Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/22—Oxygen

Definitions

• the present invention relates to reinforcing fillers capable of reinforcing polymer matrices or compositions, more particularly reinforcing fillers of the organic type and to their use for reinforcing such matrices, in particular elastomeric matrices used in the manufacture of motor vehicle tires. .
• a first subject of the invention relates to functionalized and crosslinked vinyl polymer nanoparticles, which can be used in particular as a reinforcing filler in a polymer matrix, characterized in that said vinyl polymer is a copolymer at least the following monomers, all copolymerizable by radical polymerization:
• the subject of the invention is also the use of nanoparticles according to the invention for reinforcing a polymeric matrix, in particular elastomeric matrix.
• the subject of the invention is particularly the use of nanoparticles according to the invention for the reinforcement of finished articles or semi-finished products of rubber, these articles or semi-finished products being in particular intended for any system for the ground connection of vehicles.
• automobiles such as tires, internal tire safety supports, wheels, rubber springs, elastomeric joints, other suspension elements and antivibration.
• the subject of the invention is particularly the use of nanoparticles according to the invention for reinforcing tires.
• the subject of the invention is also a masterbatch comprising nanoparticles according to the invention, embedded in a polymeric matrix, in particular elastomeric matrix.
• the subject of the invention is also a polymeric composition
• a polymeric composition comprising at least one polymer, in particular elastomer, nanoparticles according to the invention and a coupling agent ensuring the bond between the polymer and the surface of the nanoparticles.
• the vinyl polymer charge (abbreviated as "PV”) described hereinafter consists of “nanoparticles”, that is to say particles whose main dimension (diameter or length) is typically less than one micrometer, generally comprised in a range of about ten nanometers to a hundred or a few hundred nanometers.
• nanoparticles of PV are in the form of elementary particles (or "primary particles”), these elementary particles or nanoparticles being able to form aggregates (or “secondary particles") of at least two of these nanoparticles, said nanoparticles and / or aggregates may possibly in turn form agglomerates likely to disagglomerate into these nanoparticles and / or aggregates under the effect of an external force, for example under the action of mechanical work.
• nanoparticles are characterized by a transmission electron microscope (TEM), as indicated below.
• TEM transmission electron microscope
• the PV loading latex previously diluted with water (for example 8 g of feed per liter of water) is diluted approximately 50 times in isopropanol. 40 ml of the solution thus obtained are poured into a high-shape beaker (50 ml) and then dispersed with the aid of a 600 W ultrasonic probe (Vibracells probe, reference 72412, marketed by Bioblock Scientific), under a power of 100%, for 8 min in pulsed mode (Is ON / Is OFF).
• CM 200 marketed by FEI, 20O kV acceleration voltage
• camera MegaView camera II marketed by Soft Imaging System
• image analysis system AnalySIS Pro A version 3.0 Soft Imaging System
• the setting conditions of the TEM are optimized in known manner, depending on the sample and the state of aging of the filament (typically, condenser diaphragm 2 (50 ⁇ m in diameter) - objective 3 (40 ⁇ m in diameter)).
• the magnification rate of the microscope is adapted to have a sufficient resolution on the nanoparticles. For example, a magnification of 65,000 corresponds to a resolution close to 0.96 nm / pixel, on a digital image of 1248 ⁇ 1024 pixels; such a resolution allows for example the definition of a spherical nanoparticle of 40 nm in diameter with more than 1000 pixels.
• the calibration of the camera is carried out conventionally using standards (at low magnification, a gold grating of 2160 lines / mm, at high magnification, gold balls with a diameter of 0.235 nm).
• the diameter of the nanoparticles is measured using the AnalySIS Pro A version 3.0 software (with "Circle” option in the "Measure” menu). For each image and for a given nanoparticle, the operator materializes on the screen (using the mouse) three points located on the periphery of the image of the nanoparticle. The software then automatically draws the circle that passes through these three points and stores in a file (Excel) the values of the circular area, the circular perimeter and the circular diameter of the nanoparticle. Since this operation is only possible for nanoparticles whose contours are well defined, nanoparticles present in agglomerates are excluded from the measurement. The experiment is repeated at least on 2000 nanoparticles representative of the sample (from at least 10 different images, typically 50).
• PV load samples of vulcanized rubber composition are prepared in known manner by ultracryomicrotomy (see, for example, L. Sawyer and D. Grubb, Polymer Microscopy, 92, Chapman and Hall).
