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    • 专利摘要:
    The invention relates to a preparation of a masterbatch of synthetic elastomer and carbonaceous filler, which comprises the following steps: - preparing an aqueous dispersion of carbonaceous filler having a Zeta potential of opposite sign to that of an elastomer latex anionic or cationic synthetic, the difference of the potentials of the anionic or cationic elastomer latex and the aqueous dispersion of carbonaceous filler being such that its absolute value is greater than or equal to 20mV, - contacting and mixing the latex of elastomer synthetic anionic or cationic and aqueous dispersion of carbonaceous filler to obtain a coagulum, - recover the coagulum, - dry the recovered coagulum to obtain the masterbatch.
    公开号:FR3035110A1
    申请号:FR1553314
    申请日:2015-04-15
    公开日:2016-10-21
    发明作者:Francois Lallet；Marie Eloy
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The invention relates to the preparation of a masterbatch of synthetic diene elastomer and carbonaceous filler. The term "masterbatch" (commonly referred to by its English name as "masterbatch") means an elastomer-based composite in which a filler and possibly other additives have been introduced. In order to obtain the optimum reinforcing properties conferred by a load in a tire tread and thus a high wear resistance, it is known that it is generally appropriate for this filler to be present in the elastomeric matrix under final form that is both finely divided possible and distributed in the most homogeneous way possible. However, such conditions can be achieved only to the extent that this charge has a very good ability, on the one hand to incorporate into the matrix during mixing with the elastomer and to disintegrate, disperse and distribute homogeneously in this matrix.
    [0002] However, in order to improve the dispersibility of the filler in the elastomeric matrix, it is known to use a mixture of elastomer and "liquid" phase filler. To do this, it uses an elastomer in the form of latex, and an aqueous dispersion of the load, commonly called "slurry".
    [0003] In this field, as early as 1955, the problem of the uniform dispersion of the charges, and in particular of the carbon black in the rubber, was already posed. Thus, it is known from BE 541816 a process for preparing a masterbatch of rubber and carbon black in the liquid phase. This process is continuous and uses hydraulic shocks or violent mechanical agitation to achieve the dispersion of carbon black within the elastomeric matrix. Moreover, this process, if it operates with carbonaceous fillers, such as carbon blacks, which coagulate spontaneously with the natural rubber, does not make it possible to obtain coagulation with synthetic elastomers. It is therefore necessary to add an agent called "coagulation" to achieve the setting in mass, so coagulation with synthetic elastomers. The term "aqueous-phase coagulation agent" means salts such as sodium chloride, acids such as hydrogen chloride or bases such as sodium hydroxide.
    [0004] More recently, WO97 / 36724 discloses a process for preparing a masterbatch and specific equipment for improving the dispersibility of carbon black in a natural rubber latex. This technology has two objectives: the realization of the coagulation step in the absence of coagulating agent and the obtaining of a masterbatch, the distribution of the charge is uniform. However, this technology has a number of disadvantages. The equipment used is very complex and the method described relies on very specific characteristics related to this equipment, such as a geometry of the defined coagulation zone or a defined flow rate difference.
    [0005] Thus, a process for the preparation of a masterbatch leading to a masterbatch with a uniform load distribution throughout the product, whose mass yield and filler / elastomer ratio are satisfactory, is investigated. to be easy to implement from simple equipment, without the use of coagulation agent. This process is particularly advantageous for carbon black which coagulates spontaneously with natural rubber but not with synthetic elastomers. The Applicants have surprisingly discovered a method of simply obtaining a synthetic carbon-elastomer feedstock masterbatch prepared in the "liquid" phase, which makes it possible to obtain good dispersion of the feedstock in the matrix, without using coagulation agent. Such a method makes it possible, moreover, not only to achieve a very good coagulation efficiency (greater than 80% by mass) while respecting the feed rate previously introduced (a difference of 20% with respect to the feed rate initially calculated being considered acceptable). The invention thus relates to a method for preparing a synthetic elastomer and carbonaceous filler masterbatch, which comprises the steps of: preparing an aqueous dispersion of carbonaceous filler having a Zeta potential of opposite sign to that of anionic or cationic synthetic elastomer latex, the difference of the potentials of the anionic or cationic elastomer latex and of the aqueous carbonaceous filler dispersion being such that its absolute value is greater than or equal to 20 mV, - bringing into contact and mixing the anionic or cationic synthetic elastomer latex and the aqueous carbonaceous filler dispersion to obtain a coagulum. - recover the coagulum, - dry the recovered coagulum to obtain the masterbatch. For the purposes of the invention, "carbonaceous filler" means a particulate object containing in its mass only carbon atoms, "with impurities close" being understood that at the surface there may be other atoms. A carbonaceous filler can be chosen, without being exhaustive, among carbon blacks, natural and synthetic graphites, carbon fibers, graphenes, fullerenes, acetylene blacks and carbon nanotubes. According to a preferred characteristic of the invention, the synthetic elastomer is a synthetic diene elastomer. Preferably, the Zeta potentials of the anionic or cationic elastomer latex and the aqueous carbonaceous filler dispersion have a difference whose absolute value is greater than or equal to 30mV. According to another characteristic of the invention, the aqueous dispersion of carbonaceous filler contains a surfactant of opposite sign to that of the synthetic elastomer latex.
    [0006] Advantageously, the anionic or cationic synthetic elastomer latex contains at least one respectively anionic or cationic surfactant. According to one embodiment of the invention, the synthetic elastomer latex is obtained by polymerization in aqueous phase. According to another embodiment of the invention, the synthetic elastomer latex is obtained by emulsification in the aqueous phase of a diene elastomer.
