Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/25—Incorporating silicon atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
  • C08K5/31—Guanidine; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/548—Silicon-containing compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
  • C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof

Definitions

• the present invention relates to diene rubber compositions reinforced with an inorganic filler such as silica, used in particular for the manufacture of tires or semi-finished products for tires such as treads.
• an at least bifunctional coupling agent (or bonding agent) is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer.
• coupling agent is meant, in known manner, an agent capable of establishing a sufficient bond, of a chemical and / or physical nature, between the inorganic filler and the diene elastomer; such a coupling agent, at least bifunctional, has for example as simplified general formula "Y-Z-X", in which:
• Y represents a functional group ("Y" function) which is capable of binding physically and / or chemically to the inorganic filler, such a bond being able to be established, for example, between a silicon atom of the coupling agent and the surface hydroxyl (OH) groups of the inorganic filler (for example surface silanols in the case of silica);
• X represents a functional group ("X" function) capable of binding physically and / or chemically to the diene elastomer, for example via a sulfur atom;
• Z represents a divalent group making it possible to connect Y and X.
• Coupling agents in particular silica / diene elastomer have been described in a very large number of documents, the best known being bifunctional organosilanes bearing alkoxyl functions (that is to say, by definition, "alkoxysilanes") to as functions "Y” and, as functions "X", functions capable of reacting with the diene elastomer such as for example polysulfide functions.
• blocked mercaptosilanes are particularly interesting, however, given their very high reactivity, blocked mercaptosilanes are generally used. It is recalled here that the blocked mercaptosilanes, in a manner well known to those skilled in the art, are precursors of silanes capable of forming mercaptosilanes during the preparation of the rubber compositions (see for example US 2002/0115767 A1 or the application International Patent WO 02/48256). The molecules of these silane precursors, hereinafter referred to as blocked mercaptosilanes, have a blocking group instead of the corresponding mercaptosilane hydrogen atom.
• the blocked mercaptosilanes are capable of being released by replacement of the blocking group by a hydrogen atom, during mixing and firing, to lead to the formation of a more reactive mercaptosilane, defined as a silane whose molecular structure contains at least one thiol (-SH) (mercapto) group bonded to a carbon atom and at least one silicon atom.
• a more reactive mercaptosilane defined as a silane whose molecular structure contains at least one thiol (-SH) (mercapto) group bonded to a carbon atom and at least one silicon atom.
• These blocked mercaptosilane coupling agents are thus generally used in the presence of blocked mercaptosilane activator whose role is to initiate, accelerate or enhance the activity of the blocked mercaptosilane, as specified in particular in US Pat. 590.
• Such an activator or "deblocking agent” for tire rubber compositions generally consists of guanidine, particularly ⁇ , ⁇ '-diphenylguanidine, DPG.
• guanidine particularly ⁇ , ⁇ '-diphenylguanidine, DPG.
• DPG diphenylguanidine
• rubber compositions comprising, as coupling agent, specific blocked mercaptosilanes, which are both free or virtually devoid of guanidine derivatives, and which are devoid of or almost free of zinc oxide, make it possible to to obtain a compromise of properties similar to that obtained with the same mercaptosilanes in the presence of guanidine derivatives and zinc oxide.
• guanidine derivatives is intended to mean organic compounds having a guanidine function as their main function, such as those known in tire compositions, in particular as vulcanization accelerators, for example diphenylguanidine (DPG) or diorthotolylguanidine (DOTG).
• DPG diphenylguanidine
• DAG diorthotolylguanidine
• vulcanization of diene elastomers by sulfur is widely used in the rubber industry, in particular in that of the tire.
• a relatively complex vulcanization system comprising, in addition to sulfur, various vulcanization accelerators as well as one or more vulcanization activators, in particular zinc derivatives such as zinc oxide (ZnO) is used.
• zinc derivatives such as zinc oxide (ZnO)
• ZnO zinc oxide
• a medium-term objective of tire manufacturers is to remove zinc or its derivatives from their rubber formulations, because of the relatively toxic nature of these compounds, particularly with respect to water and chemicals. aquatic organisms (R50 classification according to European Directive 67/548 / EC of 9 December 1996).