• the apparatus used here is a Leica ultracryomicrotome ("EMFCS") equipped with a diamond knife.
• EMFS Leica ultracryomicrotome
• the sample is cut in the form of a truncated pyramid with a rectangular base, the truncated face from which the cuts measuring less than 600 ⁇ m are made. This truncated pyramid is held firmly during cutting.
• the sample is cooled to a suitable temperature (close to the glass transition temperature of the sample) to be hard enough to allow cutting, the knife temperature being typically close to that of the sample.
• the speed and the cutting thickness are preferably between 1 and 2 mm / s and between 20 and 30 nm, respectively.
• aqueous sucrose solution 40 g in 40 ml of water
• the sections are recovered in the ultracryomicrotome chamber and then deposited on a TEM grid at room temperature.
• the sucrose is then removed by depositing the grid on the surface of a crystallizer filled with distilled water.
• the sections may undergo a staining step with osmium tetraoxide (OsO 4 ), according to a method well known to those skilled in the art (LC Sawyer et al.
• the sections are observed on CM 200 microscope (200 kV voltage). To optimize the contrast, the observations are made in conventional energy filtered imaging (energy window ⁇ E equal to about 15 eV), with a GIF (Gatan Imaging Filter) and associated software (Filter Control and Digital Micrograph 3.4 ).
• the nanoparticles of the invention have the essential characteristic of being composed of a functionalized and crosslinked vinyl polymer, said vinyl polymer (abbreviated "PV") being a copolymer of at least the following monomers, all copolymerizable by polymerization by radical:
• PV vinyl polymer
• X represents a hydroxyl group or a hydrolysable monovalent group; o a monomer "C” crosslinking that is to say at least bifunctional from the point of view of said polymerization.
• definition means
• vinyl monomer means any monomer bearing at least one vinyl group
• non-aromatic vinyl monomer any vinyl monomer other than a monomer of the vinylaromatic type, that is to say alpha-substituted by an aromatic group.
• non-aromatic vinyl monomer any vinyl monomer other than a monomer of the vinylaromatic type, that is to say alpha-substituted by an aromatic group.
• the above PV is a copolymer whose monomers are exclusively vinylic or in which the majority weight fraction of the monomers (preferably equal to or greater than 50%, more preferably equal to or greater than 70%) is composed of vinyl monomers (the minor fraction may be derived from one or more monomers other than vinyl).
• the monomer C in order to be able to crosslink the PV, must be at least bifunctional, that is to say carrying at least two radically polymerizable functions, unlike monomers A and B which must, from the point of view of the polymerization, be at least monofunctional that is to say carrying at least one radically polymerizable function.
• the present invention is not limited to the case of monofunctional monomers A and B from the point of view of polymerization, each of which may comprise more than one radically polymerizable function.
• a bifunctional monomer A or monomer B for example di (meth) acrylates or di (meth) acrylamides described later
• the latter could also, according to one particular embodiment of the invention.
• the functionalization Z of the PV is provided by the monomer B.
• the molar level of this monomer B is preferably greater than 5%, in particular between 5 and 30%, in particular between 5 and 20%.
• X is a halogen, in particular chlorine, or X is of the formula OR in which O is oxygen and R is hydrogen or a monovalent hydrocarbon group, linear or branched, preferably comprising from 1 to 15 atoms. of carbon.
• Z-functions chosen from the so-called "hydroxysilyl” ( ⁇ Si-OH) or "alkoxysilyl” ( ⁇ Si-OR 1 ) functions are more particularly suitable, R 'being a monovalent hydrocarbon radical preferably comprising from 1 to 15 carbon atoms, more preferably selected from alkyl, alkoxyalkyl, cycloalkyl and aryl, in particular from alkyl C 1 -C 8 alkoxyalkyls, C 2 C6 alkyl, cycloalkyl, C 5 -C 10 aryl and C 6 -C 12.
• Z corresponds to one of the formulas below:
• R 1 substituted or unsubstituted, identical or different, are selected from the group consisting of alkyl Ci-Cs cycloalkyl, C 5 -C 8 aryl and C 6 -C 2; the R radicals, substituted or unsubstituted, identical or different, are selected from the group consisting of hydroxyl, alkoxyls and C 8 cycloalkoxyls C 5 -C 8.
• radicals R 1 are chosen from the group consisting of C 1 -C 4 alkyls, cyclohexyl and phenyl, in particular from C 1 -C 4 alkyls, more particularly from methyl and ethyl; -
• the radicals R 2 are chosen from the group consisting of hydroxyl and C 6 -C 6 alkoxyls, especially from hydroxyl and C 1 -C 4 alkoxyls, more particularly from hydroxyl, methoxyl and ethoxyl.
