Classifications

• • 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
  • C08K5/544—Silicon-containing compounds containing nitrogen
  • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
• • 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
  • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F136/08—Isoprene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08L7/00—Compositions of natural rubber

Definitions

• the present invention relates to compositions of diene elastomers reinforced with an inorganic filler such as silica, intended for the manufacture of tires or semi-finished products for tires, in particular to the treads of these tires.
• an inorganic filler such as silica
• Coupled agent inorganic filler / elastomer
• Y represents a functional group ("Y" function) which is capable of binding physically and / or chemically to the feedstock such a bond can be established, for example, between a silicon atom of the coupling agent and the hydroxyl groups (OH) surface of the inorganic filler (for example the surface silanols when it comes to 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;
• the coupling agents must not be confused with simple inorganic filler agents which, in a known manner, may comprise the active "Y” function with respect to the inorganic filler but are in any case without the function "X" active vis-à-vis the diene elastomer.
• Coupling agents in particular (silica / diene elastomer), have been described in a large number of patent documents, the best known being bifunctional sulphide silanes, in particular alkoxysilanes, which are nowadays considered as products providing, for vulcanizates loaded with silica, the best compromise in terms of safety when roasting, ease of implementation and strengthening power.
• TESPT bis 3-triethoxysilylpropyl tetrasulfide
• the need is particularly present in the case of rubber matrices based on an isoprene elastomer such as those used in the treads of heavy-duty tires, in which, in known manner, an effective bond with the elastomer is much more difficult to obtain compared to the use of carbon black.
• - G 1 identical or different, each represent a monovalent hydrocarbon group selected from alkyls, linear or branched, substituted or unsubstituted, having from 1 to 18 carbon atoms, cycloalkyls or aryls, substituted or unsubstituted, having 5 to 18 carbon atoms,
• G 2 which are identical or different, each represent a hydroxyl group or a monovalent group in the form (G 3 ) n -OG 1 in which G 3 is a divalent linking group comprising from 1 to 18 carbon atoms and containing one or more heteroatoms selected from O, S, Si and N, and n is a number greater than or equal to 0 and less than or equal to 18.
• Z represents a divalent linking group comprising from 1 to 18 carbon atoms, a is equal to 1, 2 or 3.
• the diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• the reinforcing inorganic filler is a siliceous or aluminous filler.
• the invention also relates to a tire or semi-finished product comprising a rubber composition as described above, and further relates to a tire tread comprising such a rubber composition.
• the rubber compositions are characterized, before and after firing, as indicated below. Traction tests
• the secant modulus (or apparent stress, in MPa, referred to strain, without unit) at 100 is measured as a second elongation (Le., After an accommodation cycle at the extension rate provided for the measurement itself).
• the dynamic property tan ( ⁇ ) max is 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, is recorded according to the ASTM D standard. 1349 - 99.
• a strain amplitude sweep of 0.1 to 90% (forward cycle) and then 90% to 0.1% (return cycle) are performed.
• the result exploited is the loss factor (tan ⁇ ).
• the maximum value of tan ⁇ observed (tan ( ⁇ ) max) is given between the values at 0, 1% and at 50% deformation (Payne effect).
• compositions of the invention are therefore based on at least one diene elastomer, an inorganic filler as reinforcing filler and an azosilane compound of formula (I) as inorganic filler coupling agent. diene elastomer.
• 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).
• the percentages (%) indicated are% by weight.
• 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:
• 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-methyl styrene, the commercial "vinyl-toluene" mixture, para-tertiobutyl styrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
• the copolymers may contain from 99% to 20% by weight of diene units and from 1% to 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.
• a coupling agent for example, functional groups comprising a C-Sn bond or amino functional groups such as benzophenone for example;
• a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2,740,778 or US Pat. No.
• alkoxysilane groups such as as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445) or groups polyethers (as described for example in EP 1 127 909 or US Pat. No. 6,503,973).
• functionalized elastomers mention may also be made of elastomers (such as SBR, BR, R or IR) of the epoxidized type.
• Tg glass transition temperature
• styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in -1,2 bonds of the butadiene part; between 4% and 75%, a content (mol%) of 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 of between -25.degree.
• butadiene-styrene-isoprene copolymers those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, in particular an isoprene content of between 15% and 50% by weight are suitable.