• guanidine derivatives and zinc oxide in compositions comprising silica and specific blocked mercaptosilanes as coupling agent, surprisingly allows the coupling agent to react without need the presence of a deblocking agent and without degradation of the properties of this composition.
• the subject of the invention is therefore a zinc-free rubber composition or one containing less than 0.5 parts per hundred parts of elastomer, phr, of zinc, and devoid of guanidine derivatives or containing less than or 0.5 phr of derivatives.
• guanidiques based on at least one diene elastomer, an inorganic filler as a reinforcing filler, a blocked mercaptosilane corresponding to the general formula (I):
• R 1 which are identical or different, each represent a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms;
• R 2 which are identical or different, each represent hydrogen or a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms;
• the symbol A represents hydrogen or a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms and linear or branched alkoxyalkyls having from 2 to 8 carbon atoms;
• the symbol Z represents a divalent linking group comprising from 1 to 18 carbon atoms;
• a is an integer equal to 1, 2 or 3.
• the subject of the invention is also a finished or semi-finished article comprising such a composition, in particular a tire tread.
• the invention also relates to a tire or semi-finished product comprising at least one composition as mentioned above.
• the rubber compositions, in which the coupling agents are tested, are characterized before and after firing, as indicated below.
• the dynamic properties AG * and tan ( ⁇ ) max are measured on a viscoanalyzer (Metravib VA4000) according to ASTM D 5992-96.
• the response of a sample of vulcanized composition (cylindrical specimen 4 mm in thickness and 400 mm 2 in section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, at 23 ° C., is recorded.
• a strain amplitude sweep of 0.1 to 50%> (forward cycle) is performed, followed by 50%> to 1% (return cycle).
• the results exploited are the complex dynamic shear modulus (G *) and the loss factor (tan ⁇ ).
• G * complex dynamic shear modulus
• tan ⁇ the loss factor
• the maximum observed value of tan ⁇ (tan ( ⁇ ) max ) and the complex modulus difference (AG *) between the 0.1%> and 50%> deformation values are indicated. (Payne effect).
• base-based composition in the present application a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents (for example the coupling agent). being capable of, or intended to react with each other, at least in part, during the different phases of manufacture of the compositions, in particular during their vulcanization (cooking).
• elastomer or “diene” rubber is generally meant an elastomer derived at least in part (i.e. a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).
• the diene elastomers in known manner, can be classified into two categories: those said to be “essentially unsaturated” and those termed “essentially saturated”.
• essentially unsaturated diene elastomer is meant 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%).
• diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within this definition and may instead be referred to as "essentially saturated” diene elastomers. "(low or very low diene origin, always less than 15%).
• the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
• iene elastomer can be understood more particularly to be used in the compositions according to the invention: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;
• diene elastomer any type of diene elastomer
• the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
• 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di-(C 1 -C 5) -l-3-butadienes are especially suitable.
• Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene and divinylbenzene. vinyl naphthalene.
• the copolymers may contain between 99% and 20% by weight of diene units and between 80% and 80% by weight of vinyl aromatic 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 block, statistical, sequenced, microsequenced, 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.
• silanol or polysiloxane functional groups having a silanol end (such as described for example in FR 2,740,778 or US 6,013,718), alkoxysilane groups (as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402).
• Tg glass transition temperature
• styrene content between 5%> and 60%> by weight and more particularly between 20%> and 50%>, a content (%> molar) in -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 to -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 - 25 ° C and - 50 ° C.
• butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%.
• the diene elastomer of the composition according to the invention is chosen from the group of diene elastomers (highly unsaturated) consisting of polybutadienes (BR), synthetic polyisoprenes (IR), rubber natural (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• diene elastomers highly unsaturated consisting of polybutadienes (BR), synthetic polyisoprenes (IR), rubber natural (NR), butadiene copolymers, 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), isoprene-copolymers of butadiene-styrene (SBIR) and mixtures of such copolymers.
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR isoprene-copolymers of butadiene-styrene
• the diene elastomer is predominantly (ie, for more than 50 phr) an SBR, whether it is an emulsion-prepared SBR ("ESBR") or an SBR prepared in solution (“SSBR”), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), BR / NR (or BR / IR), or SBR / BR / NR (or SBR / BR / IR).
