them with a reduction in their viscosity and an improvement in their dynamic properties while retaining their mechanical properties. It thus advantageously allows an improvement of the hysteresis / reinforcement compromise.
[0002] The present invention firstly proposes a new process for the preparation of precipitated silica using, during or after the disintegration operation, at least one polycarboxylic acid. In general, the preparation of precipitated silica is carried out by precipitation reaction of a silicate, such as an alkali metal silicate (sodium silicate for example), with an acidifying agent (sulfuric acid for example), and then separation filtration, obtaining a filter cake, precipitated silica obtained, then disintegration of said filter cake and finally drying (generally by atomization). The mode of precipitation of the silica may be arbitrary: in particular, addition of acidifying agent to a silicate base stock, total or partial simultaneous addition of acidifying agent and silicate on a base of water or silicate. One of the objects of the invention is a new process for the preparation of a precipitated silica of the type comprising the precipitation reaction between a silicate and an acidifying agent, whereby a suspension of precipitated silica is obtained, followed by separation. and drying said suspension, characterized in that it comprises the following successive steps: - the precipitation reaction is carried out in the following manner: (i) an aqueous base having a pH of between 2.0 and 5.0, (ii) at the same time, said silicate and acidifying agent are added to said base stock, such that the pH of the reaction medium is maintained between 2.0 and 5.0, (iii) one stops the addition of the acidifying agent while continuing the addition of silicate in the reaction medium until a pH value of the reaction medium of between 7.0 and 10.0 is obtained, (iv) in the reaction medium, simultaneously with silicate and acidi In such a way that the pH of the reaction medium is maintained between 7.0 and 10.0, (v) the addition of the silicate is stopped while continuing the addition of the acidifying agent in the reaction medium until obtaining a pH value of the reaction medium of less than 6.0, the silica suspension obtained is filtered, the filtration cake obtained after the filtration is subjected to a disintegration operation, said process being characterized in that at least one polycarboxylic acid (for example a mixture of acids) is added to the filter cake, either during the disintegration process or after the disintegration operation and before the drying stage. polycarboxylic). According to the invention, the filter cake is subjected to a disintegration operation during which or after which at least one polycarboxylic acid is introduced. The mixture then obtained (suspension of precipitated silica) is then dried (generally by atomization). The disintegration operation is a fluidification or liquefaction operation, in which the filter cake is made liquid, the precipitated silica being in suspension. In a first variant of the invention, this disintegration operation is carried out by subjecting the filter cake to a chemical action by addition of at least one polycarboxylic acid, preferably coupled to a mechanical action (for example by passing through a tray continuously stirred or in a colloid mill) which usually induces a grain size reduction of the suspended silica. The suspension (in particular aqueous) obtained after disintegration has a relatively low viscosity.
[0003] In a second variant, this disintegration operation is carried out by subjecting the filter cake to a mechanical action (for example by passing through a continuously agitated tank or in a colloidal mill) which usually induces a grain size reduction of the silica. suspension. In this second variant, at least one polycarboxylic acid is added after the disintegration operation, that is to say to the silica cake disintegrated. The filter cake to be subjected to the disintegration operation may be composed of a mixture of several filter cakes, each of said cakes being obtained by filtration of a part of the silica suspension obtained at the end of the step ( v) (this suspension being, prior to filtration, divided into several parts).
[0004] According to the invention, the term "polycarboxylic acid" means polycarboxylic acids comprising at least two carboxylic acid functional groups. The term "carboxylic acid functional group" is taken here in its usual sense and refers to the -COOH functional group.
[0005] The polycarboxylic acid employed according to the invention may have two, three, four or more carboxylic acid functional groups. According to the invention, the polycarboxylic acid is preferably chosen from dicarboxylic acids and tricarboxylic acids. According to the invention, the polycarboxylic acid employed can be a linear or branched polycarboxylic acid, saturated or unsaturated, aliphatic having from 2 to 20 carbon atoms or aromatic. The polycarboxylic acid may optionally include hydroxyl groups and / or halogen atoms. The aliphatic polycarboxylic acid may optionally comprise heteroatoms on the main chain, for example N, S. Generally, the polycarboxylic acid used according to the invention is chosen from the group consisting of linear or branched, saturated or unsaturated aliphatic polycarboxylic acids. having from 2 to 16 carbon atoms and aromatic polycarboxylic acids. Among the aliphatic polycarboxylic acids, there may be mentioned linear polycarboxylic acids, saturated or unsaturated, having from 2 to 14 carbon atoms, preferably from 2 to 12 carbon atoms. The polycarboxylic acid employed may have 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. Advantageously, the polycarboxylic acid employed may have 4, 30, 76, 45, 6, 7, 8, 9 or 10 carbon atoms, preferably 4, 5, 6, 7 or 8 carbon atoms. For example, the polycarboxylic acid employed may have 4, 5 or 6 carbon atoms. In particular, non-limiting examples of linear aliphatic polycarboxylic acids used in the invention include the acids selected from the group consisting of oxalic acid, malonic acid, tricarballylic acid, succinic acid, and the like. glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid. Among the branched polycarboxylic acids, there may be mentioned methylsuccinic acid, ethylsuccinic acid, oxalosuccinic acid, methyladipic acid, methylglutaric acid and dimethylglutaric acid. By methylglutaric acid is meant both 2-methylglutaric acid and 3-methylglutaric acid as well as the mixture of these two isomers in all proportions. The term "2-methylglutaric acid" is used to indicate both the (S) and (R) forms of the compound and the racemic mixture. Unsaturated polycarboxylic acids include maleic acid, fumaric acid, itaconic acid, muconic acid, aconitic acid, traumatic acid and glutaconic acid. Among the polycarboxylic acids comprising hydroxyl groups, mention may be made of malic acid, citric acid, isocitric acid and tartaric acid. Among the aromatic polycarboxylic acids, there may be mentioned phthalic acids, namely phthalic acid, orthophthalic acid, isophthalic acid, trimesic acid and trimellitic acid. Preferably, the polycarboxylic acid employed in the process according to the invention is selected from the group consisting of oxalic acid, malonic acid, tricarballylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methylsuccinic acid, ethylsuccinic acid, methyladipic acid, methylglutaric acid, dimethylglutaric acid, malic acid, citric acid, isocitric acid, tartaric acid. Preferably, the dicarboxylic and tricarboxylic acids are chosen from adipic acid, succinic acid, ethylsuccinic acid, glutaric acid, methylglutaric acid, oxalic acid and citric acid. The polycarboxylic acid may also be selected from the group consisting of oxalic acid, malonic acid, tricarballylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methylsuccinic acid, ethylsuccinic acid, methyladipic acid, methylglutaric acid, dimethylglutaric acid, malic acid, citric acid, isocitric acid, tartaric acid. Preferably, the polycarboxylic acid may be chosen from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid. , azelaic acid, sebacic acid, methylsuccinic acid, ethylsuccinic acid, methyladipic acid, methylglutaric acid, dimethylglutaric acid, malic acid, citric acid, isocitric acid , tartaric acid. Most preferably, the polycarboxylic acid may be selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and the like. sebacic acid, methylsuccinic acid, ethylsuccinic acid, methyladipic acid, methylglutaric acid, dimethylglutaric acid, malic acid, citric acid, tartaric acid. In a first embodiment of the invention, a single polycarboxylic acid is added to the filter cake. Preferably, the polycarboxylic acid is then succinic acid. Preferably, when the polycarboxylic acid is succinic acid, it is added to the filter cake after the disintegration operation. In a second preferred embodiment of the invention, a mixture of polycarboxylic acids is added to the filter cake, said mixture comprising at least two polycarboxylic acids as defined above. The mixture may comprise two, three, four or more than four polycarboxylic acids. Preferably, the polycarboxylic acids of the mixture are then chosen from adipic acid, succinic acid, ethylsuccinic acid, glutaric acid, methylglutaric acid, oxalic acid and citric acid. According to the invention, the mixture of polycarboxylic acids is preferably a mixture of dicarboxylic and / or tricarboxylic acids, in particular a mixture of at least two, preferably at least three, dicarboxylic and / or tricarboxylic acids, in particular a mixture of three dicarboxylic and / or tricarboxylic acids. Preferably, the mixture of polycarboxylic acids is a mixture of dicarboxylic acids, especially a mixture of at least three dicarboxylic acids, in particular a mixture of three dicarboxylic acids. In general, the mixture consists of three dicarboxylic acids, although impurities may be present in an amount not generally greater than 2.00% by weight of the total mixture.
[0006] According to a preferred variant of the invention, the polycarboxylic acid mixture used in the invention comprises the following acids: adipic acid, glutaric acid and succinic acid. For example, the mixture of polycarboxylic acids comprises 15.00 to 35.00% by weight of adipic acid, 40.00 to 60.00% by weight of glutaric acid and 15.00 to 25.00% by weight. of succinic acid. The mixture of polycarboxylic acids according to this first preferred variant of the invention may be derived from a process for the manufacture of adipic acid. According to another preferred variant of the invention, the mixture of polycarboxylic acids used in the invention comprises the following acids: methylglutaric acid, ethylsuccinic acid and adipic acid. The three acids can be present in the mixture in all proportions. For example, the mixture of polycarboxylic acids comprises 60.00 to 96.00% by weight of methylglutaric acid, 3.90 to 20.00% by weight of ethylsuccinic acid and 0.05 to 20.00% by weight. of adipic acid. The mixture of polycarboxylic acids according to this second preferred variant of the invention may be derived from a process for the manufacture of adipic acid. Advantageously, the mixture of polycarboxylic acids according to this second preferred variant of the invention can be obtained by acid hydrolysis, preferably by basic hydrolysis, of a mixture of methylglutaronitrile, ethylsuccinonitrile and adiponitrile derived from the process of manufacture of adiponitrile by hydrocyanation of butadiene, adiponitrile being an important intermediate for the synthesis of hexamethylenediamine.