    [0007] Preferably, the synthetic elastomer latex is a butadiene copolymer latex and styrene, SBR, and even more preferably the synthetic elastomer latex is an emulsion prepared SBR. According to an alternative embodiment of the invention, the carbonaceous feedstock consists of carbon black, preferably the amount of carbonaceous filler when two aqueous dispersions are brought into contact, ranging from 2 phr to 150 phr, parts by weight. percent of organic matter. The subject of the invention is also a masterbatch of synthetic diene elastomer and of carbonaceous filler obtained according to the method mentioned above, as well as a composition based on at least one such masterbatch. The invention also relates to a finished or semi-finished article comprising a composition as mentioned above, a tire tread comprising such a composition and a tire or semi-finished product comprising at least one such composition. MEASUREMENTS AND TESTS 1.1 Zeta potential measurement As used herein, the Zeta potential is a scientific term for the electrokinetic potential in colloidal systems. In the literature of colloidal chemistry, it is generally designated using the Greek letter Zeta, hence potential.. The Zeta potential is a measure of the magnitude of repulsion or attraction between particles. The Zeta potential is an index of the magnitude of colloidal particle interaction, and Zeta potential measurements are used to gain access to the stability of colloidal systems. Most colloidal dispersions in aqueous media carry a surface charge.
    [0008] If acid groups are present on the surface of a particle, it will tend to develop a negative surface charge. In contrast, if basic groups are present on the surface of a particle, it will tend to develop a positive surface charge. The magnitude of the surface charge depends on the acidic or basic strength of the surface groups and the pH of the solution. The surface charge can be reduced to zero by removing surface ionization by reducing the pH in the case of negatively charged particles or increasing the pH in the case of positively charged particles. Surfactants can be specifically adsorbed on the surface of a particle, which leads, in the case of cationic surfactants, to a positive charge surface, and in the case of anionic surfactants, to a surface of negative charge. See "Zeta 25 Potential an Introduction in 30 Minutes", technical note from the Zêtasizer Nano series, p. 3 (before September 2010). The appearance of a net charge on the surface of a particle affects the distribution of ions in the surrounding interfacial region, which results in an increased concentration of counter-ions, ions of charge opposite to that of the particle, near the surface. Thus, there is a double electric layer around each particle. The liquid layer surrounding the particle is in two parts: an inner region (Stern layer) where the ions are strongly bound and an outer region (diffuse layer) where they are less well associated. In the diffuse layer, there is an imaginary boundary within which ions and particles form a stable entity. When a colloidal particle moves (e.g., under the effect of thermal agitation), the ions within the boundary move with it. The ions beyond the border remain with the dispersant volume. The potential at the boundary (hydrodynamic shear surface) is the Zeta potential. From a theoretical point of view, the Zeta potential is an electrical potential in the interfacial double layer (DL) at the location of the sliding plane with respect to a point in the fluid volume far away from the interface. In other words, the Zeta potential is the potential difference between the dispersion medium and the stationary fluid layer attached to the dispersed particle. The Zeta potential is widely used for quantizing the magnitude of the electric charge at the double layer level. Zeta potential should not be confused with electrode potential or electrochemical potential (because electrochemical reactions are not generally involved in the occurrence of Zeta potential).
    [0009] In aqueous media, the pH of the sample affects its Zeta potential. For example, if an alkali is added to a suspension with a negative Zeta potential, the particles tend to acquire a more negative charge. If an acid is added in sufficient quantity to the suspension, then a point will be reached where the charge will be neutralized. The addition of an additional amount of acid will cause a positive charge build-up.
    [0010] The Zeta potential is not directly measurable, but it can be calculated using theoretical models and experimentally determined electrophoretic mobility or electrophoretic mobility. Electrokinetic phenomena and electroacoustic phenomena are the usual sources of data for calculating the Zeta potential. However, for purposes of this application, the Zeta potential is calculated using electrokinetic phenomena, in particular electrophoresis. Electrophoresis is used to estimate the Zeta potential of particles, while the potential / flow current is used for porous bodies and flat surfaces.
    [0011] Electrophoresis is the movement of a charged particle with respect to the liquid where it is suspended under the influence of an applied electric field. When an electric field is applied through an electrolyte, charged particles suspended in the electrolyte are attracted to the opposite charging electrode. The viscous forces acting on the particles tend to oppose this movement. When equilibrium is reached between these two opposing forces, the particles move at a constant rate. The velocity depends on the intensity of the electric field or the voltage gradient, the dielectric constant of the medium, the viscosity of the medium and the Zeta potential. The velocity of the particle in a unit electric field is called its electrophoretic mobility. The Zeta potential is related to electrophoretic mobility by the Henry equation: UE = (2gf (ca)) / 311 where UE = electrophoretic mobility, = = Zeta potential, E - dielectric constant, rl = viscosity and f ( ca) = Henry's function. The unit of x, called the Debye length, is the inverse of a length and K-1 is often considered as a measure of the "thickness" of the electric double layer. The parameter 'a' refers to the radius of the particle, and therefore Ka measures the ratio between the radius of the particle and the thickness of the electric double layer. Electrophoretic determinations of the Zeta potential are most often made in an aqueous medium and at a moderate electrolyte concentration; in this case, f (ca) is 1.5 which corresponds to the Smoluchowski approximation. Therefore, calculation of the Zeta potential from mobility is simple for those systems for which the Smoluchowski model is suitable, ie particles larger than about 0.2 μm (200 nm) dispersed in the Smoluchowski model. electrolytes containing more than 10-3M (M = mole.L-1) of salt. For small particles in low dielectric constant media (eg, non-aqueous media), f (ca) becomes 1.0 and allows such a simple calculation. This is called Huckel's approximation.
    [0012] Thus, the particles within the dispersion with a Zeta potential will migrate to the opposite charge electrode with a rate proportional to the magnitude of the Zeta potential. The essence of a conventional microelectrophoresis system is a capillary cell with electrodes at both ends to which a potential is applied. The particles move towards the electrode, their velocity is measured and expressed in a field of unit intensity such as their mobility. The first methods involved the process of direct observation of individual particles using ultramicroscopic techniques and manual tracking of their progress over a measured distance. This procedure, although still used by many groups in the world, suffers from several disadvantages, starting with the significant effort required to make a measurement, particularly with small or weakly diffusing particles. More generally, this speed is measured using the laser Doppler anemometer technique. The frequency shift or phase shift of an incident laser beam caused by these moving particles is measured as the mobility of the particles, and this mobility is converted to Zeta potential by introducing the viscosity and dielectric permittivity of the dispersant, and applying Smoluchowski's theories. The ZETASIZER NANO series available from Malvern Instruments, UK, utilizes a combination of laser Doppler velocimetry and scattered light phase analysis (PALS) in a patented technique called M3-PALS to measure the electrophoretic mobility of a particle. A Zeta potential measurement system of the ZÊTASIZER NANO series available from Malvern Instruments consists of six main components. First, a laser is used to provide a light source for illuminating the particles within the sample. For Zeta potential measurements, this light source is separated to obtain an incident beam and a reference beam. The incident laser beam passes through the center of the sample cell, and light scattered at an angle of about 13 ° is detected. When an electric field is applied to the cell, any particle moving in the measurement volume causes a fluctuation of the detected light intensity 40 with a frequency proportional to the particle velocity, and this information is transferred to a digital signal processor then to a computer. The ZÊTASIZER NANO software generates a frequency spectrum from which the electrophoretic mobility and thus the Zeta potential are calculated. The intensity of the scattered light detected must lie in a specific range for the detector to measure it correctly. To achieve this, an attenuator is used, which adjusts the intensity of the light reaching the sample and thus the intensity of the scattering. To correct any difference in cell wall thickness and refraction of the dispersant, compensation optics are provided to maintain optimal alignment.