• SBR emulsion-prepared SBR
• SSBR SBR prepared in solution
• an SBR elastomer 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 to 35% by weight, is used in particular. 45%, a vinyl ring 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 between -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.
• the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer.
• the compositions of the invention are intended to constitute, in tires, the rubber matrices of certain treads (for example for industrial vehicles), crown reinforcing plies (for example work webs, protective webs or hoop webs), carcass reinforcement plies, flanks, beads, protectors, underlayments, rubber blocks and other internal gums providing the interface between aforementioned areas of the tires.
• isoprene elastomer in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
• NR natural rubber
• IR synthetic polyisoprenes
• isoprene copolymers mention will in particular be made of copolymers of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).
• This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
• the composition according to the invention may contain at least one substantially 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 mixture with highly unsaturated diene elastomers as mentioned above, in particular NR or IR, BR or SBR.
• the rubber composition comprises a blend of one (or more) diene elastomers called "high Tg” having a Tg between -70 ° C and 0 ° C and d one (or more) diene elastomers known as "low Tg” between -110 ° C and -80 ° C, more preferably between -105 ° C and -90 ° C.
• the high Tg elastomer is preferably selected from the group consisting of S-SBR, E-SBR, natural rubber, synthetic polyisoprenes (having a (mol%) content of cis-1,4 linkages of preferably greater than 95%), BIRs, SIRs, SBIRs, and mixtures of these elastomers.
• the low Tg elastomer preferably comprises butadiene units at a level (mol%) of at least 70%; it consists preferably of a polybutadiene (BR) having a content (mol%) of cis-1,4 linkages greater than 90%>.
• the rubber composition comprises, for example, from 30 to 100 phr, in particular from 50 to 100 phr, of a high Tg elastomer in a blend with 0 to 70 phr, in particular from 0 to 50 phr, of a low Tg elastomer; according to another example, it comprises for all 100 pce one or more SBR prepared (s) in solution.
• the diene elastomer of the composition according to the invention comprises a blend of a BR (as low elastomer Tg) having a rate (mol%) of cis chains -1.4 greater than 90%>, with one or more S-SBR or E-SBR (as elastomer (s) high Tg).
• compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
• reinforcing inorganic filler is meant here, in known manner, any inorganic or inorganic filler, regardless of its color and origin (natural or synthetic), also called “white” filler, “clear” filler “or” non-black filler “charge as opposed to carbon black, this inorganic filler being able to reinforce on its own, without any other means than a coupling agent intermediate, a rubber composition for the manufacture of a tread of tires, in other words able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade, in particular for tread; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
• -OH hydroxyl groups
• the reinforcing inorganic filler is a filler of the siliceous or aluminous type, or a mixture of these two types of filler.
• the silica (SiO 2 ) used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface area both less than 450 m 2 / g, preferably 30 to 400 m 2 / g.
• Highly dispersible precipitated silicas are preferred, in particular when the invention is used for the manufacture of tires having a low rolling resistance;
• examples of such silicas include Ultrasil 7000 silicas from Degussa, Zeospil 1,155 MP, 1,135 MP and 1115 MP from Rhodia, Hi-Sil EZ150G silica from PPG, Zeopol silicas 8715, 8745 or 8755 of the Huber Society.
• the reinforcing alumina (Al 2 O 3) preferably used is a highly dispersible alumina having a BET surface area ranging from 30 to 400 m 2 / g, more preferably from 60 to 250 m 2 / g, an average particle size of at most 500 nm. more preferably at most equal to 200 nm.
• aluminas "Baikalox Al 25" or "CR125” (Ba ⁇ kowski company), "APA-100RDX” (Congrua), "Aluminoxid C” (Degussa) or "AKP-G015 "(Sumitomo Chemicals).
• inorganic filler suitable for use in the tread rubber compositions of the invention mention may also be made of aluminum (oxide) hydroxides, aluminosilicates, titanium oxides, silicon carbides or nitrides, all of the reinforcing type as described for example in the applications WO 99/28376, WO 00/73372, WO 02/053634, WO 2004/003067, WO 2004/056915.