[0007] A part or all of the polycarboxylic acid (s), in particular dicarboxylic and / or tricarboxylic acids, employed according to the invention may be in the form of a carboxylic acid derivative, namely in the form of anhydride, ester, salt (carboxylate) of alkali metal (for example sodium or potassium), salt (carboxylate) alkaline earth metal (for example calcium) or salt (carboxylate) ) of ammonium. The term "carboxylate" will be used hereinafter to designate derivatives of carboxylic acid functional groups as defined above.
[0008] For example, the mixture of polycarboxylic acids may be a mixture comprising: methylglutaric acid (in particular from 60.00 to 96.00% by weight, for example from 90.00 to 95.50% by weight) ethylsuccinic anhydride (in particular from 3.90 to 20.00% by weight, for example from 3.90 to 9.70% by weight), adipic acid (in particular from 0.05 to at 20.00% by weight, for example from 0.10 to 0.30% by weight). The mixture of polycarboxylic acids may also be a mixture comprising: methylglutaric acid (in particular from 10.00 to 50.00% by weight, for example from 25.00 to 40.00% by weight), methylglutaric anhydride (in particular from 40.00 to 80.00% by weight, for example from 55.00 to 70.00% by weight), ethylsuccinic anhydride (in particular 3.90% by weight), to 20.00% by weight, for example from 3.90 to 9.70%), adipic acid (in particular from 0.05 to 20.00% by weight, for example from 0.1 to 0 3% by weight). The mixtures used according to the invention may optionally contain impurities. The polycarboxylic acids used in the invention may optionally be preneutralized (in particular by pretreating them with a base, for example of the sodium or potassium hydroxide type) before being added to the filter cake. This makes it possible in particular to modify the pH of the silica obtained. The polycarboxylic acids may be employed as an aqueous solution. The amount of polycarboxylic acid (s) employed is generally such that the ratio of polycarboxylic acid (s) to the amount of silica expressed as SiO 2 contained in the filter cake (at the time of addition of at least one polycarboxylic acid) is between 0.50 and 2.00% by weight, preferably between 0.60 and 2.00% by weight, in particular between 0.55 and 1.75% by weight, in particular between 0.60 and 1.50% by weight, for example between 0.65 and 1.25% by weight. In the invention, the filter cake may optionally be washed. The implementation, during or after the disintegration operation, of at least one polycarboxylic acid and the succession of particular steps, and in particular the presence of a first simultaneous addition of acidifying agent and silicate in an acidic medium at pH between 2.0 and 5.0 and a second simultaneous addition of acidifying agent and silicate in a basic medium at a pH of between 7.0 and 10.0, gives the products obtained their characteristics and properties. special. The choice of acidifying agent and silicate is in a manner well known per se.
[0009] A strong mineral acid such as sulfuric acid, nitric acid or hydrochloric acid or an organic acid such as acetic acid, formic acid or carbonic acid is generally used as the acidifying agent. The acidifying agent may be diluted or concentrated; its normality can be between 0.4 and 36 N, for example between 0.6 and 1.5 N.
[0010] In particular, in the case where the acidifying agent is sulfuric acid, its concentration may be between 40 and 180 gil, for example between 60 and 130 gil. Any common form of silicates such as metasilicates, disilicates and preferably an alkali metal silicate such as sodium or potassium silicate can be used as the silicate. The silicate may have a concentration (expressed as SiO2) of between 40 and 330 g / l, for example between 60 and 300 gil, in particular between 60 and 260 g / l. Preferably, the acidifying agent used is sulfuric acid and, as a silicate, sodium silicate. In the case where sodium silicate is used, it generally has a weight ratio SiO 2 / Na 2 O of between 2.0 and 4.0, in particular between 2.4 and 3.9, for example between 3.1 and 3.8. Firstly, in step (i), an aqueous starter having a pH of 2.0 to 5.0 is formed. Preferably, the stock formed has a pH between 2.5 and 5.0, especially between 3.0 and 4.5; this pH is for example between 3.5 and 4.5. This initial stock can be obtained by adding an acidifying agent to water so as to obtain a pH value of the bottom of the tank between 2.0 and 5.0, preferably between 2.5 and 5, 0, especially between 3.0 and 4.5 and for example between 3.5 and 4.5. It can also be obtained by adding an acidifying agent to a water + silicate mixture so as to obtain this pH value. It can also be prepared by adding acidifying agent to a stock base containing silica particles previously formed at a pH below 7.0, so as to obtain a pH value between 2.0 and 5.0, preferably between 2.5 and 5.0, especially between 3.0 and 4.5 and for example between 3.5 and 4.5. The stock stem formed in step (i) may comprise an electrolyte. Preferably, the stock formed in step (i) contains an electrolyte. The term electrolyte is here understood in its normal acceptation, that is to say that it signifies any ionic or molecular substance which, when in solution, decomposes or dissociates to form ions or charged particles. As electrolyte, mention may be made of a salt of the group of alkali and alkaline earth metal salts, in particular the salt of the starting silicate metal 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 sulfate in the case of the reaction of a sodium silicate with sulfuric acid. Preferably, when sodium sulfate is used as the electrolyte in step (i), its concentration in the initial stock is in particular between 8 and 40 g / l, in particular between 10 and 20 g / l. g / L, for example between 13 and 18 g / l.
[0011] The second step (step (ii)) consists of a simultaneous addition of acidifying agent and silicate, in such a way (particularly at such flow rates) that the pH of the reaction medium is maintained between 2.0 and 5.0, preferably between 2.5 and 5.0, especially between 3.0 and 4.5, for example between 3.5 and 4.5. This simultaneous addition is advantageously carried out in such a way that the pH value of the reaction medium is constantly equal (within ± 0.2) to that reached at the end of the initial step (i). Then, in a step (iii), the addition of the acidifying agent is stopped while continuing the addition of silicate in the reaction medium so as to obtain a pH value of the reaction medium of between 7.0 and 10, 0, preferably between 7.5 and 9.5. It may then be advantageous to carry out immediately after this step (iii) and therefore just after stopping the addition of silicate, a ripening of the reaction medium, in particular at the pH obtained at the end of step (iii) , and in general with stirring; this curing can for example last from 2 to 45 minutes, in particular from 5 to 25 minutes, and preferably does not comprise any addition of acidifying agent or addition of silicate. After step (iii) and the optional ripening, a new simultaneous addition of acidifying agent and silicate, in such a way (particularly at such rates) that the pH of the reaction medium is maintained between 7, 0 and 10.0, preferably between 7.5 and 9.5. This second simultaneous addition (step (iv)) is advantageously carried out in such a way that the pH value of the reaction medium is constantly equal (within ± 0.2) to that reached at the end of the previous step.
[0012] It should be noted that it is possible, between step (iii) and step (iv), for example between, on the one hand, the eventual maturing according to step (iii), and, of on the other hand, step (iv), adding to the reaction medium of the acidifying agent, the pH of the reaction medium at the end of this addition of acid is however between 7.0 and 9.5, preferably between 7.5 and 9.5. Finally, in a step (v), the addition of the silicate is stopped while continuing the addition of acidifying agent in the reaction medium so as to obtain a pH value of the reaction medium of less than 6.0, preferably between 3.0 and 5.5, in particular between 3.0 and 5.0, for example between 3.0 and 4.5.
[0013] It may then be advantageous to carry out after this step (y) and therefore just after stopping the addition of acidifying agent, maturing of the reaction medium, especially at the pH obtained at the end of the step (y ), and in general with stirring; this curing can for example last from 2 to 45 minutes, in particular from 5 to 20 minutes, and preferably does not include any addition of acid or addition of silicate. The reaction chamber in which the entire reaction of the silicate with the acidifying agent is carried out is usually provided with appropriate stirring equipment and heating equipment.
[0014] The overall reaction of the silicate with the acidifying agent is generally carried out between 70 and 95 ° C, in particular between 75 and 95 ° C. According to a variant of the invention, the entire reaction of the silicate with the acidifying agent is carried out at a constant temperature, usually between 70 and 95 ° C, in particular between 75 and 95 ° C.
[0015] According to another variant of the invention, the end of reaction temperature is higher than the reaction start temperature: thus, the temperature is maintained at the beginning of the reaction (for example during steps (i) to (iii) )) preferably between 70 and 85 ° C, then the temperature is increased, preferably to a value between 85 and 95 ° C, at which point it is maintained (for example during steps (iv) and ( y)) until the end of the reaction. At the end of the steps which have just been described, a silica slurry is obtained which is then separated (liquid-solid separation).
[0016] The separation used in the preparation process according to the invention usually comprises a filtration, followed by washing if necessary. The filtration is carried out by any suitable method, for example by means of a band filter, a vacuum filter or, preferably, a filter press. The filter cake is then subjected to a disintegration operation. In accordance with the above discussion, at least one polycarboxylic acid is added during or after the disintegration operation. The disintegrated filter cake is then dried. This drying can be done by any means known per se. Preferably, the drying is done by atomization. For this purpose, any suitable type of atomizer may be used, such as a turbine, nozzle, liquid pressure or two-fluid atomizer. In general, when the filtration is carried out using a filter press, a nozzle atomizer is used, and when the filtration is carried out using a vacuum filter, a turbine atomizer is used. . When the drying is carried out by means of a nozzle atomizer, the precipitated silica which can then be obtained is usually in the form of substantially spherical balls. At the end of this drying, it may optionally proceed to a grinding step on the recovered product; the precipitated silica that can then be obtained is generally in the form of a powder. When the drying is carried out with the aid of a turbine atomizer, the precipitated silica which may then be obtained may be in the form of a powder. Finally, the product dried (in particular by a turbine atomizer) or milled as indicated above can optionally be subjected to an agglomeration step, which consists, for example, of a direct compression, a wet granulation (that is, that is, using a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction. When the latter technique is used, it may be advisable, before compacting, to deaerate (operation also called pre-densification or degassing) the pulverulent products so as to eliminate the air included in these products. ci and ensure a more regular compaction. The precipitated silica that can then be obtained by this agglomeration step is generally in the form of granules. The invention also relates to precipitated silicas obtained or obtainable by the process according to the invention.