• %> 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%>, a content (%> molar) in units -1,2 of the butadiene part of between 4%> and 85% o, a content (%> molar) in trans units -1,4 of the butadiene part of between 6%> and 80 % o, a content (%> molar) in units -1,2 plus -3,4 of the isoprene part of between 5%> and 70%> and a content (%> molar) in trans units -1,4 of the isoprene portion of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg of between -20 ° C and -70 ° C.
• 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 (R), rubber natural (R), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• diene elastomers highly unsaturated consisting of polybutadienes (BR), synthetic polyisoprenes (R), rubber natural (R), 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 butadiene-styrene (SBIR) and mixtures of such copolymers.
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR isoprene-copolymers 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 (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 45%>, a vinylic content of the butadiene part of between 15%> and 70%>, a content (%> molar) in trans-1,4 bonds of between 15%> and 75%> and a Tg between -10 ° C and -55 ° C;
• a BR preferably having more than 90% (%> molar) 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 (R), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
• R 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 less than an 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 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 chains 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.
• any inorganic or mineral filler regardless of its color and origin (natural or synthetic), also called “white” charge, “clear” charge or “non-black filler” as opposed to carbon black, this inorganic filler being able to reinforce on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of a tread of tires, in other words able to replace, in its reinforcing function, a conventional carbon black 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, especially any precipitated or fumed silica having a BET surface and a CTAB specific surface area both less than 450 m 2 / g, preferably 30 at 400 m / g.
• Highly dispersible precipitated silicas are preferred, in particular when the invention is implemented for the manufacture of tires having low rolling resistance; examples of such silicas are the “Ultrasil 7000" silicas from Degussa, the “Zeosil 1165 MP, 1135 MP and 1115 MP” silicas from Rhodia, and the “Hi-Sil EZ150G” silica from PPG. , the silicas “Zeopol 8715, 8745 or 8755" of the Huber Company.
• 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 A125” or "CR125” (Baikowski company), "APA-100RDX” (Condea), "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 in 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.
• the person skilled in the art will be able to adapt the degree of reinforcing inorganic filler according to the nature of the inorganic filler used and according to the type of tire concerned, for example a tire for a motorcycle, for a passenger vehicle or for a commercial vehicle such as a van or a truck.
• 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 more preferably still less than 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, more precisely according to the French standard F 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, it is preferably lower than that of the reinforcing metal hydroxide.
• carbon black is used in a very small proportion, at a preferential rate less than 10 phr. In the ranges indicated, it benefits from the coloring properties (black pigmentation agent) and anti-UV carbon blacks, without otherwise penalizing the typical performance provided by the reinforcing inorganic filler.
• the composition of the invention may be completely devoid of carbon black.
• the azosilane compound according to the invention, used as coupling agent has the formula:
• - G 1 identical or different, each represent a monovalent hydrocarbon group selected from alkyls, linear or branched, substituted or unsubstituted, having from 1 to 18 carbon atoms, cycloalkyls or aryls, substituted or unsubstituted, having 5 to 18 carbon atoms,
• G 2 which are identical or different, each represent a hydroxyl group or a monovalent group in the form (G 3 ) n -OG 1 in which G 3 is a divalent linking group comprising from 1 to 18 carbon atoms and containing one or more heteroatoms selected from O, S and N, and n is a number greater than or equal to 0 and less than or equal to 18
• Z represents a divalent linking group comprising from 1 to 18 carbon atoms
• - - a is equal to 1, 2 or 3.
• Z may contain one or more heteroatoms chosen from O, S, N and Si.
• a is 3.
• Z is chosen from C 1 -C 18 alkylenes and C 6 -C 12 arylenes, preferably from C 1 -C 10 alkylenes, more preferably Z is chosen from C 1 -C 4 alkylenes, and even more preferably Z is propylene.
• n is greater than or equal to 1.
• G 3 is a C 1 -C 12 alkyleneoxy, more preferably G 3 is a C 1 -C 4 alkyleneoxy, and even more preferably G 3 is an ethyleneoxy or propyleneoxy.
• the following coupling agents of formula (I) are particularly suitable for the invention:
• Z ' identical or different, each represent an oxygen atom, an H or NA 1 radical, where A 1 is a C 1 -C 12 alkyl or aryl group,
• G 4 which may be identical or different, each represents a hydrogen atom, a Cl-Cl 8 alkyl group, a benzyl group (-CH 2 -C 6 H 5 ) or an alkyl group (CH 2 -CH 2 -O) p - G 5 or (CH (CH 3 ) -CH 2 -O) p -G 5 , where p is between 1 to 18 and G 5 , which are identical or different, represent a saturated or unsaturated, branched or unbranched, monovalent hydrocarbon chain, in C1-C32.