• the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 60 and 350 m 2 / boy Wut.
• An advantageous embodiment of the invention consists in using a reinforcing inorganic filler, in particular a silica, having a high BET specific surface area, in a range of 130 to 300 m 2 / g, because of the high reinforcing power of such charges.
• a reinforcing inorganic filler in particular a silica, having a BET specific surface area of less than 130 m 2 / g, preferably in such a case of between 60 and 130 m 2. / g (see for example WO03 / 002648 and WO03 / 002649).
• the physical state under which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• the term "reinforcing inorganic filler” also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described above.
• this level of reinforcing inorganic filler will be chosen between 20 and 200 phr, more preferably between 30 and 150 phr, in particular greater than 50 phr, and even more preferably between 60 and 140 phr.
• the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” Vol. 60, page 309, February 1938, specifically according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: time at 160 ° C - relative pressure range p / po: 0.05 at 0.17).
• the CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
• the reinforcing inorganic filler can be used also associated with an organic reinforcing filler, in particular carbon black, for example a black of the HAF, ISAF, SAF type, conventionally used in tires and particularly in the treads of tires (for example).
• carbon black for example a black of the HAF, ISAF, SAF type, conventionally used in tires and particularly in the treads of tires (for example).
• These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
• the carbon blacks could for example already be incorporated into the elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).
• the amount of carbon black present in the total reinforcing filler can vary within wide limits, however the reinforcing inorganic filler is preferably the majority reinforcing filler.
• carbon black is used in a very small proportion, at a preferential rate of less than 10 phr.
• the coloring properties (black pigmentation agent) and the anti-UV properties of the carbon blacks are advantageously observed, without penalizing by elsewhere the typical performances provided by the reinforcing inorganic filler.
• the composition of the invention may be completely devoid of carbon black.
• a blocked mercaptosilane of general formula (I) is used:
• R 1 which are identical or different, each represent a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms;
• R 2 which are identical or different, each represent hydrogen or a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms;
• the symbol A represents hydrogen or a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms and linear or branched alkoxyalkyls having from 2 to 8 carbon atoms;
• the symbol Z represents a divalent linking group comprising from 1 to 18 carbon atoms;
• a is an integer equal to 1, 2 or 3.
• Z may contain one or more heteroatoms chosen from O, S and N.
• a is equal to 3 and at least one of the symbols R 2 represents a monovalent hydrocarbon group chosen from alkyls, linear or branched, cycloalkyls or aryls, having from 1 to 18 carbon atoms. carbon.
• the symbols R 2 represent a monovalent hydrocarbon group chosen from linear or branched alkyls, cycloalkyls or aryls having from 1 to 18 carbon atoms. According to a preferred variant of this second embodiment, the following characteristics are verified:
• R 1 and R 2 are chosen from methyl, ethyl, n-propyl and isopropyl, preferably from methyl and ethyl;
• A is among alkyls having from 1 to 18 carbon atoms and the phenyl radical;
• Z is selected from alkylenes and Ci-Cis arylene C 6 -C 12.
• Z is chosen from methylene, ethylene or propylene, more particularly propylene.
• R 1 , R 2 are ethyl
• A is heptyl
• Z is propylene.
• S-octanoylmercaptopropyltriethoxysilane mention will be made of S-octanoylmercaptopropyltriethoxysilane.
• a is equal to 1.
• a is equal to 1.
• R 1 are chosen from methyl, ethyl, n-propyl and isopropyl, preferably from methyl and ethyl,
• R 2 is selected from methyl and ethyl
• A is chosen from alkyls having 1 to 18 carbon atoms and the phenyl radical
• Z is selected from alkylenes and Ci -C s arylene, C 6 -C 12.
• Z is chosen from C1-C10 alkylenes, and even more preferably Z is chosen from C1-C4 alkylenes.
• the symbols R 1 are methyls; more particularly A is chosen from alkyls having from 1 to 7 carbon atoms and the phenyl radical. Even more preferably, the symbols R 1 are methyls, A is a heptyl, R 2 is an ethyl and Z is a propylene.
• the blocked mercaptosilanes of formula (I) are such that the symbol R 2 represents hydrogen.