[0017] In general, these precipitated silicas have at their surface molecules of the polycarboxylic acid (s) employed and / or of the carboxylate (s) corresponding to the acid (s) ) polycarboxylic (s) used.
[0018] The present invention further relates to a precipitated silica with particular characteristics, in particular usable as an alternative filler for the polymer compositions which advantageously provides a reduction in their viscosity and an improvement in their dynamic properties while retaining their mechanical properties.
[0019] In the following description, the BET surface area is determined according to the method of BRUNAUER - EMMET - TELLER described in "The Journal of the American Chemical Society", Vol. 60, page 309, February 1938 and corresponding to standard NF ISO 5794-1 appendix D (June 2010). The CTAB specific surface is the external surface, which can be determined according to standard NF ISO 5794-1 appendix G (June 2010). The corresponding polycarboxylic acid + carboxylate content (C), expressed as total carbon, can be measured using a sulfur-containing carbon analyzer such as Horiba EMIA 320 V2. The principle of the sulfur carbon analyzer is based on the combustion of a solid sample in a flow of oxygen in an induction furnace (set at about 170 mA) and in the presence of combustion accelerators (about 2 grams of tungsten (in particular Lecocel 763-266) and about 1 gram of iron). The analysis lasts about 1 minute.
[0020] The carbon contained in the sample to be analyzed (mass of about 0.2 gram) combines with oxygen to form CO2, CO. These decomposition gases are then analyzed by an infrared detector. The moisture of the sample and the water produced during these oxidation reactions is removed by passing through a cartridge containing a dehydrating agent: magnesium perchlorate so as not to interfere with the infrared measurement. The result is expressed as a percentage by mass of carbon element. The presence of polycarboxylic acid (s) in the acid form and / or in the carboxylate form can be established by surface infrared or ATR-diamond (Attenuated Total Reflection). Infrared surface analysis (by transmission) is carried out on a Bruker Equinoxe 55 spectrometer on a pellet of pure product. The pellet is obtained after grinding the silica as it is in an agate mortar and pelletizing at 2 T / cm 2 for 10 seconds. The diameter of the pellet is 17 mm. The weight of the pellet is between 10 and 20 mg. The pellet thus obtained is placed in the secondary vacuum chamber (10-7 mbar) of the spectrometer for one hour at room temperature before the transmission analysis. The acquisition takes place under secondary vacuum (acquisition conditions: from 400 cm-1 to 6000 cm-1, number of scans: 100, resolution: 2 cm-1). The ATR-diamond analysis, carried out on a Bruker Tensor 27 spectrometer, consists in depositing on the diamond a tip of silica spatula previously ground in an agate mortar and then exerting a pressure. The infrared spectrum is recorded on the spectrometer in 20 scans, from 650 cm -1 to 4000 cm -1. The resolution is 4 cm-1.
[0021] The centrifugal sedimentation XDC granulometric analysis method, on the one hand, is used to measure the object size distribution widths of the silica, and on the other hand, the XDC mode, illustrating its size of objects, is described below: Materials needed - BI-XDC centrifugal sedimentation granulometer (BROOKHAVEN-INSTRUMENT X DISC CENTRIFUGES) marketed by the Brookhaven Instrument Corporation) - beaker tall form of 50 ml graduated cylinder of 50 ml probe BRANSON 1500 watt, no-tip, 19 mm diameter swirl water exchanger - crystallizer filled with ice magnetic stirrer Measuring condition - Windows version 3.54 software (supplied by the manufacturer of the particle size analyzer) fixed mode - rotational speed: 5000 rpm - duration of the analysis: 120 minutes - density (silica): 2.1 - volume of the suspension to be taken: 15 ml Preparation of the sample Add in the beaker high form 3.2 grams of sili this and 40 ml of deionized water. Put the beaker containing the suspension in the crystallizer filled with ice.
[0022] Immerse the ultrasound probe in the beaker. Deagglomerate the suspension for 16 minutes using the 1500 watts BRANSON probe (generally used at 60% of maximum power). When the disaggregation is complete, put the beaker on a magnetic stirrer.
[0023] Cool the dispersion obtained at room temperature (21 ° C). Preparation of the granulometer Switch on the appliance and let it heat for at least 30 minutes. Rinse the disc twice with deionized water. Enter in the software the measurement conditions mentioned above.
[0024] Measurement of the blank: Introduce 10 ml of deionized water into the disc, stir the balance and measure the signal. Remove the permuted water. Measurement of the samples: Introduce 15 ml of the sample to be analyzed into the disc, stir the balance and measure the signal. Take the measurements. When measurements have been made: Stop the rotation of the disc.
[0025] Rinse the disc several times with deionized water. Stop the device. Results In the device register, record the values of the diameters increasing to 16%, 50% (or median, size for which one has 50% in mass of the aggregates of size smaller than this size) and 84% (% mass) thus that the value of the Mode (the derivative of the cumulative granulometric curve gives a frequency curve whose abscissa of the maximum (abscissa of the main population) is called the Mode). The width Ld of object size distribution, measured by XDC granulometry, after ultrasonic deagglomeration (in water), corresponds to the ratio (d84 - d16) / d50 in which dn is the size for which one is%. of particles (in mass) of size smaller than this size (the width Ld of distribution is thus calculated on the cumulative granulometric curve, taken in its entirety).
[0026] The width The d of the object size distribution less than 500 nm, measured by XDC granulometry, after ultrasound disagglomeration (in water), corresponds to the ratio (d84 - d16) / d50 in which dn is the size for which one% of particles (in mass), with respect to the particles of size smaller than 500 nm, of size smaller than this size (the width The distribution d is thus calculated on the cumulative granulometric curve, truncated above 500 nm). The porous volumes and pore diameters are measured by mercury porosimetry (Hg), using a MICROMERITICS Autopore 9520 porosimeter, and are calculated by the WASHBURN relationship with a theta contact angle equal to 140 ° and a voltage superficial gamma equal to 484 Dynes / cm (DIN 66133 standard). The preparation of each sample is as follows: each sample is pre-dried for 2 hours in an oven at 200 ° C. V (d5 - d50) represents the pore volume constituted by the pores with diameters between d5 and d50, and V (d5 - oo) represents the pore volume constituted by the pores with diameters between d5 and d100, dn being here the diameter of pores for which n% of the total surface of all the pores is brought by the pores of diameter greater than this diameter (the total surface of the pores (So) can be determined from the mercury intrusion curve).
[0027] The porous distribution width Idp is obtained from the porous distribution curve, as shown in FIG. 1, pore volume (ml / g) as a function of the pore diameter (nm): the coordinates of the point S are recorded corresponding to the main population, namely the values of the diameter (nm) Xs and the pore volume (ml / g) Ys; we draw a line of equation Y = Ys / 2; this line intersects the porous distribution curve at two points A and B having abscissa (nm) respectively XA and XB on either side of Xs; the porous distribution width ldp is equal to the ratio (XA - Xs) Xs. Depending on the source of the raw materials used for the silicate, the precipitated silicas according to the invention may contain additional elements, such as for example metals. Among said additional elements, mention may be made of aluminum. The aluminum content noted (AI) is generally less than 1200 ppm, preferably less than 700 ppm, in particular less than 600 ppm, more preferably less than 500 ppm.
[0028] The dispersive component of the surface energy ysd is determined by reverse gas chromatography. Grinding of the silica is generally necessary when it is in the form of granules, followed by sieving, for example, at 106 μm -250 μm. The technique used to calculate the dispersive component of surface energy Ysd is Infinite Dilution Inverse Gas Chromatography (CGI-DI) at 110 ° C using a series of (normal) alkanes ranging from 6 to 10 carbon atoms. carbon, a technique based on gas chromatography, but where the role of the mobile phase and the stationary phase (filling) are reversed. Here, the stationary phase in the column is replaced by the material (solid) to be analyzed, here precipitated silica. As for the mobile phase, it consists of the carrier gas (helium) and "probe" molecules chosen according to their interaction capacity. The measurements are carried out successively with each probe molecule. For each measurement, each probe molecule is injected into the column, in a very small quantity (infinite dilution), mixed with methane. Methane is used to determine the tO, the dead time of the column.