• radicals R 1 are chosen from methyl and ethyl and the radicals R 2 are chosen from hydroxyl, methoxyl and ethoxyl.
• the comonomer B is chosen from the group consisting of hydroxysilyl-(C 1 -C 4 ) alkyl acrylates and methacrylates, (C 1 -C 4 ) alkylsilyl-alkyl acrylates and methacrylates. (C 1 -C 4 ), and mixtures of such monomers.
• it is selected from the group consisting of hydroxy-, methoxy-, ethoxy-silyl-(C 1 -C 4 ) alkyl acrylates and methacrylates, and mixtures of such monomers, in particular from acrylates and hydroxy-, methoxy-, ethoxy-silylpropyl methacrylates, more particularly from trimethoxysilylpropyl acrylate and methacrylate.
• the comonomer B is selected from the group consisting of styryl-alkyl (C] -C 4) -hydroxysilanes, the styryl-alkyl (Ci-C 4) -alkoxy (C -C 4) silanes and mixtures of such monomers.
• styryl-C 1 -C 4 alkylhydroxy-, methoxy-, ethoxy-silanes and mixtures of such monomers in particular from styrylethylhydroxysilanes, styrylethylmethoxysilanes and styrylethylethoxysilanes; styrylethyltrimethoxysilane (or trimethoxysilylethylstyrene) is more particularly used.
• this comonomer B carrying the Z function is used according to a weight ratio which is preferably greater than 10%, more preferably between 10 and 30%, especially between 15 and 30%.
• Type B comonomers are well known, especially those selected from the group consisting of trimethoxysilylpropyl methacrylate (abbreviated "MTSP"), trimethoxysilylpropyl acrylate (or “ATSP”) and trimethoxysilylethylstyrene (or “TSES”) or styrylethyl-trimethoxysilane, of the following formulas:
• MTSP trimethoxysilylpropyl methacrylate
• ATSP trimethoxysilylpropyl acrylate
• TSES trimethoxysilylethylstyrene
• MTSP Trimethoxysilylpropyl methacrylate
• TSES Trimethoxysilylethylstyrene
• radical R 3 is chosen from the group consisting of hydrogen and C 1 - alkyls
• R 'and R which are identical or different, are chosen from the group consisting of alkyls, linear, branched or cyclic, containing from 1 to 12 atoms of carbon, and aryls, aralkyls or alkaryls containing from 6 to 20 carbon atoms, R 'and R "being able to comprise at least one heteroatom chosen from halogens (preferably chlorine), oxygen, nitrogen and sulfur.
• N, N-dimethyl- (meth) acrylamide, N, N-diisopropyl- (meth) acrylamide, N-methyl, N-isopropylacrylamide (for the carbamoyl radical Y C (O) N (R'R ");
• R 3 is selected from the group consisting of hydrogen and CpC 6 alkyl
• Y is selected from the group consisting of chlorine, the radicals C (O) OH, C (O) OR ', C (O) N (R'R ") and OC (O) R'. More preferably still, the following characteristics are verified:
• Y is the group C (O) OR ';
• R 3 is hydrogen or methyl.
• Methyl acrylate or methyl methacrylate, more preferably still methyl methacrylate is preferably used.
• monomers A of the bifunctional type could be used monomers of formula (H) above in which the radical Y is carrying a second radical-free radical copolymerizable vinyl or vinylidene group.
• the functionalized PV Z is further in a crosslinked state, i.e. in a three-dimensional form, so as to maintain the morphology of the charge at high temperature.
• the crosslinking is provided by at least one starting comonomer (monomer C) polymerizable by addition reaction and bifunctional from the point of view of the polymerization, that is to say carrying at least one second function capable of creating a three-dimensional network of PV during the polymerization.
• This cross-linking monomer C may be vinylic or non-vinylic, aromatic or aliphatic.
• DIB diisopropenylbenzene
• DVD divinylbenzene
• TVB trivinylbenzene
• Ethylene glycol dimethacrylate (abbreviated as “EGDMA")
• PGDMA Propylene glycol dimethacrylate
• Hexamethylene glycol dimethacrylate (abbreviated “HGDMA")
• the PV of the nanoparticles of the invention is a polyacrylate or polymethacrylate, or a copolymer derived from (meth) acrylate units in a majority weight fraction (preferably at least equal to or greater than 50%, plus preferably equal to or greater than 70%), for example a copolymer selected from the group consisting of MMA-MTSP-EGDMA, MMA-MTSP-PGDMA, MMA-MTSP-HGDMA and MMA-MTSP-DVB copolymers.