• a is equal to 2 or to 1. And preferably:
• R 1 is selected from methyl, ethyl, n-propyl and isopropyl, preferably from methyl and ethyl;
• - A is chosen from alkyls having 1 to 18 carbon atoms and the phenyl radical
• Z is selected from alkylenes and Ci -C s arylene, C 6 -C 12.
• Z is chosen from C1-C10 alkylenes. and more particularly Z is chosen from C1-C4 alkylenes.
• R 1 is methyl, and preferably A is chosen from alkyls having from 1 to 7 carbon atoms and phenyl radical, in particular R 1 is methyl, Z is propylene and A is a heptyl.
• S-octanoylmercaptopropyhydroxydimethylsilane and S-cocatoylmercaptopropyldihydroxymethylsilane are particularly suitable.
• the blocked mercaptosilane content is preferably between 2 and 15 phr. Below the minimum indicated, the effect may be insufficient, while beyond the maximum recommended, there is generally no improvement, while the costs of composition increase; for these various reasons, this content is more preferably still between 4 and 12 phr.
• the rubber compositions according to the invention may also comprise all or part of the usual additives normally used in the compositions elastomers for the manufacture of tires, in particular treads, such as for example plasticizers or extension oils, the latter being of aromatic or non-aromatic nature, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M) as described, for example in the application WO 02/10269, a crosslinking system based on either sulfur, or sulfur and / or peroxide and / or bismaleimide donors, vulcanization accelerators, vulcanization activators, excluding, of course, zinc base (or in compliance with the maximum 0.5 phr of zinc in the composition, and preferably less than 0.3 phr).
• plasticizers or extension oils the latter being of aromatic or non-aromatic nature, pigment
• 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, ester (especially trioleate) oils.
• glycerol the hydrocarbon plasticizing resins having a high Tg preferably greater than 30 ° C, and mixtures of such compounds.
• compositions may also contain, in addition to the coupling agents, coupling activators, covering agents (comprising, for example, the only Y function) of the reinforcing inorganic filler or, more generally, processing aid agents capable of in a known manner, thanks to an improvement of the dispersion of the inorganic filler in the rubber matrix and to a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes (especially alkyltriethoxysilanes), polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol amines), hydroxylated or hydrolyzable POSs, for example ⁇ , ⁇ -dihydroxy-polyorganosiloxanes (in particular ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes), fatty acids such as, for
• the rubber compositions of the invention are manufactured in appropriate mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called phase “non-productive") 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 "productive" phase) at a lower temperature, typically below 120 ° C, by example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization.
• a first phase of work or thermomechanical mixing sometimes called phase "non-productive”
• a second mechanical working phase sometimes referred to as "productive” phase
• all the basic constituents of the compositions of the invention with the exception of the vulcanization system, namely the reinforcing inorganic filler, the coupling agent of formula (I) and the carbon black are intimately incorporated, by kneading, with the diene elastomer during the first so-called non-productive phase, that is to say that it is introduced into the mixer and kneaded thermomechanically, in one or more steps, at least these various basic constituents until reaching the maximum temperature between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C.
• the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible coating agents, are introduced into a suitable mixer such as a conventional internal mixer. or other complementary additives and other additives, with the exception of the vulcanization system.
• the total mixing time in this non-productive phase is preferably between 1 and 15 minutes.
• the vulcanization system is then incorporated at low temperature, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• a coating agent When a coating agent is used, its incorporation can be carried out entirely during the non-productive phase, together with the inorganic filler, or in full during the productive phase, together with the vulcanization system, or still split over the two successive phases.
• the vulcanization system itself is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator.
• a primary vulcanization accelerator in particular a sulfenamide type accelerator.
• various known secondary accelerators or vulcanization activators excluding zinc and any zinc derivative 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), with a zinc content of the composition of less than 0.5 phr, and preferably less than 0.3 phr, and so on.
• the sulfur content is preferably between 0.5 and 3.0 phr, that of the primary accelerator is preferably between 0.5 and 5.0 phr.
• 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 that can be used, for example, as a tread. tire for passenger vehicle.