[0029] The subtraction of this dead time tO at the retention time of the injected probe leads to the net retention time (tN) thereof. These operating conditions, suitable for infinite dilution, mean that these retention times only reflect the interactivity of the sample with respect to these molecules. Physically, tN corresponds to the average time that the probe molecule has passed in contact with the stationary phase (the analyzed solid). For each injected probe molecule, three net retention times tN are measured. The mean value and the corresponding standard deviation are used to determine the specific retention volumes (Vg °) based on the following relation (formula [1]). ## EQU1 ## This corresponds to the volume of carrier gas (brought back to 0 ° C.) necessary to elute the probe molecule for 1 gram of stationary phase (solid examined). This standard size makes it possible to compare the results regardless of the carrier gas flow rate and the stationary phase mass used. The formula [1] uses: Ms, the solid mass in the column, Dc the carrier gas flow rate and T the measurement temperature. The specific retention volume is then used to access LGa, the free adsorbtion enthalpy variation of the probe, according to formula [2], with R the universal constant of perfect gases (R = 8.314 JK-1.mo1 -1), on the solid contained in the column. AG, = RT.Ln (Vg °) formula [2] This magnitude LGa is the starting point for the determination of the dispersive component of the surface energy (ysd). This is obtained by plotting the straight line representing the free adsorption enthalpy variation (AGa) as a function of the carbon number of the n-alkane probes as indicated in the table below. Probes n-alkanes n-hexane 6 n-heptane 7 n-octane 8 n-nonane 9 n-decane The dispersive component of the surface energy Ysd can then be determined from the slope JGa (CH2) of the right of the normal alkanes, corresponding to the free enthalpy of adsorption of the methylene group, obtained for a measurement temperature of 110 ° C. The dispersive component of the surface energy ysd is then connected to the free adsorption enthalpy JGa (CH2) of the methylene group (Dorris and Gray method, J. Colloid Interface Sci., 77 (180), 353-362). by the following relation: d (AGaH 2) 2 YS 2 2 4N A-aCH 2 * YCH 2 in which NA is the number of Avogadro (6.02.223 mol "), acH 2 the area occupied by an adsorbed methylene group (0, 06 nm2) and ycH2 the surface energy of a solid consisting solely of methylene group and determined on polyethylene (35.6 mJ / m 2 at 20 ° C.) The technique used to measure the water uptake generally consists in placing under predetermined conditions of relative humidity and for a predefined period of time, the previously dried silica sample, the silica is then hydrated, which causes the mass of the sample to have an initial value m (at the dried state) to a final value m + dm Specifically referred to as "water recovery" of a silica, in particular to relate throughout the rest of the presentation, the ratio dm / m (ie the mass of water incorporated in the sample relative to the mass of the sample in the dry state) expressed as a percentage calculated for a silica sample subjected to the following conditions during the measurement method: - preliminary drying: 8 hours at 150 ° C; hydration: 24 hours, at 20 ° C., and at a relative humidity of 70%. The experimental protocol used consists of successively: weighing exactly 2 grams of the silica to be tested; drying the silica thus weighed for 8 hours in an oven set at a temperature of 105 ° C .; - Determine the mass m of the silica obtained at the end of this drying; - Place for 24 hours, at 20 ° C, the dried silica in a closed container such as a desiccator containing a mixture of water / glycerin, so that the relative humidity of the closed medium is 70%; - Determine the mass (m + dm) of the silica obtained following this treatment of 24 hours at 70% relative humidity, the measurement of this mass being carried out immediately after removing the silica from the desiccator, so as to avoid a variation the mass of the silica under the influence of the change of hygrometry between the medium at 70% relative humidity and the laboratory atmosphere. The ability to disperse and disaggregate silicas can be quantified by means of the specific disagglomeration test below. The cohesion of the agglomerates is assessed by a granulometric measurement (by laser diffraction), carried out on a suspension of silica previously deagglomerated by ultra-sonification; the ability of the silica to deagglomerate (rupture of the objects from 0.1 to a few tens of microns) is thus measured. Ultrasonic deagglomeration is carried out using a VIBRACELL BIOBLOCK (600 W) sonicator, used at 80% of the maximum power, equipped with a 19 mm diameter probe. The particle size measurement is carried out by laser diffraction on a MALVERN granulometer (Mastersizer 2000) by implementing the Fraunhofer theory. 1 gram (+/- 0.1 gram) of silica is introduced into a 50 ml beaker (height: 7.5 cm and diameter: 4.5 cm) and is added to 50 grams by addition of 49 grams. (+/- 0.1 gram) of permutated water. An aqueous suspension with 2% of silica is thus obtained. Deagglomeration is then carried out under ultrasound for 7 minutes. The particle size measurement is then carried out by introducing into the tank 35 of the granulometer the whole of the homogenized suspension. The median diameter 050m (or Malvern median diameter), after ultrasound deagglomeration, is such that 50% of the particles in volume are smaller than 050m and 50% are larger than 050m. The value of the median diameter 050m that is obtained is even lower than the silica has a high ability to deagglomerate. It is also possible to similarly determine the Malvern FDm deagglomeration factor by a particle size measurement (laser diffraction), carried out on a silica suspension previously deagglomerated by ultra-sonification; the ability of the silica to deagglomerate (rupture of the objects from 0.1 to a few tens of microns) is thus measured. Ultrasonic deagglomeration is carried out using a VIBRACELL BIOBLOCK (600 W) sonicator, used at 80% of the maximum power, equipped with a 19 mm diameter probe. The particle size measurement is carried out by laser diffraction on a MALVERN granulometer (Mastersizer 2000) by implementing the Fraunhofer theory. 1 gram (+/- 0.1 gram) of silica is introduced into a 50 ml beaker (height: 7.5 cm and diameter: 4.5 cm) and is added to 50 grams by addition of 49 grams. (+/- 0.1 gram) of permutated water. An aqueous suspension with 2% of silica is thus obtained. Deagglomeration is then carried out under ultrasound for 7 minutes. The particle size measurement is then carried out by introducing into the tank 20 of the granulometer the whole of the homogenized suspension. This deagglomeration factor is determined by the ratio (10 x darkness value of the blue laser / obscuration value of the red laser), this optical density corresponding to the actual value detected by the granulometer during the introduction of the silica. This ratio (Malvern Fm deagglomeration factor) is indicative of the rate of particles smaller than 0.1 am which are not detected by the particle size analyzer. This ratio is higher when the silica has a high deagglomeration ability. The pH is measured according to the following method derived from ISO 787/9 (pH of a 5% suspension in water): Apparatus: calibrated pH meter (1 / 100th reading accuracy) combined glass electrode 35 beaker of 200 ml 100 ml test specimen with a precision of 0,01 g. Procedure 5 grams of silica are weighed to the nearest 0.01 gram in the 200 ml beaker. 95 ml of water measured from the graduated cylinder are then added to the silica powder. The suspension thus obtained is stirred vigorously (magnetic stirring) for 10 minutes. The pH measurement is then performed.
[0030] According to a first variant of the invention, the precipitated silica according to the invention is characterized in that it has: a BET specific surface area of between 45 and 550 m 2 / g, in particular between 70 and 370 m 2 / g, in particular between 80 and 350 m 2 / g, a CTAB specific surface area of between 40 and 525 m 2 / g, in particular between 70 and 350 m 2 / g, in particular between 80 and 310 m 2 / g, a content (C) of polycarboxylic acid. + corresponding carboxylate, expressed as total carbon, of at least 0.15% by weight, especially at least 0.20% by weight, - a width Ld ((d84 - d16) / d50) of size distribution objects measured by XDC particle size after ultrasound deagglomeration of at least 0.91, in particular of at least 0.94 and, - a distribution of the pore volume such as the ratio V (d5 d50) N (d5 - dloo) is at least 0.65, in particular at least 0.66, in particular at least 0.68. The silica according to this variant of the invention has for example: a width Ld (d8 4 - d16) / d50) of size distribution of object size distribution measured by XDC granulometry after ultrasonic deagglomeration of at least 1.04 and - a distribution of the pore volume such as the ratio V (d5 d50) N (d5 d100) is at least 0.70, especially at least 0.71. This silica may have a ratio V (d5 - d50) N (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. According to a second variant of the invention, the precipitated silica according to the invention is characterized in that it has: a BET specific surface area of between 45 and 550 m 2 / g, in particular between 70 and 370 m 2 / g, Particularly between 80 and 350 m 2 / g, a CTAB specific surface area of between 40 and 525 m 2 / g, in particular between 70 and 350 m 2 / g, in particular between 80 and 310 m 2 / g, a content (C) in corresponding polycarboxylic acid + carboxylate, expressed as total carbon, of at least 0.15% by weight, especially at least 0.20% by weight, a porous distribution width Idp greater than 0.65, in particular greater than 0.70, in particular greater than 0.80. This silica may have a porous distribution width ldp of greater than 1.05, for example at 1.25 or even 1.40.
[0031] The silica according to this variant of the invention preferably has a width Ld ((d84 - d16) / d50) of size distribution of size of objects measured by XDC granulometry after disintegration with ultrasound of at least 0 , 91, in particular of at least 0.94, for example of at least 1.0.
[0032] The precipitated silicas according to the invention (that is to say, in accordance with one of the two variants of the invention) may in particular have a BET specific surface area of between 100 and 320 m 2 / g, in particular between 120 and 300 m 2. m2 / g, for example between 130 and 280 m2 / g. The precipitated silicas according to the invention may in particular have a CTAB specific surface area of between 100 and 300 m 2 / g, in particular between 120 and 280 m 2 / g, for example between 130 and 260 m 2 / g. In general, the precipitated silicas according to the invention have a BET specific surface area / CTAB surface area ratio of between 0.9 and 1.2, that is to say that it has a low microporosity. The precipitated silicas according to the invention may in particular have a content (C) of polycarboxylic acid + corresponding carboxylate, expressed as total carbon, of at least 0.24% by weight, in particular at least 0.30% by weight. weight, for example at least 0.35% by weight, or even at least 0.45% by weight. They generally have a content of polycarboxylic acid + carboxylate (C) of at most 10.00% by weight, in particular at most 5.00% by weight. The presence of the polycarboxylic acids and / or carboxylates corresponding to the polycarboxylic acids on the surface of the silicas according to the invention can be illustrated by the presence of shoulders characteristic of the C-O and C = O bonds, visible on the infrared spectra, obtained especially by surface infrared (transmission) or ATR-diamond (in particular between 1540 and 1590 cm-1 and between 1380 and 1420 cm-1 for C-0, and between 1700 and 1750 cm-1 for C = 0 ).
[0033] In general, the precipitated silicas according to the invention have on their surface molecules of the aforementioned polycarboxylic acid (s), in particular polycarboxylic acids of the abovementioned mixtures, and / or of carboxylate (s) corresponding to the aforementioned polycarboxylic acid (s), in particular corresponding to the polycarboxylic acids of the abovementioned mixtures. For example, they may have on their surface: adipic acid molecules in acid form and / or in carboxylate form, and glutaric acid molecules in acid form and / or in carboxylate form, and succinic acid in acid form and / or in carboxylate form.