    [0013] The Zeta potential measurement is performed on a Nano-ZS ZetaSizer device marketed by Malvern Instrument, on a sample of diluted x100 latex or slurry in a 10-3M NaCl solution. The sample preparation protocol for zeta potential measurement is as follows: Prepare 1000mL of a 10-3M NaC1 stock solution by introducing 58mg NaCl in a volumetric flask of 1000mL and make up with ultra-violet water. pure to the mark. Prepare the measurement sample by introducing 1 mL of latex or slurry into a 100 mL volumetric flask and make up to the mark with the 1M 3M NaC1 stock solution.
    [0014] Thus, according to the invention, Zeta potentials 1 1 and 2 2 respectively of the charge dispersion and the synthetic elastomer latex, of opposite signs, the difference of these Zeta potentials, ΔC, has an absolute value. 1341 corresponding to Ki - Ç2I; this value 1.41 must be greater than or equal to 20mV to be in accordance with the invention, and more preferably greater than or equal to 30 mV. 1.2 ATG (or TGA) Loading Rate Measurement The purpose of this procedure is to quantify the categories of constituents of the rubber mixes. There are 3 temperature ranges that each correspond to a category of constituents: 1. between 250 ° C and 550 ° C organic materials: elastomers, oils, vulcanizing agents, etc. 2. between 550 ° C and 750 ° C the carbonaceous charges. 3. Above 750 ° C ashes: ZnO, and silica if necessary. It applies to both raw and cooked mixes. 3035110 - 8 - (a) - Apparatus - Thermogravimetric analysis set on a METTLER 5 TOLEDO brand analyzer: TGA 851 or TGA DSC1 model. - Balance 1/100 mg mark and scale model. - Alumina crucibles 700 (without lid) Mettler Toledo ref 00024123. - Miscellaneous laboratory equipment: pliers, scissors etc. B) - Principle The weight losses of a mixing sample subjected to an increase in temperature are monitored. The latter is done in two stages: Heating from 25 ° C. to 550 ° C. under an inert atmosphere (N 2) to evaporate the volatile materials and to pyrolyze the organic materials. The volatility of the resulting products results in a corresponding weight loss in the first time (before 250 ° C) to the volatile materials and then to the organic materials initially present in the mixture. 20 - Continuation of heating up to 750 ° C under oxidizing atmosphere (Air or 02) to achieve the combustion of black (and / or charcoal). The resulting volatility of the products results in a weight loss corresponding to the initial amount of black (and / or charcoal material). The products that remain after these treatments constitute ashes. These are usually inorganic materials such as ZnO, silica etc. c) - Measures c) -1- Preparation of samples The quantity of product analyzed must be weighed to 0.01mg and between 20mg and 30mg. It is then placed in a 70111 alumina crucible (without lid). C) -2- Definition of the "method" (temperature program) - The following segments are successively defined: the segment: dynamic of 25 ° C. at 550 ° C. at 50 ° C./min, under nitrogen (40 ml / min), 2nd segment: dynamic range of 550 ° C. to 750 ° C. at 10 ° C./min, under air (or 02) (40m1 / min). - Activate the field "subtract curve to blank".
    [0015] 5 Any measurement is automatically corrected for a blank curve. The latter is made under the same conditions as the measurement, with empty crucible. It is stored and used for all the following measurements (no new blank test required before each measurement). 10 c) -3- Start of the measurement Make sure beforehand, by consulting the control window of the oven, that the nitrogen and air flow rates are correctly adjusted (401.11 / min). Otherwise adjust them using the settings on the "gas box". 15 - Blank curve The blank curve is carried out following the procedure described in the TGA user manual. Measurement Measurement is carried out following the procedure described in the TGA User Manual. c) -4- Exploitation of the curve By following the instructions of the user manual of the TGA one selects and opens the curve to be exploited, one delimits on this curve the bearing, corresponding to the volatile materials, between respectively 25 ° C and about 250 ° C., the loss of weight corresponding to the volatile matter content (in%) is calculated, the 28th stage, corresponding to the organic materials, is delineated on this curve between, respectively, the temperature of the bearing approximately 250 ° C. ° C. and 550 ° C., the loss of weight corresponding to the organic matter content (in%) is calculated, the 3rd stage, corresponding to the losses, is delineated on this curve between 550.degree. C. and 750.degree. C., respectively. the loss of weight corresponding to these losses (in%), the residue or ash rate in% is calculated. The presence of volatile compounds For certain mixtures containing volatile compounds which can evaporate at room temperature, there is a risk of loss of material between the sample preparation and the actual departure. of the measure. These losses are not taken into account by the device. To take into account these losses and to have the actual composition of the mixture, one can proceed as follows: The steps c) -1 to c) -3 previously described are carried out with the following 2 instructions: in the preparation of the sample: note the weight of the empty crucible (P0) and the weight of the sample Pl, - when launching the measurement: enter the "crucible weight" field by 15 PO and the "sample weight" field by P1. For operation (step c) -4), the TGA takes into account, in order to determine the losses, the mass of the sample P2 which it calculates at the effective start of the measurement from the weight of the crucible, which is essential for the calculation of the residue; P2 is calculated by the TGA taking into account the mass P3 (crucible + sample) at the time TO - P0. The calculation of the levels of the various constituents and the residue is carried out with respect to the sample weight P1 defined during the preparation and not with respect to P2. The rate of volatiles then calculated by the apparatus is erroneous since a portion of 25 MV volatiles (P1 - P2) evaporated during the wait between the preparation and the actual start of the measurement. The MVs must therefore be manually recalculated: In mass: MV mg = (P1 - P2) mg + losses 1st step mg. - In rate: Tx MV% = MV mg / Pl * 100 or 100 - residue 1% bearing. 30 c) -6- Charge rate in pcmo The charge rate is expressed in pcmo, (pcmo = parts in weight per hundred parts of organic matter) and it is obtained by the calculation, when one interprets the measurement of ATG 35 with the following formula: Tx charge (pcmo) = [(C) / (B + D)] * 100 3035110 Where B is the percentage of organic matter (range 250 ° C to 550 ° C), C is percentage of losses (between 550 ° C and 750 ° C) and D the percentage of residue (above 750 ° C).