• crosslinking comonomer could also be used comonomer B bearing the aforementioned Z function or comonomer A, provided of course that comonomer B or this comonomer A is itself at least bifunctional and copolymerizable radically with the other comonomers.
• the weight content of crosslinking comonomer C is preferably greater than 1%, more preferably greater than 5%, in particular between 10 and 30%.
• Various other monomers such as, for example, diene monomers such as butadiene, isoprene, piperylene, may be optionally added in a minor amount, preferably less than 20% by total weight of monomers.
• the monomers A, B and C are different and all are vinylic, in particular all are non-aromatic vinyls.
• the monomers A and B carry a single addition-polymerizable function
• the cross-linking monomer C carries only two radically polymerizable functions
• the functionalized Z and cross-linked PV can be prepared by any synthesis method adapted to the functionalization of a vinyl copolymer.
• This synthesis is preferably carried out by radical polymerization of the various monomers.
• Such a technique is in its general known principle, it has been applied in particular to radical polymerization in emulsion of functionalized polystyrene Z (alkoxysilane or hydroxysilane) in the presence of MTSP (see for example Macromolecules 2001, 34, 5737 and Macromolecules 2002, 35, 6185), or the synthesis of cross-linked (but non-functionalized) polystyrene in the presence of DVB (Polymer 2000, 41, 481).
• the non-aromatic vinyl monomer A is an acrylate or methacrylate monomer
• functionalizing comonomer B carrier of the Z function
• the crosslinking comonomer C is itself a vinyl compound, preferably chosen from the group consisting of HGDMA, PGDMA, EGDMA, DVB and the mixtures of these monomers.
• Z-functionalized and crosslinked PV nanoparticles can thus be obtained, in emulsion in water, that is to say in the form of latex (typically, for example, 100 g of polymer per liter of water).
• latex typically, for example, 100 g of polymer per liter of water.
• these nanoparticles of PV are preferably in a substantially spherical form (thus in the form of nanobeads), either in the state isolated either in aggregates themselves possibly agglomerated.
• the number of nanoparticles per aggregate is typically between 2 and 100.
• the average diameter of these nanobeads is preferably between 10 and 100 nm, more preferably between 10 and 60 nm, especially between 10 and 40 nm.
• the nanoparticles of PV according to the invention described above are advantageously usable for the reinforcement of polymer matrices
• the polymer of these matrices can be of any kind, for example a thermoplastic material, a thermosetting material, a diene or non-diene elastomer.
• the level of PV nanoparticles is preferably between 10 and 100 parts by weight per hundred parts of polymer. Due to the low density of these nanoparticles, this level is advantageously between 10 and 80 parts, preferably between 20 and 50 phr and more preferably still strictly greater than 30 phr.
• the charge PV constitutes moreover more than 80%, more preferably more than 90% (% by volume) of the totality of the reinforcing filler, a minor fraction (preferably less than 20%, more preferably less than 10% in volume) of this totality may be constituted by another reinforcing filler, for example an inorganic filler or carbon black.
• the nanoparticles of PV may advantageously constitute all of the reinforcing filler in said polymer matrices.
• the PV nanoparticles previously described are advantageously incorporated into their polymer matrix via a masterbatch, that is to say that these particles are premixed with at least one polymer to facilitate their subsequent incorporation into the polymer matrix. final.
• masterbatch or “masterbatch” must be understood in known manner the mixture of at least one polymer (for example an elastomer or a mixture of elastomers) and a reinforcing filler, precursor mixture of the polymer matrix final, ready for use.
• this masterbatch can be prepared by a method comprising the following steps:
• the polymer latex may consist of a polymer already available in emulsion or, for example, a polymer initially in solution which is emulsified in a mixture of organic solvent and water, generally by means of a surfactant (the organic solvent disappearing at the time of coagulation or precipitation).
• the intimate mixing operation of the two latices is carried out in such a way as to disperse the nanoparticles of PV into the polymer, homogenize the assembly to form a latex mixture with a concentration of solid preferably between 20 and 500 g / l, more preferably between 50 and 350 g / l.
• the two starting latices are diluted with water before mixing (for example 1 volume of water per 1 volume of latex).