[0034] For example, they may have on their surface: molecules of methylglutaric acid in acid form and / or in carboxylate form, and molecules of ethylsuccinic acid in acid form and / or in carboxylate form, and molecules adipic acid in acid form and / or carboxylate form. Preferably, the silicas according to the invention have a dispersive component of the surface energy ysd of less than 52 mJ / m 2, especially less than 50 mJ / m 2, in particular at most 45 m 2 / m 2, for example less than at 40 mJ / m2, or even less than 35 mJ / m2. Preferably, the silicas according to the invention have a width d ((d84-d16) / d50) of an object size distribution of less than 500 nm, measured by XDC granulometry after ultrasonic deagglomeration, of at least 0.95. In the silicas according to the invention, the pore volume provided by the larger pores is usually the largest part of the structure. They may have both an object size distribution width Ld of at least 1.04 and an object size distribution width d (less than 500 nm) of at least 0.95.
[0035] The width Ld of object size distribution of the silicas according to the invention may in certain cases be at least 1.10, in particular at least 1.20; it can be at least 1.30, for example at least 1.50, or even at least 1.60. Similarly, the width D of the object size distribution (less than 500 nm) of the silicas according to the invention may be, for example, at least 1.0, in particular at least 1.10, in particular from at least 1.20. The precipitated silicas according to the invention may have a water uptake of greater than 6%, in particular greater than 7%, especially greater than 7.5%, for example greater than 8%, or even greater than 8.5%. In general, the precipitated silicas according to the invention have dispersibility (especially in elastomers) and high deagglomeration. The precipitated silicas according to the invention may have a median diameter 050 μm after deagglomeration with ultrasound of at most 10.0 μm, preferably at most 9.0 μm, in particular between 3.5 and 8.5 μm. pm. The precipitated silicas according to the invention may have a deagglomeration factor with FDM ultrasound greater than 5.5 ml, in particular greater than 7.5 ml, for example greater than 12.0 ml. The precipitated silicas according to the invention preferably have a pH of between 3.5 and 7.5, more preferably between 4.0 and 7.0, in particular between 4.5 and 6.5. The physical state in which the precipitated silicas according to the invention occur may be any, that is to say that they may be in the form of substantially spherical beads (microbeads), powder or granules. They may thus be in the form of substantially spherical beads of average size of at least 80 μm, preferably at least 150 μm, in particular between 150 and 270 μm; this average size is determined according to standard NF X 11507 (December 1970) by dry sieving and determination of the diameter corresponding to a cumulative refusal of 50%. They may also be in the form of a powder of average size of at least 15 μm, in particular at least 20 μm, preferably at least 30 μm. They may be in the form of granules (generally of substantially parallelepiped shape) of size of at least 1 mm, for example between 1 and 10 mm, especially along the axis of their largest dimension. The silicas according to the invention are preferably obtained by the process described above. Advantageously, the silicas precipitated according to the present invention or (capable of being obtained) by the process according to the invention described above confer on the polymer compositions (elastomer (s)) in which they are introduced, a compromise of very satisfactory properties, in particular a reduction in their viscosity and preferably an improvement in their dynamic properties while retaining their mechanical properties. They thus advantageously make it possible to improve the compromise implemented / reinforcement / hysteretic properties. Preferably, they exhibit good dispersibility and disagglomeration in the polymer (s) (elastomer (s)) compositions. The silicas precipitated according to the present invention or (capable of being obtained) by the method described above can be used in many applications. They can be used, for example, as a catalyst support, as absorbent for active substances (in particular a liquid carrier, especially used in foodstuffs, such as vitamins (vitamin E), choline chloride), in polymer compositions. (S), especially elastomer (s), silicone (s), as a viscosizing, texturizing or anti-caking agent, as an element for battery separators, as an additive for toothpaste, for concrete, for paper. However, they find a particularly interesting application in the reinforcement of polymers, natural or synthetic. The polymer compositions in which they can be used, especially as a reinforcing filler, are generally based on one or more polymers or copolymers (especially bipolymers or terpolymers), in particular one or more elastomers. , preferably having at least a glass transition temperature of between -150 ° and + 300 ° C, for example between -150 and + 20 ° C. Possible polymers that may be mentioned include diene polymers, in particular diene elastomers.
[0036] For example, it is possible to use polymers or copolymers (in particular bipolymers or terpolymers) derived from aliphatic or aromatic monomers, comprising at least one unsaturation (such as, in particular, ethylene, propylene, butadiene, isoprene or styrene). acrylonitrile, isobutylene, vinyl acetate), butyl polyacrylate, or mixtures thereof; mention may also be made of silicone elastomers, functionalized elastomers, for example by chemical groups arranged all along the macromolecular chain and / or at one or more of its ends (for example by functions capable of reacting with the surface of the silica) and halogenated polymers. Polyamides and fluorinated polymers (such as polyvinylidene fluoride) may be mentioned. Thermoplastic polymers such as polyethylene can also be mentioned. The polymer (copolymer) may be a bulk polymer (copolymer), a polymer latex (copolymer) or a polymer solution (copolymer) in water or any other suitable dispersing liquid. Examples of diene elastomers that may be mentioned are polybutadienes (BR), polyisoprenes (IR), butadiene copolymers, isoprene copolymers, or mixtures thereof, and in particular styrene-butadiene copolymers ( SBR, in particular ESBR (emulsion) or SSBR (solution)), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-butadiene-styrene copolymers (SBIR), ethylene-propylene-diene terpolymers (EPDM) as well as the associated functionalized polymers (having, for example, polar groups included in the chain, during or at the chain end and capable of interacting with silica). Mention may also be made of natural rubber (NR) and epoxidized natural rubber (ENR). The polymer compositions may be vulcanized with sulfur (vulcanizates are obtained) or crosslinked, in particular with peroxides or other crosslinking systems (for example diamines or phenolic resins). In general, the polymer compositions (s) further comprise at least one coupling agent (silica / polymer) and / or at least one covering agent; they may also include, inter alia, an antioxidant. Coupling agents that may be used as non-limiting examples include polysulphide silanes, called "symmetrical" or "asymmetrical" silanes; mention may be made more particularly of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4) silyl-C 1 -C 4 alkyl), such as, for example, bis polysulfides ( 3- (trimethoxysilyl) propyl) or polysulfides of bis (3- (triethoxysilyl) propyl), such as triethoxysilylpropyl tetrasulfide. Mention may also be made of monoethoxydimethylsilylpropyl tetrasulfide. Mention may also be made of silanes with thiol function, masked or otherwise, with amine function. The coupling agent may be grafted onto the polymer beforehand. It can also be used in the free state (that is to say, not previously grafted) or grafted to the surface of the silica. The same is true of the possible collector.
[0037] 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 coupling agent. The proportion by weight of silica in the polymer composition (s) can vary within a fairly wide range. It is usually 0.1 to 3.0 times by weight, in particular 0.1 to 1.2 times by weight, especially 0.2 to 1.5 times by weight, for example 0.2 to 1.2 times by weight. weight, or even 0.3 to 0.8 times by weight, of the amount of the polymer (s). The silica according to the invention may advantageously constitute all of the reinforcing inorganic filler, and even the whole of the reinforcing filler, of the polymer composition (s). However, to this silica according to the invention may be optionally associated with at least one other reinforcing filler, such as in particular a commercially highly dispersible silica such as for example Z1165MP, Z1115MP, a precipitated silica treated (for example "doped" with using a cation such as aluminum or treated with a coupling agent such as a silane); another reinforcing inorganic filler such as, for example, alumina, or even a reinforcing organic filler, especially carbon black (optionally covered with an inorganic layer, for example silica). The silica according to the invention then preferably constitutes at least 50% or even at least 80% by weight of the totality of the reinforcing filler. As nonlimiting examples of finished articles comprising at least one (in particular based on) said polymer compositions (s) described above (in particular based on the vulcanizates mentioned above), the soles of shoes (preferably in the presence of a coupling agent (silica / polymer), for example triethoxysilylpropyl tetrasulfide), floor coverings, gas barriers, fire-retardant materials and also technical parts such as ropeway rollers, appliances, liquid or gas line joints, brake system joints, hoses, ducts (including cable ducts), cables, motor mounts, battery separators, conveyor belts, transmission belts, or, preferably, tires, in particular tire treads (especially for light vehicles or pedestrians). our heavy goods vehicles (trucks for example)). The following examples illustrate the invention without, however, limiting its scope.
[0038] EXAMPLES EXAMPLE 1 Into a 2000 liter reactor, 700 liters of industrial water are introduced. This solution is heated to 80 ° C. by heating by direct injection of steam. With stirring (95 rpm), sulfuric acid, concentration equal to 80 g / l, is introduced until the pH reaches a value of 4.
[0039] A solution of sodium silicate (SiO 2 / Na 2 O weight ratio equal to 3.52) having a concentration of 230 g / l at a flow rate of 190 l / h and sulfuric acid is introduced simultaneously into the reactor for 35 minutes. , of concentration equal to 80 g / l, at a regulated flow rate so as to maintain the pH of the reaction medium at a value of 4.
[0040] At the end of the 35 minutes of simultaneous addition, the introduction of acid is stopped until the pH has reached a value equal to 8. A new simultaneous addition is then carried out for 40 minutes with a flow of sodium silicate 190 l / h (same sodium silicate as for the first simultaneous addition) and a sulfuric acid flow rate, concentration equal to 80 g / l, regulated so as to maintain the pH of the reaction medium to a value of 8. At the end of this simultaneous addition, the reaction medium is brought to a pH of 5.2 with sulfuric acid of concentration equal to 80 g / l. The medium is cured for 5 minutes at pH 5.2. The slurry is filtered and washed under a filter press and a precipitated silica cake having a solids content of 22% is obtained. EXAMPLE 2 A portion of the silica cake obtained in Example 1 is then subjected to a disintegration step.
[0041] During the disintegration operation, a solution of a 34% by weight MGA mixture is used (mixture of polycarboxylic acids: 94.8% by weight of methylglutaric acid, 4.9% by weight of ethylsuccinic anhydride, 0.2% by weight of adipic acid, 0.1% other).