    [0016] The percentage difference in the target load rate TCn is calculated with the following expression in which TC, T, represents the load ratio measured by ATG with the preceding formula: E (%) = [(TC, -n - TC,) / (TCn)] * 100 10 This quantity is complementary to the coagulation yield to evaluate the level of control of the technology. Measurement of coagulation yield The coagulation yield corresponds to the ratio of the recovered dry mass (from which the mass of volatiles as defined in the ATG measurement protocol has been removed in the preceding paragraphs). the target mass initially, multiplied by one hundred.
    [0017] II. DETAILED DESCRIPTION OF THE INVENTION The method for preparing a synthetic elastomer and carbonaceous filler masterbatch according to the invention comprises the steps of: preparing an aqueous carbonaceous filler dispersion having a Zeta potential of opposite sign to that anionic or cationic synthetic elastomer latex, the difference of the potentials of the anionic or cationic elastomer latex and the aqueous carbonaceous filler dispersion being such that its absolute value is greater than or equal to 20 mV, put in contact and mixing the anionic or cationic synthetic elastomer latex and the aqueous carbonaceous filler dispersion to obtain a coagulum, recovering the coagulum, drying the recovered coagulum to obtain the masterbatch.
    [0018] II.1 Synthetic Elastomer Latex For the purposes of the present invention, elastomer in the form of latex is intended to mean an elastomer in the form of elastomer particles dispersed in water. The invention relates to synthetic elastomer latices, and more particularly to diene elastomers which are defined as follows: By elastomer or "diene" rubber, it is to be understood in known manner an elastomer derived at least in part (ie, a homopolymer or a copolymer) of monomers dienes (monomers carrying two carbon-carbon double bonds, conjugated or not). These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is understood to mean in particular a diene elastomer having a degree of diene origin units (conjugated dienes) which is greater than 50%. As these definitions are given, the term "diene elastomer" that can be used in the compositions according to the invention is more particularly understood to mean: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms; (B) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having 8 to 20 carbon atoms; (c) - a ternary copolymer obtained by copolymerization of ethylene, of an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained with from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; (d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
    [0019] As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene and divinylbenzene. vinyl naphthalene.
    [0020] The copolymers may contain from 99% to 20% by weight of diene units and from 1% to 80% by weight of vinylaromatic units. The elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used. The elastomers can be for example 10 blocks, statistics, sequenced, micro sequences, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization. For coupling with carbon black, there may be mentioned, for example, functional groups comprising a C-Sn bond or amine functional groups such as aminobenzophenone for example; for coupling to a reinforcing inorganic filler such as silica, there may be mentioned, for example, silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2 740 778 or US Pat. No. 6,013,718, and WO 2008/141702). ), alkoxysilane groups (as described for example in FR 2 765 882 or US Pat. No. 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US Pat. No. 6,815,473, WO 2004/096865 or US Pat. 2006/0089445) or polyether groups (as described for example in EP 1 127 909 or US 6,503,973, WO 2009/000750 and WO 2009/000752). As other examples of functionalized elastomers, mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
    [0021] Suitable polybutadienes and in particular those having a content (mol%) in units -1.2 of between 4% and 80% or those having a content (mol%) of cis-1,4 greater than 80%, polyisoprenes , butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418) between 0 ° C. and -70 ° C. and more particularly between -10 ° C. and -60 ° C. C, a styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) of -1,2 bonds of the butadiene part of between 4% and 75%, a content (mol%) in trans-1,4 bonds of between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of -40 ° C. At -80 ° C., the isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg between -5 ° C. and -50 ° C. In the case of butadiene-styrene-isoprene copolymers, those having a styrene content of between 5% and 50% by weight and more particularly between 10% and 40% are especially suitable. an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40% by weight. %, a content (mol%) in -1,2 units of the butadiene part of between 4% and 85%, a content (mol%) in trans units -1,4 of the butadiene part of between 6% and 80% , a content (mol%) in units -1.2 plus -3.4 of the isoprene part of between 5% and 70% and a content (mol%) in trans units -1.4 of the isoprene part between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg between -5 ° C and -70 ° C. In summary, the diene elastomer (s) of the composition according to the invention are preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR), copolymers of butadiene, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene copolymers. -butadiene-styrene (SBIR). The synthetic diene elastomer latex (or synthetic rubber latex) may consist of a synthetic diene elastomer already available in emulsion form (for example a butadiene and styrene copolymer, SBR, prepared in emulsion), or in one form. synthetic diene elastomer initially in solution (for example a SBR prepared in solution) which is emulsified in a mixture of organic solvent and water, generally by means of a surfactant. Particularly suitable for the invention is an SBR latex, especially an emulsion-prepared SBR ("ESBR") or a solution-prepared SBR ("SSBR"), and more particularly an emulsion-prepared SBR. There are two main types of emulsion copolymerization processes of styrene and butadiene, one of them, or hot process (carried out at a temperature close to 50 ° C), being suitable for the preparation of SBR while the other, or cold process (implemented at a temperature ranging from 15 ° C to 40 ° C), allows to obtain more linear SBR. For a detailed description of the effectiveness of several emulsifiers that can be used in said hot process (as a function of the levels of said emulsifiers), reference may be made, for example, to the two articles of C.W. Carr. M. Kolthoff, E. J. Meehan, University of Minnesota, Minneapolis, Minnesota, who appeared in Journal of Polymer Science, 1950, Vol. V, No. 2, pp. 201-206, and 1951, Vol. VI, No. 1, pp. 73-81. With regard to comparative examples of implementation of said cold process, reference may be made, for example, to Article 1/2 Industrial and Engineering Chemistry, 1948, Vol. 40, No. 5, pp. 932-937, E.J. Vandenberg, G.E.Hulse, Hercules Powder Company, Wilmington, Delaware + and 1/2 Industrial and Engineering Chemistry, 1954, 3035110 - Vol. 46, No. 5, pp. 1065-1073, J.R. Miller, H.E. Diem, B.F. Goodrich Chemical Co., Akron, Ohio +. In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 20% and 35% by weight, or a high styrene content, for example 35% by weight, is used in particular. % to 45%, a vinyl content of the butadiene part of between 15% and 70%, a content (mol%) of trans-1,4 bonds of between 15% and 75% and a Tg of -10 ° C and -55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% (mol%) of cis-1,4 bonds. By anionic or cationic elastomer latex is meant a latex whose Zeta potential is strictly less than OmV or strictly greater than OmV, and whose absolute value is greater than or equal to 10mV. Indeed, this lower limit makes it possible to ensure the stability of the measurement made. 11.2 Preparation of the aqueous dispersion of carbonaceous filler For the invention can be used any carbonaceous filler, such as carbon blacks, natural and synthetic graphites, carbon fibers, graphenes, fullerenes, acetylene blacks and carbon nanotubes. Carbon blacks conventionally used in tires (so-called pneumatic grade blacks) are particularly suitable for the invention. Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or else, according to the targeted applications, the blacks of higher series 500, 600 or 700, for example the blacks N550, N660, N683, N772 (ASTM grades).