• Precipitation of the mixture of the two latices can be carried out by any method known to those skilled in the art, for example by a mechanical action or preferably by the action of a coagulating agent.
• the coagulating agent is any liquid compound, miscible with water but not solvent (or bad solvent) of the polymer, for example an aqueous saline solution, preferably an alcohol or a mixture of solvents comprising at least one alcohol (for example alcohol and water, alcohol and toluene). More preferably, the coagulating agent is an alcohol alone such as methanol or isopropanol.
• Coagulation is preferably carried out with stirring, at room temperature, in a large volume of coagulant; typically, a volume of alcohol is used which is at least twice the cumulative total volume of the two diluted latexes. During this step, it is preferred to pour the mixture of the two latexes on the coagulant, and not the other way around.
• the masterbatch is obtained in the form of "crumbs" of polymer, comprising at least the chosen polymer and the nanoparticles of PV embedded in the polymer matrix.
• additives may be incorporated into the masterbatch, whether they are intended for the masterbatch itself (for example a stabilizing agent, carbon black to as a coloring and anti-UV agent, a plasticizer, an antioxidant, etc.) or to the final polymer matrix for which the masterbatch is intended.
• a stabilizing agent for example a stabilizing agent, carbon black to as a coloring and anti-UV agent, a plasticizer, an antioxidant, etc.
• the polymer of the masterbatch may be any polymer, identical or not to that (or those) of the final polymer matrix. It may be advantageous to use the same polymer and adjust the PV level in the masterbatch to the final target rate, so as not to have to add polymer later, during the manufacture of the final polymeric composition comprising the nanoparticles of the invention, as a reinforcing filler, and the polymer thus reinforced.
• the nanoparticles according to the invention previously described are preferably used for the reinforcement of tires or semi-finished products for tires, these semi-finished products being chosen in particular from the group constituted by the treads, the sub-layers intended for example to be placed under these treads, crown reinforcement plies, flanks, carcass reinforcement plies, heels, protectors, inner tubes, tubeless tire inner liner, gums internal sidewall reinforcements and other erasers for supporting the load in the event of flat tire running.
• rubber compositions based on at least: (i) one (i.e. at least one) diene elastomer are used; (ii) one (i.e. at least one) PV charge according to the invention and (iii) a (i.e. at least one) coupling agent providing the bond between this PV charge and this diene elastomer.
• based on a composition comprising the mixture and / or the reaction product of the various basic constituents used, some of these constituents being able to react and / or being intended to react with one another, at least partially, during the various phases of manufacture of the composition, or during its subsequent cooking.
• elastomer or rubber (both terms being synonymous) of the "diene” type, is meant 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).
• the diene elastomer is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as BR), polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• the diene elastomer is predominantly, that is to say for more than 50 phr, a styrene-butadiene copolymer (SBR), whether it is an SBR prepared in emulsion (“E-SBR") or solution-prepared SBR ("S-SBR”), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), or BR / NR (or BR / IR).
• SBR styrene-butadiene copolymer
• the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer, that is to say a homopolymer or a copolymer of isoprene selected from the group consisting of natural rubber (NR), the synthetic polyisoprenes (IR), the various isoprene copolymers and the mixtures of these elastomers.
• an isoprene elastomer that is to say a homopolymer or a copolymer of isoprene selected from the group consisting of natural rubber ( NR), the synthetic polyisoprenes (IR), the various isoprene copolymers and the mixtures of these elastomers.
• This isoprene elastomer is preferably natural rubber or a cis-polyisoprene.
• the rubber composition may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (optionally chlorinated or brominated), that these copolymers are used alone or in admixture with highly unsaturated diene elastomers as mentioned above, in particular NR or IR, BR or SBR.
• the coupling agent (or bonding agent) is intended to establish a sufficient connection between the surface of the PV particles and the polymer to which these particles are intended, so that the latter can fully perform their function of reinforcing filler.
• Coupling agents are well known to those skilled in the art and have been described in a very large number of documents. Any coupling agent capable of efficiently ensuring, in a diene rubber composition which can be used for the manufacture of tires, the bonding between a reinforcing inorganic filler such as a silica and a diene elastomer, in particular organosilanes or polyorganosiloxanes, may be used. multifunctional.
• organosilanes include of bis (alkoxyl (C] -C 4) alkyl silyl (Ci-C 4)) such as polysulphides of bis (3-trimethoxysilylpropyl) or of bis (3-triethoxysilylpropyl), in particular bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S 2 ] 2 or bis-disulfide; (triethoxysilylpropyl), abbreviated as TESPD, of formula [(C 2 H 5 O) 3 Si (CH 2 ) S S] 2 .