[0042] The cake obtained in the filtration stage is subjected to a disintegration operation in a continuously stirred reactor with addition of 36.8 grams of the MGA solution to the cake (MGA / SiO 2 mixture weight ratio of 1%). This disintegrated cake (having a solids content of 22% by weight) is then dried by means of a bi-fluid nozzle atomizer by spraying the disintegrated cake through a 2.54 mm SU5 (Spraying System) nozzle with a pressure of 1 bar under the following medium flow and temperature conditions: Average inlet temperature: 250 ° C Average outlet temperature: 135 ° C Average flow rate: 15 1 / h. The characteristics of the silica S1 obtained (in the form of substantially spherical beads) are then as follows: BET (m 2 / g) 217 Content of polycarboxylic acid + carboxylate (C) (%) 0.42% of aluminum (AI) (%) ) 0.08 CTAB (m2 / g) 214 ysd (mJ / m2) 42.8 Width Ld (XDC) 1.02 V (d5-d50) N (d5-d100) 0.71 Porous distribution width ldp 1, 07 Width The d (XDC) 0.95 Resumption of water (%) 8.4 050m (pm) after deagglomeration with ultrasound 4.1 FDM after deagglomeration with ultrasound 16.1 pH 3.96 3 0 1 EXAMPLE 3 (Comparative) A portion of the silica cake obtained in Example 1 is then subjected to a disintegration step. The cake obtained in the filtration stage is subjected to a disintegration operation in a continuously stirred reactor with simultaneous addition to the cake of 27.8 grams of a sodium aluminate solution (Al / SiO 2 , 3%) and 29.8 grams of a 7.7% by weight sulfuric acid solution. This disintegrated cake (having a solids content of 22% by weight) is then dried by means of a bi-fluid nozzle atomizer by spraying the disintegrated cake through a 2.54 mm SU5 (Spraying System) nozzle. with a pressure of 1 bar under the following average flow and temperature conditions: Average inlet temperature: 250 ° C Average outlet temperature: 135 ° C 20 Average flow rate: 15 1 / h. The characteristics of the silica C1 obtained (in the form of substantially spherical beads) are then as follows: BET (m 2 / g) 221 content of polycarboxylic acid + carboxylate (C) (%) - content of aluminum (AI) (%) 0 , 4 CTAB (m2 / g) 206 ysd (7.1 d / m2) 59.6 Width Ld (XDC) 1.08 V (d5-d50) N (d5-d100) 0.69 Porous distribution width Idp 1.06 Width D (XDC) 0.97 Water recovery (%) 8.9 050m (dam) after ultrasound deagglomeration 6.2 F Dm after ultrasound deagglomeration 15.3 pH 6.47 25 EXAMPLE 4 In a Brabender-type internal mixer (380 ml), the elastomeric compositions are prepared, the composition of which, expressed in part by weight per 100 parts of elastomers (phr), is given in Table I below: TABLE I Sample Composition 1 Composition 1 SBR (1) 70 70 BR (1) 30 Silica Cl (2) 75 Silica S1 (3) 75 Coupling agent (4) 6.6 6.6 Plasticizer (5) 20 20 Carbon black (N330 ) 5.0 5.0 ZnO 2.5 2.5 Stearic acid 2.0 2.0 Antioxidant (6) 1.9 1.9 DPG (7) 2.0 2.0 CBS (8) 1.7 1.7 Sulfur 1.5 1.5 (1) S-SBR (HPR355 from JSR) functionalized with 57% vinyl patterns; 27% styrene units; Tg close to -27 ° C / BR (Buna CB 25 from Lanxess) (2) Silica Cl (disintegration with simultaneous addition of sodium aluminate and sulfuric acid (example 3 - comparative)) (3) Silica S1 according to the present invention (disintegration with addition of a mixture of MGA acids (Example 2 above)) (4) Bis-triethoxysilylpropyldisulfidosilane (JH-S75 TESPD from Castle Chemicals) (5) TDAE type plasticizing oil ( Vivatec 500 from Hansen & Rosenthal KG) (6) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine (Santoflex 6-PPD from Flexsys) (7) Diphenylguanidine (Rhenogran DPG-80 from the company RheinChemie) (8) N-cyclohexyl-2-benzothiazyl-sulfenamide (Rhenogran CBS-80 from RheinChemie) Process for preparing the elastomeric compositions: The process for preparing the rubber compositions is carried out in two successive preparation phases. A first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C. This phase allows the introduction of the vulcanization system. The first phase is carried out by means of a mixing apparatus, internal mixer type Brabender brand (capacity of 380 ml). The filling factor is 0.6. The initial temperature and the speed of the rotors are fixed each time so as to reach mixing temperatures of the vicinity of 115-170 ° C. Decomposed here in two passes, the first phase allows to incorporate in a first pass, the elastomers and then the reinforcing filler (fractional introduction) with the coupling agent and stearic acid. For this pass, the duration is between 4 and 10 minutes. After cooling the mixture (temperature below 100 ° C.), a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular). The duration of this pass is between 2 and 5 minutes. After cooling the mixture (temperature below 100 ° C), the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes. Each final mixture is then calendered in the form of plates 2-3 mm thick. On these so-called raw mixtures obtained, an evaluation of their rheological properties makes it possible to optimize the duration and the vulcanization temperature. Then, the mechanical and dynamic properties of vulcanized mixtures at the optimum of firing (T98) are measured. Rheological properties - Viscosity of raw mixtures: The Mooney consistency is measured on the compositions in the uncured state at 100 ° C. by means of a MV 2000 rheometer as well as the determination of the Mooney stress relaxation rate according to the NF ISO standard. 289.
[0043] The value of the torque read after 4 minutes after preheating for one minute (Mooney Large (1 + 4) - at 100 ° C) is shown in Table II. The test is carried out after making the raw mixtures and then after aging for 3 weeks at a temperature of 23 +/- 3 ° C.
[0044] Table II References Control 1 Composition 1 ML (1 + 4) - 100 ° C Initial 166 136 Initial Mooney Relaxation 0.204 0.229 ML (1 + 4) - 100 ° C After 17 days 182 154 (23 +/- 3 ° C) Relaxation Mooney After 17 days 0,175 0,206 (23 +/- 3 ° C) ML (1 + 4) - 100 ° C After 21 days (23,183 155 +/- 3 ° C) Mooney Relaxation After 21 days (23 0,183 0,201 + / - 3 ° C) It is found that the silica S1 of the present invention (Composition 1) allows a consequent reduction of the initial green viscosity, compared to the value of the mixture with the reference (Control 1).
[0045] It is also found that the silica S1 of the present invention (Composition 1) makes it possible to maintain the advantage in raw reduced viscosity, with respect to the value of the mixture with the reference (Control 1), after 3 weeks of storage.
[0046] This type of behavior over time is very useful for those skilled in the art in the case of the implementation of rubber mixtures containing silica. Rheometry of the compositions: The measurements are carried out on the compositions in the green state. The results relating to the rheology test, which is conducted at 160 ° C. using an ODR MONSANTO rheometer according to the NF ISO 3417 standard, are shown in Table III.
[0047] According to this test, the composition to be tested is placed in the controlled test chamber at a temperature of 160 ° C. for 30 minutes, and the resistive torque opposite the composition is measured at a low amplitude oscillation (3 °). a biconical rotor included in the test chamber, the composition completely filling the chamber in question. From the curve of variation of the torque as a function of time, one determines: the minimum torque (Cmin) which reflects the viscosity of the composition at the temperature considered; - the maximum torque (Cmax); - the delta-pair (AC = Cmax - Cmin) which reflects the degree of crosslinking caused by the action of the crosslinking system and, if necessary, coupling agents; the time T98 necessary to obtain a state of vulcanization corresponding to 98% of the complete vulcanization (this time is taken as the vulcanization optimum); and the toasting time TS2 corresponding to the time required to have a rise of 2 points above the minimum torque at the temperature under consideration (160 ° C.) and which reflects the time during which the mixtures can be used. at this temperature without initiation of vulcanization (the mixture cures from TS2). The results obtained are shown in Table III. Table III Compositions Control 1 Composition 1 Cmin (dN.m) 32.6 28.1 Cmax (dNm) 73.9 69.3 Delta couple (dN.m) 41.3 41.2 TS2 (min) 3, 1, 4.6 T98 (min) 27.1 27.2 The use of the silica S1 of the present invention (Composition 1) makes it possible to reduce the minimum viscosity (sign of an improvement in the raw viscosity) with respect to to the control mixture (Control 1) without penalizing the vulcanization behavior. It is also found that the use of the silica S1 of the present invention (Composition 1) makes it possible to improve the toasting time TS2 with respect to the control mixture (Control 1) without penalizing the time T98.
[0048] Mechanical Properties of the Vulcanizates: The measurements are carried out on the optimally vulcanized compositions (T98) for a temperature of 160.degree. The uni-axial tensile tests are carried out in accordance with the NF ISO 37 standard with specimens of type H2 at a speed of 500 mm / min on an INSTRON 5564. The modules x%, corresponding to the stress measured at x % tensile strain, and tensile strength are expressed in MPa; the elongation at break is expressed in%. It is possible to determine a reinforcement index (I.R.) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus. The Shore A hardness measurement of the vulcanizates is carried out according to ASTM D 2240. The given value is measured at 15 seconds. The measured properties are collated in Table IV. Table IV Compositions Control 1 Composition 1 Module 10% (Mpa) 0.91 0.93 Module 100% (Mpa) 3.1 3.1 Module 300% (Mpa) 12.2 11.9 Resistance rupture (MPa) 16, 1 16.7 Elongation at break (%) 373 387 IR 3.9 3.8 Shore hardness A-15s (pts) 73 70 The use of a silica S1 of the present invention (Composition 1) makes it possible to obtain a satisfactory level of reinforcement compared to the control mixture (Control 1) and in particular to maintain a high level of the 300% deformation module. Dynamic properties of vulcanizates: Dynamic properties are measured on a viscoanalyzer (Metravib VA3000) according to ASTM D5992. The loss factor (tan δ) and complex modulus values in dynamic compression (E *) are recorded on vulcanized samples (cylindrical specimen of section 95 mm 2 and height 14 mm). The sample is subjected initially to a pre-deformation of 10% then to a sinusoidal deformation in alternating compression of +/- 2%. The measurements are carried out at 60 ° C. and at a frequency of 10 Hz. The results, presented in Table V, are thus the complex modulus in compression (E * -60 ° C.-10 Hz) and the loss factor (tan). b - 60 ° C - 10 Hz).
[0049] Table V Compositions Control 1 Composition 1 E * - 60 ° C - 10 Hz (MPa) 13.6 13.3 Tan δ - 60 ° C - 10 Hz 0.164 0.160 The use of a silica S1 of the present invention (Composition 1) makes it possible to maintain the dynamic properties at the level of that of the control mixture (control 1). Examination of the different Tables II to V shows that the composition according to the invention (Composition 1) makes it possible to obtain a good compromise implementation / reinforcement / hysteretic properties with respect to the control composition (Control 1) and in particular a consequent gain in raw viscosity which remains stable storage over time.