    [0022] The carbonaceous filler is then dispersed in water, preferably so as to obtain a dispersion whose viscosity is sufficient to be easily "manipulable". Thus, for carbon black, a mass concentration of black in the dispersion of between 1% and 15% will be preferred. For example, an aqueous dispersion of carbon black with a black content in water of 4% by weight can be produced.
    [0023] Advantageously, in order to carry out the carbon black dispersion, it is possible to use a homogenizer (such as a device with the trade name "Ultra Turrax" marketed by the company IKA) and then a microfluidizer (marketed by the company Microfluidicscorp). In a second optional step, a defined quantity of aqueous surfactant solution is introduced into the aqueous dispersion of carbonaceous filler in order to control the Zeta potential of the particles of the dispersion so that the latter is such that the difference in potentials anionic or cationic elastomer latex and the aqueous carbonaceous filler dispersion has an absolute value greater than or equal to 20mV. Preferably, the carbonaceous feedstock comprises carbon black, and even more preferably, the carbonaceous feedstock consists of carbon black. 11.3 Contacting the two dispersions According to one embodiment of the method, the contacting and mixing of the elastomer latex and the aqueous carbonaceous feed dispersion can be carried out continuously.
    [0024] According to a preferred embodiment of the method, the contacting and mixing of the elastomer latex and the aqueous carbonaceous filler dispersion are carried out batchwise or batchwise.
    [0025] In the case of a "batch" contacting, a defined quantity of aqueous dispersion of carbonaceous feedstock is introduced into a defined quantity of elastomer latex, in particular according to the following protocol: a defined quantity of In a 200 mL beaker, a magnetic stir bar is introduced into the beaker and the elastomer latex is placed under magnetic stirring. A defined quantity of aqueous carbonaceous feed dispersion is weighed into a beaker of 200 ml. aqueous dispersion of carbonaceous filler at once in the beaker containing the elastomer latex with magnetic stirring. The masses of elastomer latex and aqueous carbon charge dispersion to be weighed are defined directly by the mass of the masterbatch targeted, the target charge rate in the masterbatch and the respective mass fractions of the elastomer latex and The aqueous dispersion of carbonaceous filler. The masses of elastomer latex mi, and aqueous dispersion of carbonaceous charge ms to be weighed are defined from the following expressions: 40 mi, (100 / FMI) * [(mMBc) / (1 + (TCc / 100)) ] = (100 / FMs) * [(100 / FML) * (TCc / 100)] With FML the mass fraction of the elastomer latex expressed in%; FMs the mass fraction of the aqueous carbonaceous feed dispersion expressed in%; TCc the target charge rate expressed in pcmo and mMBc the mass of masterbatch targeted. Advantageously, the target carbon feed rate for the masterbatch ranges from 2 phr to 150 phr (parts by weight per hundred parts organic matter). In particular, when the carbonaceous feedstock mainly comprises carbon black, the target level is preferably from 30 phr to 110 phr and more preferably from 40 phr to 100 phr. To achieve contacting and mixing of these two dispersions, it is also possible to use any type of apparatus allowing an "effective" mixture of two products in the liquid phase, so it will be possible to use a mixer producing a high shear such as mixers marketed by TOKUSHU KIKA KOGYO Co., Ltd., or by the company PUC in Germany, by CAVITRON in Germany or by SILVERSON in the United Kingdom. It is clear that the more efficient the mixing step, the better the dispersion. Therefore mixers such as high shear mixers are preferred.
    [0026] During this phase of mixing the two dispersions, a coagulum of elastomer and carbonaceous filler is formed either in the form of a single solid element in the solution, or in the form of several separate solid elements (coagulum and aqueous effluents). 11.4 Recovery of the solid formed The recovered solid (s) are filtered or centrifuged. Indeed, the filtering operation that can be performed using a filter screen, may be unsuitable when the coagulum is in the form of many small and solid elements. In such a case, an additional centrifugation operation is preferably carried out. At the end of this filtering or centrifugation step, the coagulum obtained is dried, for example in an oven. At the end of this operation, the ATG loading rate and the coagulation yield are measured. 11.5 Rubber composition Advantageously, the masterbatches thus produced are capable of being used in rubber compositions, in particular for tires. The tire rubber compositions based on the masterbatches according to the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, in particular belts. such as plasticizers or extension oils, whether these are aromatic or non-aromatic in nature, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M) as described for example in application WO 02/10269, a crosslinking system based on of sulfur, either of sulfur and / or peroxide and / or bismaleimide donors, vulcanization accelerators, vulcanization activators.