• the vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the cooking temperature, the system of vulcanization adopted and the kinetics of vulcanization of the composition under consideration.
• the invention relates to the rubber compositions described above both in the so-called “raw” (i.e., before firing) state and in the so-called “cooked” or vulcanized (i.e., after crosslinking or vulcanization) state.
• the compositions according to the invention can be used alone or in a blend (i.e., in a mixture) with any other rubber composition that can be used for the manufacture of tires.
• III-1 Blocked Mercaptosilanes Used III-1.1 Silane NXT (Mercaptosilane “Ml")
• S-octanoylmercaptopropylhydroxydimethylsilane of formula: The preparation of S-octanoylmercaptopropylethoxydimethylsilane A of CAS number [1024594-66-8] is described in the patent application Michelin FR 2940301 / WO 2010072682.
• Product B is prepared by hydrolysis in a catalytic acid medium.
• demineralized water 60 ml
• acetone 300 ml
• S-octanoylmercaptopropylethoxydimethylsilane A 59.0 g, 0.194 mol
• the solution is stirred for 1.5-2 hours at room temperature.
• the mixture obtained is chromatographed on a silica column (eluent mixture of petroleum ether and ethyl acetate in a ratio of 1: 1).
• an oil 41 g, 0.148 mol, yield of 76%) is obtained.
• NMR analysis confirms the structure of S-octanoylmercaptopropylhydroxydimethylsilane obtained with a molar purity higher than 97%. NMR analysis is carried out in acetone-d6.
• the intermediate product G can be prepared in biphasic medium according to the procedure described in WO 2005007660. Another possibility is to prepare it according to the following procedure. To a solution of 3-mercaptopropyldimethoxymethylsilane F of CAS number [31001- 77-1] (20.0 g, 0.111 mol) and triethylamine (11.2 g, 0.111 mol) in cyclohexane (200 mL) maintained at 5 ° Under an inert atmosphere, octanoyl chloride (18.0 g, 0.111 mol) is added dropwise over 30 minutes. The temperature of the reaction medium remains between 5 and 8 ° C. The reaction medium is then stirred for 15 hours at room temperature.
• the crystals are filtered and dried on filter for 30 min and then 2-3h under reduced pressure.
• the product obtained (24.9 g) has a melting point of 63 ° C.
• the residue obtained is recrystallized a second time in pentane (80 ml) for 4-5 hours at -20 ° C. This second fraction (6.5 g) has a melting point of 63 ° C.
• NMR analysis confirms the structure of S-octanoylmercaptopropyldihydroxymethylsilane H obtained with a molar purity greater than 93.5%. If a higher purity is required, a final crystallization in a mixture of petroleum ether (500 mL) ethanol (7 mL) for 15 hours gives a solid (16.9 g, 44% yield) of molar purity greater than 99% (melting point 66 ° C).
• a rallyldimethylchlorosilane A of CAS number [4028-23-3] (45.1 g, 0.335 mol) is added at room temperature thioacetic acid (25.5 g, 0.335 mol) under argon. The reaction is exothermic. The reaction medium is stirred for 3.5 hours at 85-95 ° C. After cooling to room temperature, the non-isolated intermediate silane B is added dropwise to a solution of triethylamine (51.2 g, 0.506 mol) in absolute ethanol (200 mL) for 15-20 min at 0 ° C. argon. After stirring for 15 hours at room temperature, the precipitate of triethylamine hydrochloride Et3N * HCl is filtered.
• the diene elastomer (SBR and BR cutting), the diene elastomer (SBR and BR) are introduced into an internal mixer, 70% filled and having an initial tank temperature of about 90.degree. silica supplemented with a small amount of carbon black, the coupling agent and then, after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization system.
• Thermomechanical work (non-productive phase) is then carried out in one step (total mixing time equal to about 5 minutes), until a maximum temperature of "fall” of about 165 ° C. is reached.
• compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or in the form of usable profiles. directly, after cutting and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as treads of tires.