权利要求:
Claims (32)
[0001]
CLAIMS 1- A process for the preparation of a precipitated silica of the type comprising the precipitation reaction between a silicate and an acidifying agent, whereby a suspension of precipitated silica is obtained, characterized in that it comprises the following steps: performs the precipitation reaction in the following manner: (i) forming an aqueous base stock having a pH of between 2.0 and 5.0, preferably between 2.5 and 5.0, (ii) adding to said at the same time, silicate and acidifying agent, in such a way that the pH of the reaction medium is maintained between 2.0 and 5.0, (iii) the addition of the acidifying agent is stopped while continuing the addition of silicate in the reaction medium until a pH value of the reaction medium of between 7.0 and 10.0 is reached; (iv) silicate and sodium silicate are added simultaneously to the reaction medium; the acidifying agent, so that the pH of the reaction medium is maintained between 7.0 and 10.0, (V) the addition of the silicate is stopped while continuing the addition of the acidifying agent in the reaction medium until a pH value of the reaction medium is obtained. less than 6.0, the resulting silica suspension is filtered, the filtration cake obtained after the filtration is subjected to a disintegration operation, said process being characterized in that it is added to the filter cake either during the disintegration operation, or after the disintegration operation and before the drying step, at least one polycarboxylic acid.
[0002]
2- The method of claim 1, wherein, during the disintegration operation, at least one polycarboxylic acid is added to the filter cake.
[0003]
3. The method of claim 1, wherein at least one polycarboxylic acid is added to the filter cake after the disintegration operation.
[0004]
4. Method according to one of claims 1 to 3, wherein said polycarboxylic acid is selected from dicarboxylic acids and tricarboxylic acids.
[0005]
5. Method according to one of claims 1 to 4, wherein said polycarboxylic acid is selected from linear or branched polycarboxylic acids, saturated or unsaturated, aliphatic having 2 to 20 carbon atoms or aromatic.
[0006]
6. Process according to claim 4, in which the dicarboxylic acids and the tricarboxylic acids are chosen from adipic acid, succinic acid, ethylsuccinic acid, glutaric acid, methylglutaric acid and oxalic acid. citric acid.
[0007]
7- Method according to one of claims 1 to 6, wherein a mixture of polycarboxylic acids is added to the filter cake.
[0008]
The process as claimed in claim 7, wherein the mixture of polycarboxylic acids is a mixture of dicarboxylic and / or tricarboxylic acids, in particular a mixture of at least three dicarboxylic and / or tricarboxylic acids, in particular a mixture of three dicarboxylic and / or tricarboxylic acids.
[0009]
9. The process as claimed in claim 7, in which the mixture of polycarboxylic acids is a mixture of dicarboxylic acids, in particular a mixture of at least three dicarboxylic acids, in particular a mixture of three dicarboxylic acids.
[0010]
10. A process according to any one of claims 7 to 9, wherein the polycarboxylic acid mixture comprises the following acids: adipic acid, glutaric acid and succinic acid.
[0011]
11. The process according to claim 10, wherein the mixture of polycarboxylic acids comprises 15.00 to 35.00% by weight of adipic acid, 40.00 to 60.00% by weight of glutaric acid and 15, 00 to 25.00% by weight of succinic acid.
[0012]
12. The process as claimed in one of claims 7 to 9, in which the mixture of polycarboxylic acids comprises the following acids: methylglutaric acid, ethylsuccinic acid and adipic acid.
[0013]
13- The method of claim 12, wherein the mixture of polycarboxylic acids comprises 60 to 96% by weight of methylglutaric acid, 3.90 to 20.00% by weight of ethylsuccinic acid and 0.05 to 20.00 % by weight of adipic acid.
[0014]
14- Method according to one of claims 7 to 13, wherein a part or all of the polycarboxylic acids of the mixture used is in the form of anhydride, ester, salt (carboxylate) of alkali metal, salt (carboxylate ) of alkaline earth metal or ammonium salt (carboxylate).
[0015]
15. Process according to claim 14, in which the mixture of polycarboxylic acids is a mixture comprising: methylglutaric acid, in particular in a proportion of 60.00 to 96.00% by weight; ethylsuccinic acid, in particular in a proportion of 3.90 to 20.00% by weight, adipic acid, in particular in a proportion of 0.05 to 20.00% by weight.
[0016]
16. The process according to claim 14, wherein the polycarboxylic acid mixture is a mixture comprising: methylglutaric acid, in particular in a proportion of 10.00 to 50.00% by weight, methylglutaric anhydride, in particular in a proportion of 40.00 to 80.00% by weight, ethylsuccinic anhydride, in particular in a proportion of 3.90 to 20.00% by weight, of the acid adipic acid, in particular in a proportion of 0.05 to 20.00% by weight. 35
[0017]
17. Precipitated silica, characterized in that it possesses: a BET specific surface area between 45 and 550 m 2 / g, in particular between 70 and 370 m 2 / g, in particular between 80 and 350 m 2 / g, a specific surface area CTAB between 40 and 525 m2 / g, in particular between 70 and 350 m2 / g, in particular between 80 and 310 m2 / g, - a content (C) of polycarboxylic acid + corresponding carboxylate, expressed as total carbon, from minus 0.15% by weight, in particular at least 0.20% by weight, - a width Ld ((d84 - d16) / d50) of object size distribution measured by XDC granulometry after deagglomeration with ultraviolet at least 0.91 and a distribution of the pore volume such that the ratio V (d5-d50) / V (d5-dio0) is at least 0.65, in particular at least 0.66. . 10
[0018]
18- precipitated silica according to claim 17, characterized in that it has an object size distribution width Ld of at least 0.94.
[0019]
19. Precipitated silica according to one of claims 17 and 18, characterized in that its ratio V05-me / (a5-dioo) is at least 0.68.
[0020]
20- precipitated silica according to one of claims 17 to 19, characterized in that it has: - a width Ld ((d84 - d16) / d50) of object size distribution measured by XDC granulometry after deagglomeration at ultrasound of at least 1.04 and - a distribution of the pore volume such that the ratio V (d5 - d50) Ai (d5 - d100) is at least 0.70, in particular at least 0.71 .
[0021]
21- Precipitated silica, characterized in that it has: a BET specific surface area of between 45 and 550 m 2 / g, in particular between 70 and 370 m 2 / g, in particular between 80 and 350 m 2 / g, specific CTAB between 40 and 525 m2 / g, especially between 70 and 350 m2 / g, in particular between 80 and 310 m2 / g, - a content (C) corresponding polycarboxylic acid + carboxylate, expressed as total carbon, at least 0.15% by weight, in particular at least 0.20% by weight, a porous distribution width ldp greater than 0.65, in particular greater than 0.70, in particular greater than 0.80. . 35
[0022]
22- precipitated silica according to claim 21, characterized in that it has a width Ld ((d84 - d16) / d50) of object size distribution measured by XDC granulometry after disintegration with ultrasound of at least 0 , 91, in particular of at least 0.94.
[0023]
23- precipitated silica according to one of claims 17 to 22, characterized in that it has a BET specific surface area of between 100 and 320 m2 / g, in particular between 120 and 300 m2 / g.
[0024]
24- precipitated silica according to one of claims 17 to 23, characterized in that it has a specific surface CTAB between 100 and 300 m2 / g, in particular between 120 and 280 m2 / g.
[0025]
25- precipitated silica according to one of claims 17 to 24, characterized in that it has a content (C) corresponding polycarboxylic acid + carboxylate, expressed as total carbon, at least 0.24% by weight, in at least 0.30% by weight.
[0026]
26- Precipitated silica according to one of claims 17 to 25, characterized in that it has a dispersive component of the surface energy ysd less than 52 mJ / m 2, especially less than 50 mJ / m 2, in particular of at most 45 mJ / m2, for example less than 40 mJ / m2.
[0027]
27- Precipitated silica according to one of claims 17 to 26, characterized in that it has a water recovery greater than 6%, in particular greater than 7%.
[0028]
28- Use as reinforcing filler for polymers, especially for tires, a precipitated silica according to one of claims 17 to 27 or obtained by the method according to one of claims 1 to 16.
[0029]
29- Use of a precipitated silica according to one of claims 17 to 27 or obtained by the method according to one of claims 1 to 16 in a polymer composition, to reduce the viscosity of said composition.
[0030]
30- Composition of polymers comprising a precipitated silica according to one of claims 17 to 27 or obtained by the method according to one of claims 1 to 16.
[0031]
31- Article comprising at least one composition according to claim 30, this article consisting of a shoe sole, a floor covering, a gas barrier, a flame-retardant material, a cable-car wheel, a joint of household appliances, a gasket liquid or gas lines, braking system gasket, pipe, sheath, cable, motor support, battery separator, conveyor belt, transmission belt, or, preferably, tire .
[0032]
Tire according to claim 31.5