• the aminosilanes of general formula B can be produced by trans-esterification of aminosilanes also of formula B in which G 2 is an OH group, a substituted or unsubstituted C1-C18 alkoxyl group, an alkoxyl group or a C5-C18 cycloalkoxyl group. with a HO (CH 2 -CH 2 -O) n -R 3 or HO (CH (CH 3) -CH 2 -O) n-R 3 group, such as in particular described in European Patent EP 1285926.
• the acylation reaction is preferably carried out in the presence of a solvent, in particular a non-alcoholic solvent, under an inert atmosphere atmosphere, at a temperature preferably of between -25 ° C. and 25 ° C.
• a solvent in particular a non-alcoholic solvent
• the composition comprises a second coupling agent used in a blend with the azosilane compound of formula (I).
• sulfurized silane compounds corresponding to formula (II) are particularly suitable:
• x is a decimal number ranging from 2 to 8, preferably from 2 to 5;
• Z 1 and Z 2 identical or different, each represent a divalent hydrocarbon radical having 1 to 18 carbon atoms;
• radicals R1 substituted or unsubstituted, identical or different from each other, represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl group;
• radicals R 1, substituted or unsubstituted, which are identical to or different from each other, represent a hydroxyl, C 1 -C 18 alkoxyl or C 5 -C 18 cycloalkoxyl group.
• Z 1 and Z 2 are chosen from the group consisting of C 1 -C 10 alkylenes, preferably C 1 -C 4 alkylenes, and more preferably Z 1 and Z 2 represent propylene.
• the radicals R 1 are chosen from C 1 -C 4 alkyls, preferably represent methyl.
• the radicals are chosen from the group consisting of hydroxyl and C 1 -C 4 alkoxyls, preferably from the group consisting of hydroxyl, methoxyl and ethoxyl.
• organosilane content of formula (I) according to the particular embodiments of the invention, in particular the amount of reinforcing inorganic filler used, the preferential rate representing between 2% and 20% by weight relative to the amount of reinforcing inorganic filler; levels below 15% are more particularly preferred.
• the overall level of coupling agent is between 2 and 15 phr, preferably between 2 and 12 phr.
• the rubber compositions in accordance with 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 treads, for example plasticizers or oils. of extension, whether the latter are 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 donors and / or or peroxide and / or bismaleimides, vulcanization accelerators, vulcanization activators.
• plasticizers or oils for example plasticizers or oils.
• these compositions comprise, as preferred non-aromatic or very weakly aromatic plasticizing agent, at least one compound selected from the group consisting of naphthenic, paraffinic, MES, TDAE oils, esters (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 hydroxylated or hydrolyzable silanes such as alkylalkoxy silanes (especially alkyltriethoxysilanes), polyols, polyethers (For example polyethylene glycols), esters, primary, secondary or tertiary amines (for example trialkanolamines), hydroxylated or hydrolysable POSs, mixtures of such compounds, for example, ⁇ -dihydroxy-polyorganosiloxanes (especially , ⁇ -dihydroxy-polydimethylsiloxanes
• reinforcing filler that is to say the reinforcing inorganic filler plus carbon black, if appropriate, can also be added, depending on the intended application, inert (ie, non-reinforcing) fillers such as clay particles, bentonite, talc, chalk, kaolin, usable for example in colored tire sidewalls or treads.
• inert ie, non-reinforcing fillers
• clay particles such as clay particles, bentonite, talc, chalk, kaolin, usable for example in colored tire sidewalls or treads.
• the crosslinking system is preferably a vulcanization system, that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• a vulcanization system that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• various known secondary accelerators or vulcanization activators such as zinc oxide. , stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine), or known vulcanization retarders.
• Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
• the primary vulcanization accelerator is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
• accelerator any compound capable of acting as accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of the thiuram type, zinc dithiocarbamates.
• accelerators are for example selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), tetrabenzylthiuram disulfide (“TBZTD”), N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N dicyclohexyl-2-benzothiazyl sulphenamide (“DCBS”), N-tert-butyl-2-benzothiazyl sulphenamide (“TBBS”), N-tert-butyl-2-benzothiazyl sulphenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ ZBEC “), 1-phenyl-2,4-dithiobiuret (“ DTB “), zinc dibuthylphosphorodithioate (“ ZBPD “), zinc 2-ethylhexylphosphorodithioate (“ ZDT / S "), bis-0,0-di disulf
• 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 lower temperature, typically below 120 ° C, for 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 roller mixer; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• Incorporation of the coating agent can be carried out entirely during the non-productive phase (Le., In the internal mixer), at the same time as the inorganic filler, or entirely during the phase productive (with the external mixer), or fractionated over the two successive phases.