    [0027] Preferably, these compositions comprise, as preferential non-aromatic or very weakly aromatic plasticizing agent, at least one compound chosen from the group consisting of naphthenic, paraffinic, MES, TDAE and ester oils (in particular trio). glycerol leates), the hydrocarbon plasticizing resins having a high Tg preferably greater than 30 ° C, and mixtures of such compounds. 11.6 Manufacture of rubber compositions The rubber compositions of the invention are manufactured in suitable mixers, using two successive preparation steps according to a general procedure well known to those skilled in the art: a first phase of work or mixing thermomechanical system (sometimes referred to as a "non-productive" phase) at a high temperature, up to a maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second mechanical working phase (sometimes referred to as a "productive" phase) at a lower temperature, typically less than 120 ° C., for example between 60 ° C. and 100 ° C., finishing phase during which the crosslinking system is incorporated or vulcanization. By way of example, the first (non-productive) phase is carried out in a single thermomechanical step, during which all the constituents necessary except for the usual mixer are introduced into a suitable mixer such as a conventional internal mixer. vulcanization system. The total duration of the kneading, in this non-productive phase, is preferably between lmin and 15min. After cooling the mixture thus obtained during the first non-productive phase, the low temperature vulcanization system is then incorporated, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 2min and 15min. The vulcanization system itself is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator. To this vulcanization system may be added, incorporated during the first non-productive phase and / or during the productive phase, various known secondary accelerators or vulcanization activators, excluding zinc and any derivative zinc such as ZnO or with a zinc content of the composition of less than 0.5 phr, and preferably less than 0.3 phr, such as, for example, fatty acids such as stearic acid, guanidine derivatives (in particular diphenylguanidine), etc. The sulfur content is preferably between 0.5 phr and 3.0 phr, that of the primary accelerator is preferably between 0.5 phr and 5.0 phr.
    [0028] The final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded in the form of a rubber profile which can be used for example as a strip of tire rolling for passenger vehicle.
    [0029] III EXAMPLES OF THE INVENTION 1.11.1 Preparation of the aqueous dispersion of carbonaceous filler The preparation of an aqueous dispersion of carbonaceous filler consists in a first step in mechanically dispersing the filler, here carbon black N234 marketed by Cabot Corporation, in aqueous phase according to the following protocol: Weigh a defined mass of ultrapure water in a 1000rnL beaker.
    [0030] Weigh a defined mass of carbonaceous feed into the same beaker. Carry out a first dispersion step with an IKA model T25 Digital Ultra-Turrax® homogenizer / disperser with S 25 N-25 G-ST type rotor-stator at a speed of 18000rpm for 10 min in the same beaker. Perform a second dispersion step with a microfluidizer model M-110P with 871am diameter dispersion cell sold by MICROFLUIDICS, the entire volume of aqueous dispersion of carbonaceous filler contained in the beaker with a 8711m cell. The ultrapure water and filler masses to be introduced into the beaker are defined directly by the target filler rate in the aqueous carbonaceous filler dispersion and the total amount of aqueous carbon filler dispersion to be produced. For all these examples, the mass fraction of N234 slurry (FMs) is 4%. For calculating the amount of SDS solution or CTAC1 solution to be introduced into the N234 slurry before contacting, an optimal adsorption rate equal to 1.4 molecules / nm 2 is assumed on the surface of the black for the SDS. as for the CTAC1, which makes it possible to deduce the quantities of SDS and CTAC1 to be introduced knowing the specific surface of the N234: 120 m 2 / g.
    [0031] For a detailed description of the technical origin of the optimal rate chosen from 1.4 molecules / nm 2 of SDS or CTAC1 to be adsorbed on the surface of N234, reference may be made to the article by Martinez-Pedrero, F., Alousque, F. From Gaudemaris, B., Berriot, J., Gaboriaud, F., Bremond, N., Bibette, J. published in Soft Matter of 2012, Vol. VIII, No. 33, pp. 8752-8757.
    [0032] The following table 1 indicates, for the carbon black dispersions with the surfactant under consideration, the Zeta potential values obtained according to the sample preparation method described above and according to the measurement protocol described in the the user of the ZetaSizer Nano-ZS from Malvern Instruments. 111.2 Preparation of Synthetic Elastomer Latexes Three separate latexes were used to carry out the following tests: an e-SBR latex at a mass fraction of 20.6% marketed under the name "SB Latex 1502" by the company SYNTHOS; designated here by Latexl, an e-SBR latex with a mass fraction of 50.4% marketed under the name "Litex SX 1024" by the company SYNTHOMER; designated here by Latex 2, a latex e-SBR with a mass fraction of 4.5% synthesized according to the process described in patent application WO96 / 19511 hereinafter referred to as Latex 3.
    [0033] Table 2 indicates for the aforementioned elastomer latices the Zeta potential values obtained according to the previously described sample preparation method and according to the measurement protocol described in the ZetaSizer Nano-ZS user's manual. Malvern Instruments. III.3 Preparation of masterbatches Masterbatches are made by batch contacting, a defined amount of aqueous dispersion of N234 carbon black prepared according to the teaching of the MA paragraph is introduced in a defined amount of elastomer latex according to the following protocol: a defined quantity of elastomer latex is weighed into a beaker of 200 ml, a magnetic stir bar is introduced into the beaker and the elastomer latex is placed under magnetic stirring; Weigh a defined amount of aqueous carbonaceous feedstock dispersion into a 200 ml beaker and introduce the aqueous carbonaceous feedstock dispersion at once into the beaker containing the elastomer latex with magnetic stirring.
    [0034] For each target filler level in the masterbatches, the following are the elastomer latex, aqueous carbon black dispersion, surfactant used and the mass fractions indicated in Table 3 below. respective elastomeric latex and the aqueous carbon black dispersion.
    [0035] In this phase of mixing the two dispersions, a coagulum of elastomer and carbonaceous filler is formed either as a single solid element in the solution or as a plurality of separate solid elements.