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TW201542458A|2015-11-16|

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FR3017610B1|2016-03-18|

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法律状态:
2015-02-10| PLFP| Fee payment|Year of fee payment: 2 |

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2016-01-08| PLFP| Fee payment|Year of fee payment: 3 |

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2017-01-12| PLFP| Fee payment|Year of fee payment: 4 |

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2018-01-11| PLFP| Fee payment|Year of fee payment: 5 |

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2020-01-13| PLFP| Fee payment|Year of fee payment: 7 |

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2021-01-13| PLFP| Fee payment|Year of fee payment: 8 |

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2022-01-18| PLFP| Fee payment|Year of fee payment: 9 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1400415A|FR3017610B1|2014-02-14|2014-02-14|NOVEL PROCESS FOR THE PREPARATION OF PRECIPITATED SILICES, NOVEL PRECIPITED SILICES AND THEIR USES, IN PARTICULAR FOR THE STRENGTHENING OF POLYMERS|FR1400415A| FR3017610B1|2014-02-14|2014-02-14|NOVEL PROCESS FOR THE PREPARATION OF PRECIPITATED SILICES, NOVEL PRECIPITED SILICES AND THEIR USES, IN PARTICULAR FOR THE STRENGTHENING OF POLYMERS|

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JP2016551790A| JP6580054B2|2014-02-14|2015-02-12|Novel process for the preparation of precipitated silica, novel precipitated silica, and their use, especially for reinforced polymers|

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EP15703998.3A| EP3105181A1|2014-02-14|2015-02-12|Novel method for preparing precipitated silicas, novel precipitated silicas and the uses of same, in particular for reinforcing polymers|

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PCT/EP2015/052921| WO2015121333A1|2014-02-14|2015-02-12|Novel method for preparing precipitated silicas, novel precipitated silicas and the uses of same, in particular for reinforcing polymers|

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CN201580008498.9A| CN106029567B|2014-02-14|2015-02-12|It is used to prepare the novel method of precipitated silica, novel precipitated silica and application thereof, particularly for enhancing polymer|

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CA2938865A| CA2938865A1|2014-02-14|2015-02-12|Novel method for preparing precipitated silicas, novel precipitated silicas and the uses of same, in particular for reinforcing polymers|

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KR1020167022694A| KR20160122744A|2014-02-14|2015-02-12|Novel method for preparing precipitated silicas, novel precipitated silicas, and the uses of same, in particular for reinforcing polymers|

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US15/118,716| US10259715B2|2014-02-14|2015-02-12|Method for preparing precipitated silicas, novel precipitated silicas and the uses of same, in particular for reinforcing polymers|

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MX2016010477A| MX2016010477A|2014-02-14|2015-02-12|Novel method for preparing precipitated silicas, novel precipitated silicas and the uses of same, in particular for reinforcing polymers.|

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ARP150100437A| AR099423A1|2014-02-14|2015-02-13|PROCEDURE FOR PREPARING PRECIPITATED SILKS AND PRECIPITATED SILKS OBTAINED|

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TW104105162A| TWI686353B|2014-02-14|2015-02-13|Novel process for preparing precipitated silicas, novel precipitated silicas and uses thereof, especially for reinforcing polymers|