• bis (alkoxyl (C] -C 4) alkyl silyl (Ci-C 4)) such as polysulphides of bis (3-trimethoxysilylpropyl) or of bis (3-triethoxysilylpropyl), in particular bis (3
• preferred coupling agents of bis (monoalkoxyl (Ci-C 4) -dialkyl (C -C 4) silylpropyl), particularly tetrasulfide or disulfide bis-monoéthoxy- diméthylsilylpropyl.
• coupling agents other than the above-mentioned polysulfide alkoxysilanes, mention may be made in particular of bifunctional polyorganosiloxanes or hydroxysilane polysulfides.
• the level of coupling agent is preferably less than 10 phr, more preferably less than 7 phr, in particular less than 5 phr.
• the above rubber compositions also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, such as, for example, plasticizers or extension oils, pigments, agents and the like.
• additives usually used in elastomer compositions intended for the manufacture of tires such as, for example, plasticizers or extension oils, pigments, agents and the like.
• plasticizers or extension oils such as, for example, plasticizers or extension oils, pigments, agents and the like.
• anti-ozone waxes such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing or plasticizing resins, methylene acceptors or donors, coupling activators, coating agents, agents facilitating the processability, a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators.
• two charges of functionalized (Z) and crosslinked polymethacrylate are synthesized by radical polymerization of three different monomers - methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDMA) and filler A: trimethoxysilylpropyl methacrylate (MPST) or filler B: trimethoxysilylpropyl acrylate (ATSP) - then incorporated into a tire rubber composition in the form of masterbatchs obtained by coprecipitation of a latex of the PV load and a latex of a diene elastomer ( SBR).
• MMA methyl methacrylate
• EGDMA ethylene glycol dimethacrylate
• MPST trimethoxysilylpropyl methacrylate
• ATSP trimethoxysilylpropyl acrylate
• the weight ratio of comonomer B carrying the Z function (here, MTSP or ATSP) is between 20 and 30%, that of the crosslinking comonomer C (here EGDMA) is between 10% and 30%. %.
• the different monomers are previously subjected to a nitrogen sparge, as well as all the aqueous solutions used with the exception of the solution of SDS (bubbling in the form of powder).
• the reaction is conducted in a 1.5 liter reactor equipped with mechanical stirring. After introduction of 840 ml of water and sparging with nitrogen for 30 min with stirring, 50 ml of an aqueous solution of sodium dodecyl sulphate (SDS) at a concentration of 0.9 mol / l are introduced successively.
• surfactant 50 ml to 1 mol / l of an equimolar buffer solution of sodium hydrogen phosphate and ammonium dihydrogenphosphate.
• pH 7 stirred at 350 rpm and heated to 60 ° C.
• the functionalized and crosslinked polymethacrylates thus obtained are in the form of a latex comprising approximately 10% by weight of solid (PV) and the balance (approximately 90%) of water.
• the characterization of the filler latex A is carried out in accordance with paragraph I-1-A.
• the TEM image reproduced in FIG. 1 shows that the nanoparticles (elementary particles) of the invention are here in the form of nanobeads which have a majority of a diameter of between 20 and 60 nm.
• the average circular diameter is equal to 34 nm (standard deviation 6 nm).
• charge A the polymethacrylate (charge A) is isolated and dried in order to evaluate its degree of functionalization (Z) provided by the monomer MTSP, by assaying the silicon content, by proceeding as follows:
• ICP / AES inductively coupled plasma atomic emission spectrometry
• the procedure is as follows: the sample is calcined at 525 ° C. for 2 hours. The melting is then carried out on the ashes obtained at 1150 ° C. ( ⁇ 50 ° C.) with lithium tetraborate (for example 2 g per 1 g of calcined filler) for about 25 minutes.
• the melt bead obtained is solubilized at 80 ° C. in hydrochloric acid diluted to 2% in water.
• the solution is then transferred and adjusted in a volumetric flask.
• the measurement of the silicon is then carried out, on the content of the volumetric flask, by ICP / AES: the aqueous solution is sent into an argon plasma via an introduction system, where it undergoes the phases of desolvation, atomization then excitation / ionization of the atoms present.
• the silicon emission line at 251.611 nm is then selected through a monochromator and quantified against a calibration curve prepared from a certified standard solution of the corresponding element (intensity I). the emitted line is proportional to the concentration C of the corresponding element).