• the purpose of this test is to demonstrate the improved properties of tire tread rubber compositions having silica as a reinforcing filler, devoid of guanidine derivatives, more specifically DPG-free, and zinc-free, having as its coupling agent a blocked mercaptosilane according to the invention compared firstly to a control rubber composition comprising the same blocked mercaptosilane as well as DPG and zinc and secondly to a control composition comprising the same blocked mercaptosilane as well as only zinc but devoid of DPG.
• compositions based on a diene elastomer (SBR / BR blend) reinforced with a highly dispersible silica (HDS) are prepared, and as coupling agent, the M1 mercaptosilane.
• composition Cl is a control composition containing DPG (1.5 phr) and zinc (1.5 phr of ZnO),
• composition C2 not in accordance with the invention, corresponds to the composition C1 but devoid of DPG,
• composition C3 according to the invention is devoid of DPG and devoid of zinc.
• Tables 1 and 2 give the formulation of the various compositions (Table 1 - rate of the different products expressed in phr or parts by weight per hundred parts of elastomer) as well as their properties after curing (approximately 40 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
• composition C3 according to the invention devoid of DPG and zinc, makes it possible to have a reinforcement (MA300 / MA100) comparable to that of the control composition C1, contrary to the composition C2 for which the reinforcement is significantly lower.
• the composition C3 according to the invention exhibits reduced hysteresis, as attested by tan ( ⁇ ) max and AG * values compared to control composition Cl, which are substantially decreased; this is a recognized indicator of a reduction in the rolling resistance of tires, and consequently a decrease in the energy consumption of motor vehicles equipped with such tires.
• the composition C2 only devoid of DPG has a hysteresis much higher than the control composition Cl.
• compositions based on a diene elastomer (SBR / BR blend) reinforced with a highly dispersible silica (HDS) are prepared, and as coupling agent, the M3 mercaptosilane.
• composition C4 is a control composition containing DPG (1.31 phr) and zinc (1.2 phr of ZnO),
• composition C5 not in accordance with the invention corresponds to the composition C4 but devoid of DPG
• composition C6 according to the invention is devoid of DPG and devoid of zinc.
• Tables 3 and 4 give the formulation of the various compositions (Table 3 - levels of the different products expressed in phr or parts by weight per hundred parts of elastomer) as well as their properties after curing (approximately 40 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
• Table 4 shows, as in Test 1, that the composition C6 according to the invention devoid of DPG and zinc, makes it possible to have a reinforcement (MA300 / MA100) comparable to the control composition C4. unlike the C5 composition for which the reinforcement is significantly lower. It is also found that the composition C6 according to the invention has a significantly reduced hysteresis (values of tan ( ⁇ ) max and AG * substantially decreased) compared to the control composition C4; the effect appearing superior to the C5 composition only devoid of DPG which has hysteresis also reduced compared to the control composition C4.
• the purpose of this test is to demonstrate the improved properties of tire tread rubber compositions according to the invention, having silica as a reinforcing filler, free of guanidine derivatives, more specifically free of DPG, and free of zinc. , comprising other blocked mercaptosilanes of formula (I) (M2 and M4 mercaptosilanes) compared to a control composition conventionally comprising commercial blocked mercaptosilane M1, DPG and zinc.
• composition Cl is that of the test 1,
• composition C7 according to the invention free of DPG and zinc and comprising the mercaptosilane M2,
• composition C8 free of DPG and zinc and comprising mercaptosilane M4 It will be noted that in order to compare the properties of compositions C1, C7 and C8, the blocked mercaptosilane coupling agents of compositions C7 and C8 are used at an isomolar silicon level compared to the control composition Cl.
• Tables 5 and 6 give the formulation of the various compositions (Table 5 - levels of the different products expressed in phr or parts by weight per hundred parts of elastomer) as well as their properties after curing (approximately 40 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
• Table 6 again underlines the fact that the compositions C7 and C8 according to the invention, comprising different blocked mercaptosilanes of formula (I) and devoid of DPG and zinc, make it possible to have a reinforcement (MA300 / MA100) comparable to the conventional control composition C1 containing the blocked mercaptosilane M1 as well as DPG and zinc.
• silica "ZEOSIL 1,165 MP” from Rhodia in the form of microbeads BET and CTAB: approximately 150-160 m2 / g);
• oleic sunflower oil (Agripure 80" from the company Cargiil);

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