    [0036] The mixture is kept for a few minutes with magnetic stirring before recovery of the coagulum formed. In order to have for the different tests identical conditions of the operating mode, the coagulum formed or the solids formed (commonly called "crumbs") are centrifuged, including in cases where the visual appearance of the coagulum made it possible to consider a filtering operation. According to a preferred embodiment of the method, the coagulum is separated from the effluents by centrifugation after transfer into a 250mL nalgene flask using a Sigma 4K15 scoop centrifuge marketed by the company SIGMA, at the reaction temperature. 20 ° C and at a speed of 9000rpm for 15min. The masterbatch is obtained by drying the coagulum in an oven at 60 ° C under 200mbars pressure to a moisture content of less than 1% by mass.
    [0037] The ATG loading rate (as described in detail at the beginning of the description) and the coagulation yield are then measured. The coagulation yield is expressed as the fraction by weight expressed as a% of the weight of the masterbatch mMB relative to the mass of the masterbatch targeted: ## EQU1 ## R (%) = (mMB / mMBc) * 100 The measurement of the coagulation yield makes it possible to directly quantify the effectiveness of the present generic method of coagulation. Trials By the method described above, were carried out for each of the three aforesaid latexes: master batches with a dispersion of N134 without the presence of surfactants with target charge levels of 60 pcm, 80 pcmo and 100 μg / cm 3, master batches with an SDS-containing N134 dispersion as previously described with target loading levels of 60 pcmo, 80 pcmo and 100 pcmo, master batches with N134 dispersion containing CTAC1 such as as previously described with targeted loading rates of 60 pcmo, 80 pcmo and 100 pcmo. The master batches Al, B1 and Cl are, respectively, all of the masterbatches produced according to paragraphs HIA to III.3, from Latex 1 and carbon black N234, with the following differences: - A160 is a masterbatch realized with a carbon black dispersion without surfactants and with a target charge rate of 60 pcmo, - Also is identical to A160 but with a target charge rate of 80 pcmo, - A1100 is identical to A160 but with a rate of Targeted filler of 100 pcmo, 25 - B160 is a masterbatch made with a carbon black dispersion including SDS and with a targeted loading rate of 60 pcmo, - Blso is identical to B160 but with a targeted loading rate of 80 pcmo, - B1100 is identical to B160 but with a target feed rate of 100 pcmo, - C160 is a masterbatch made with a carbon black dispersion including CTAC1 and with a target feed rate of 60 pcmo , - Cl so is identical to C160 but with a target charge rate of 80 pcmo, - Clioo is identical to C160 but with a target charge rate of 100 pcmo. Table 4 shows for the above masterbatches the values obtained from the difference at the target charge rate (measured by ATG as detailed earlier in the description) as well as the coagulation yields obtained (as also described above). In the same way, the masterbatches A2, B2 and C2 respectively all correspond to masterbatches produced according to paragraphs HIA to 111.3, starting with Latex 2 and carbon black N234, with the following differences: A260 is a masterbatch made with a dispersion of carbon black without surfactants and with a target charge rate of 60 pcm.sup.-A280 is identical to A260 but with a target charge rate of 80 pcm.sup.O. A2100 is identical to A260 but with a target feed rate of 100 pcmo, - B260 is a masterbatch made with carbon black dispersion including SDS and with a target feed rate of 60 pcmo, 10 - B280 is identical at B260 but with a target feed rate of 80 pcmo, - B2100 is identical to B260 but with a target feed rate of 100 pcmo, - C260 is a masterbatch made with a dispersion of carbon black including CTAC1 and with a targeted charge rate of 60 pcmo, - C280 is identical to C260 but with a target charge rate of 80 pcmo, 15 - C2100 is identical to C260 but with a target charge rate of 100 pcmo. Table 5 shows for the above masterbatches the values obtained from the difference at the target charge rate (measured by ATG as detailed previously in the description) as well as the coagulation yields obtained (as also described above). Finally, the master batches A3, B3 and C3 all respectively correspond to masterbatches produced according to paragraphs HIA to 111.3, starting with Latex 3 and carbon black N234, with the following differences: 25 - A360 is a mixture -master made with a dispersion of carbon black without surfactants and with a target charge rate of 60 pcmo, - A380 is identical to A360 but with a target charge rate of 80 pcmo, - A3100 is identical to A360 but with a target feed rate of 100 cfm, B360 is a masterbatch made with a carbon black dispersion including SDS and with a target feed rate of 60 cfm, B380 is identical to B360 but with a targeted load of 80 pcmo, - B3100 is identical to B360 but with a target feed rate of 100 pcmo, - C360 is a masterbatch made with a carbon black dispersion including CTAC1 and with a target feed rate of 60 pcmo, 35 - C380 is identical C360 but with a target load rate of 80 PCMO - 03100 is identical to C360 but with a target load rate 100 PCMO. Table 6 shows for the preceding masterbatches the values obtained from the difference at the target charge rate (measured by ATG as detailed previously in the description) as well as the coagulation yields obtained (as also described previously). In view of the three tables 4, 5 and 6, it can be seen that whatever the synthetic, anionic or cationic elastomer latexes, there is no coagulation between a synthetic elastomer latex and a black dispersion of carbon without surfactant (all masterbatches A1, A2 and A3) either because there is a coagulation rate much lower than 80%, or because we obtain a difference in the target charge rate greater than 20%, and this regardless of the target charge rate.
    [0038] It is also found that the masterbatches produced from an anionic synthetic elastomer latex and a zeta-negative potential charge dispersion (masterbatches BI and B2), whatever the target charge rate, do not allow to achieve a return and simultaneously a deviation at the target load rate acceptable.
    [0039] In the same way, it is observed that whatever the target charge ratio, the masterbatches produced from a synthetic cationic elastomer latex and a zeta positive charge dispersion (C3 masterbatches) do not occur. not achieve a return and simultaneously a deviation at the target load rate acceptable.