• the density of the nanoparticles of charge A is measured on the powder, using a helium pycnometer: the value obtained is equal to 1.25 g / cm 3 .
• the polymethacrylate latices are then incorporated directly into an SBR diene elastomer to obtain a masterbatch as indicated in the previous paragraph II-2.
• the polymethacrylate loading rate referred to in the masterbatch, as in the final rubber composition targeted, is 39 phr (parts by weight per hundred parts of elastomer).
• the SBR latex is prepared in a manner known to those skilled in the art under the following conditions: polymerization temperature: 50 ° C.
• surfactant sodium dodecyl sulphate; initiator: redox system iron salt II / hydroperoxide.
• the conversion is of the order of 50 to 60%.
• the amount of solids content of the SBR latex is determined by weighing, on dry extract, before preparing the masterbatch.
• the SBR latex is diluted 3 times with water, ie: Charge A: 652 ml of 177.1 g / l SBR latex (115.4 g of SBR) and 1304 ml of dilution water.
• the polymethacrylate latices are cooled to room temperature and then added to SBR latices diluted at the rate of 39 phr, ie:
• Charge B 368 ml of 84.8 g / l polymethacrylate filler latex (31.2 g load).
• a control composition (silica filler HDS) is prepared conventionally, as follows: in an internal mixer, whose initial tank temperature is approximately 90 ° C., firstly ("non-productive phase") is introduced the SBR elastomer previously extended with 37.5 phr of oil, as well as part of the load. After a suitable mixing time, of the order of 1 min, the coupling agent and the remaining portion of charge are added. The other ingredients, with the exception of the vulcanization system, are added after 2 minutes. The internal mixer is then filled to 75%. Theromechanical work is then carried out for a duration of about 6 minutes, with an average pallet speed of 70 revolutions / min, until a fall temperature of about 135 ° C. is obtained.
• the mixture obtained is recovered, cooled and then the vulcanization system (sulfur and sulfenamide type primary accelerator) is added to an external mixer at 30 ° C., mixing the whole ("productive phase”). for a suitable time (between 5 and 12 min).
• the compositions thus obtained are then either calendered in the form of plates (thickness of 2 to 3 mm) of rubber for the measurement of their mechanical properties, or extruded in the form of a semi-finished product for a tire, for example a web. rolling.
• the vulcanization (cooking) is carried out at 150 ° C. for 40 min, under pressure.
• the rubber compositions are characterized, before and after firing, as indicated below.
• the measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983).
• the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.
• the measurements are processed according to DIN 53529 - Part 2 (March 1983).
• the conversion rate constant K (in min -1 ) of order 1, calculated between 30% and 80% of conversion, is measured, which makes it possible to assess the kinetics of vulcanization (the higher K, the faster the kinetics) ).
• the dynamic properties ⁇ G * and tan ( ⁇ ) max are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard.
• the response of a sample of vulcanized composition (cylindrical specimen with a thickness of 2 mm and a section thickness of 79 mm 2 ) is recorded, subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, under normal conditions. temperature (23 ° C) according to ASTM D 1349-99.
• a peak-to-peak deformation amplitude sweep of 0.1 to 50% (forward cycle) followed by 50% to 0.1% (return cycle) was performed. ).
• the purpose of the test is to compare the performance of the nanoparticles of the invention with those of the conventional inorganic filler (HDS silica).
• the silica HDS chosen to reinforce the control composition is a pneumatic grade silica having, in a known manner, a very high reinforcing power ("Zeosil” type "1165MP" from Rhodia - density of about 2.1 g / cm 3 ).
• the diene elastomer used is SBR, the synthesis of which is described in paragraph III-2, previously extended with 37.5% of TDAE oil (ie 37.5 phr of oil per 100 phr of dry SBR). ).
• compositions tested are strictly identical to the nature of the reinforcing filler by:
• composition C-I silica HDS (control); Composition C-2: Functionalized PV MTSP (Invention), Composition C-3 (Invention): Functionalized PV Z (ATSP).
• the rate of reinforcing filler was adjusted to iso-fraction by volume of filler (same volume - ie about 19% - of filler in each composition). As the specific surface area of the polymer filler is lower, the amount of TESPT coupling agent introduced into compositions C-2 and C-3 is therefore lower.
• the PV nanoparticles represent approximately 97% (by volume) of the totality of the reinforcing filler, the latter comprising a small proportion (2 phr) of carbon black.
• Tables 1 and 2 give successively the formulation of the various compositions (Table 1 - rate of the different products expressed in phr), their properties before and after curing at 150 ° C. for 40 minutes (Table 2).
• Table 2 The examination of the different results of Table 2 shows for the compositions C-2 and C-3 reinforced nanoparticles according to the invention, compared to the control composition CI:
• the charge of functionalized (Z) and crosslinked polymethacrylate synthesized in III-1-A (charge B) by radical polymerization of three different monomers - methyl methacrylate (MMA), ethylene dimethacrylate glycol (EGDMA) and trimethoxysilylpropyl acrylate (APST) is incorporated into a rubber tire composition in the form of a masterbatch obtained by coprecipitation of the PV charge latex and a NR latex.
• the polymethacrylate latex is incorporated directly into natural rubber.
• the polymethacrylate loading rate referred to in the masterbatch is 39 phr (parts by weight per hundred parts of elastomer).
• the amount of dry matter of the NR latex is determined by weighing, on dry extract, before preparing the masterbatch.
• the NR latex is diluted 3 times with water, ie 447 ml of 178.8 g / l NR latex (80 g of NR) and 900 ml of dilution water.
• the polymethacrylate charge latex (Charge B synthesized in paragraph III-1-A) is cooled to room temperature and then added to the diluted NR latex at a rate of 39 phr, ie 368 ml of polymethylmethacrylate laticate latex. at 84.8 g / l (31.2 g load). The resulting mixture is gently homogenized. At a rate of 100 ml / min, the mixture is then added to 3500 ml of methanol stirred at 350 rpm. The precipitate thus obtained is filtered on filter paper, rinsed with water until constant residual low foaming of the washings and negative test of silver nitrate washings. The precipitate thus washed is dried under reduced pressure under nitrogen at 60 ° C. for 3 to 4 days. 110 g of dry masterbatch are thus recovered.
• composition C-4 control: silica HDS
• composition C-5 invention: PV functionalized ATSP.
• such rubber compositions are typically used in the parts of ground-engaging systems, in particular of tires, usually using NR-based rubber matrices, such as, for example, the internal supports of safety for tires, sidewalls, tire bead zones, underlays of treads and treads of these tires, particularly for heavy goods vehicles.
• NR-based rubber matrices such as, for example, the internal supports of safety for tires, sidewalls, tire bead zones, underlays of treads and treads of these tires, particularly for heavy goods vehicles.
• the degree of reinforcing filler was adjusted to iso-fraction by volume of filler (same volume - ie approximately 17% - filler in each composition). As the specific surface of the polymer filler is lower, the amount of TESPT coupling agent introduced into the composition C-5 is therefore much lower.
• the PV load represents about 97% (by volume) of the totality of the reinforcing filler, the latter comprising a small proportion (1 phr) of carbon black.
• Tables 3 and 4 give successively the formulation of the various compositions (Table 3 - rate of the different products expressed in phr), their properties before and after baking at 15O 0 C for 25 min (Table 4).
• PV at least equal if not greater than that offered by the reference HDS silica; and last but not least, which largely confirms all the previous results observed with a synthetic diene elastomer (SBR), hysteresis properties which are again strongly improved (values of (tan ( ⁇ ) max and ⁇ G * very significantly reduced ).
• SBR synthetic diene elastomer
• the PV nanoparticles according to the invention thanks to their very greatly reduced density compared to a conventional reinforcing filler such as carbon black or HDS silica, make it possible to very substantially reduce the weight of the polymeric compositions.
• This objective is achieved not only without degradation of the reinforcement, synonymous with resistance to wear or cracking, compared to these conventional loads, but also allowing a significant reduction in hysteresis, synonymous with rolling resistance or further enhanced heating over a conventional reinforcing inorganic filler such as HDS silica.
• the nanoparticles of the invention are advantageously usable as a reinforcing filler for any type of polymeric matrix, whether the polymers are in particular thermoplastics, thermosetting polymers or even elastomers (for example polyamides, polyesters, polyolefins such as polypropylene, polyethylene, PVC, polycarbonates, polyacrylics, epoxy resins, polysiloxanes, polyurethanes, diene elastomers).
• elastomers for example polyamides, polyesters, polyolefins such as polypropylene, polyethylene, PVC, polycarbonates, polyacrylics, epoxy resins, polysiloxanes, polyurethanes, diene elastomers.

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• 2006
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