    [0040] In accordance with the invention, it is found that the masterbatches made from anionic or cationic synthetic diene elastomer latex and from dispersion of charge of opposite zeta potential (masterbatches B3, C1 and C2) make it possible to target load, to have both an acceptable yield (greater than 80%) and an acceptable target load difference (less than 20%). Table 1 N234 - Surfactant N234 - SDS N234 - CTACI Zeta Potential (mV) -51 ± 2 +47 ± 2 Table 2 Latex LATEX 1 LATEX 2 LATEX 3 Potential Zeta (mV) -42 ± 2 -40 ± 2 +51 ± 2 - 26 - Table 3 Table 4 Masterbodies A160 A180 Alioo B160 B180 Blioo Cl6o C180 Clio ° Difference at target loading rate (%) 686 561 752 743 551 735 -3 6 1 Coagulation yield (%) 44.5 51 54 40 47 52.5 100 87.5 97 100 N234 - CTACI (;> O) 60 80 19.8 22.0 Charge - surfactant Target charge rate TC, (pcmo) Load fraction by volume (%) Weighs Dispersion N234 Aqueous solution of 25% CTACI in 100 ml ama mua anummanam mi mormiarmariarmum am resa Mn 53.9 48.5 N234 - SDS (; <O) 80 Aqueous solution of 20% solids SDS 60 25.0 30 , 8 25.0 30.8 246.9 250.0 187.5 187.5 0.6 60.7 24.8 277.8 0.7 0.8 0.7 60.7 24.8 277.8 0.8 246.9 250.0 0.9 48.5 19.8 53.9 22.0 - 27 - Table 5 Masterbatches A260 A280 A2100 B260 B280 B2100 0260 C280 02100 Difference at target load rate (%) 187,155,421 287 338 535 15 -17 -6 Coagulation yield (%) 56.5 63.5 57.5 46.5 52.5 55 91 83 96.5 Table 6 Masterbatches A360 A30 A3100 B360 B380 B3100 C36o C380 C3100 Target load rate difference (%) 104 84 24 4 10 6 664 537 471 Coagulation yield (%) 70.5 72.5 89 98 93 91 43 50.5 51.5
    权利要求:
    Claims (19)
    [0001]
    CLAIMS 1) Method for preparing a masterbatch of synthetic elastomer and carbonaceous filler, which comprises the following steps: - preparing an aqueous dispersion of carbonaceous filler having a Zeta potential of opposite sign to that of an anionic synthetic elastomer latex or cationic, the difference of the potentials of the anionic or cationic elastomer latex and the aqueous dispersion of carbonaceous filler being such that its absolute value is greater than or equal to 20mV, - contacting and mixing the latex of anionic synthetic elastomer or cationic and the aqueous dispersion of carbonaceous filler to obtain a coagulum, - recover the coagulum, - dry the recovered coagulum to obtain the masterbatch.
    [0002]
    2) Method according to claim 1, wherein the synthetic elastomer is a synthetic diene elastomer.
    [0003]
    3) Method according to any one of claims 1 or 2, wherein the Zeta potentials of the anionic or cationic elastomer latex and the aqueous carbonaceous feed dispersion have a difference whose absolute value is greater than or equal to 30mV.
    [0004]
    4) Method according to any one of claims 1 to 3, wherein the aqueous carbonaceous feed dispersion contains a surfactant of opposite sign to that of the synthetic elastomer latex.
    [0005]
    5) Method according to any one of claims 1 to 4, wherein the anionic or cationic synthetic elastomer latex contains at least one surfactant respectively anionic or cationic.
    [0006]
    6) Method according to any one of claims 1 to 5, wherein the synthetic elastomer latex is obtained by aqueous phase polymerization.
    [0007]
    7) Method according to claim 6, wherein the synthetic elastomer latex is obtained by emulsification in aqueous phase of a diene elastomer.
    [0008]
    8) A method according to any one of the preceding claims, wherein the synthetic elastomer latex is a latex of butadiene copolymer and styrene, SBR. 3035110 -29-
    [0009]
    9) Method according to claim 8, wherein the synthetic elastomer latex is a SBR prepared in emulsion.
    [0010]
    10. A method as claimed in any one of the preceding claims, wherein the amount of carbonaceous charge upon contacting two aqueous dispersions is from 2 phr to 150 phr, parts by weight per hundred parts of organic material.
    [0011]
    The method of claim 10, wherein the carbonaceous feedstock comprises carbon black. 10
    [0012]
    12) The method of claim 11, wherein the carbonaceous filler is carbon black.
    [0013]
    13) A method according to any one of claims 11 or 12, wherein the amount of carbonaceous filler when contacting two aqueous dispersions is from 30 pcmo to 110 pcmo.
    [0014]
    14) The method of claim 13, wherein the amount of carbonaceous filler when contacting two aqueous dispersions is from 40 pcmo to 100 pcmo. 20
    [0015]
    15) Synthetic diene elastomer and carbonaceous filler masterbatch obtained according to any one of Claims 1 to 14.
    [0016]
    16) Elastomeric composition based on at least one masterbatch according to claim 15. 25
    [0017]
    17) A finished or semi-finished article comprising a composition according to claim 16.
    [0018]
    18) A tire tread comprising a composition according to claim 16.
    [0019]
    19) Pneumatic or semi-finished product comprising at least one rubber composition according to claim 16.
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    同族专利:
    公开号 | 公开日
    EP3283554B1|2019-10-16|
    US20180079874A1|2018-03-22|
    EP3283554A1|2018-02-21|
    FR3035110B1|2017-03-24|
    WO2016166483A1|2016-10-20|
    US10280268B2|2019-05-07|
    CN107438638A|2017-12-05|
    CN107438638B|2020-04-07|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1553314A|FR3035110B1|2015-04-15|2015-04-15|PROCESS FOR THE PREPARATION OF A MASTER MIXTURE OF SYNTHETIC DIENE ELASTOMER AND CARBON CHARGE|FR1553314A| FR3035110B1|2015-04-15|2015-04-15|PROCESS FOR THE PREPARATION OF A MASTER MIXTURE OF SYNTHETIC DIENE ELASTOMER AND CARBON CHARGE|
    EP16731203.2A| EP3283554B1|2015-04-15|2016-04-14|Preparation method of a masterbatch of synthetic dienic elastomer and a carbonaceous charge|
    CN201680021853.0A| CN107438638B|2015-04-15|2016-04-14|Process for preparing a masterbatch of synthetic diene elastomer and carbon-based filler|
    US15/564,491| US10280268B2|2015-04-15|2016-04-14|Method for producing a masterbatch of synthetic diene elastomer and carbon-based filler|
    PCT/FR2016/050868| WO2016166483A1|2015-04-15|2016-04-14|Method for producing a masterbatch of synthetic diene elastomer and carbonated filler|
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