• 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” state (Le., Before firing) and in the so-called “cooked” or vulcanized state (i.e., after crosslinking or vulcanization).
• 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.
• 3-aminopropyl (triethoxy-silane) marketed by the company Evonik Degussa GmbH with a purity higher than 98%;
• Pentane and isopropanol marketed by Aldrich, Acros and Merck-
• the azosilane is obtained with a yield greater than 99% e present in the form of a bright red viscous liquid with a purity of azosilane greater than 85 mol% (NMR).
• the azosilane compound of formula (Ib) is synthesized in a manner identical to that of the azosilane of formula (Ic) described in the preceding paragraph with the exception of the trans-esterification of the amount of poly (oxyethylene) of isotridecanol used which is halved compared to the previously described synthesis.
• Ethyl carbazate and anhydrous toluene are charged at room temperature (23 ° C.) into the reactor which is placed under an argon atmosphere.
• the reactor is stirred at 300 rpm and the reaction mixture is then heated to 60 ° C.
• the reaction mixture becomes substantially homogeneous on heating.
• the 99.8 g of silane are then added in 60 min using an isobaric dropping funnel.
• the reaction mixture is stirred for 2 hours at 60 ° C. before returning to ambient temperature.
• the reaction mixture is left standing for a few hours at room temperature.
• a white solid crystallizes. It is then filtered, washed twice with 150 ml of isopropyl ether and then filtered under vacuum.
• the solid is finally dried in an oven at 60 ° C to constant weight equal to 131.5 g.
• the precursor, pyridine and dichloromethane are charged to a reactor which is placed under an argon atmosphere; the reaction medium is substantially colorless homogeneous.
• N-Bromosuccinimide is added in 30 minutes with a spatula. The temperature is kept below 25 ° C. From the first addition of NBS, the reaction medium becomes bright orange. The reaction medium is stirred at room temperature for 2 hours after the end of the addition of NBS. The reaction medium is concentrated under reduced pressure on a rotary evaporator.
• the residue which is in the form of an orange paste, is taken up in 100 ml of a heptane / iPr 2 mixture (1/1: vol / vol) and then filtered on a sintered glass (125 ml) of porosity.
• the filter cake is washed with an additional 4 x 25 ml of the above solvent mixture.
• the mother liquors are filtered a second time on the cake.
• the filtrate is concentrated under reduced pressure.
• This liquid is analyzed by NMR, its molar composition is as follows (mol%): azosilane of formula III: 94.5%;
• the diene elastomer the silica supplemented with a small quantity
• the initial vessel temperature is approximately 90.degree. of carbon black
• Thermomechanical work 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.
• the mixture thus obtained is recovered, cooled and the coating agent (when the latter is present) and the vulcanization system (sulfur and sulfenamide accelerator) are added to an external mixer (homo-finisher) at 50 ° C. mixing everything (productive phase) for about 5 to 6 minutes
• 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, either in the form of profiles that can be used directly, after cutting and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as treads of tires.
• This test is intended to demonstrate the improved properties of a rubber composition according to the invention comprising a novel coupling agent compared to a control composition using a coupling agent traditionally used in tire tread rubber compositions. having silica as a reinforcing filler.
• compositions based on a diene elastomer (natural rubber, R) reinforced with a highly dispersible silica (HDS) are prepared for this purpose, these compositions essentially differing from the following technical characteristics:
• composition C1 is a first control composition containing the compound TESPT (trade name: "Si69") as coupling agent,
• the composition C2 is a composition in accordance with the invention comprising the azosilane compound of formula (Ia) as a coupling agent with a number of moles identical to that of the TESPT of the first control composition (isomolar silicon content), the structure of the TESPT molecules having the same number of binding functions with the filler and with the elastomer as the coupling agent of formula (Ia) according to the invention,
• composition C3 is a second control composition containing the azosilane compound of formula (III), see below, as coupling agent but in which the amount of coupling agent has been adjusted so as to be isomeric relative to the amount of coupling agent of formula (Ia) of the composition C2 according to the invention, in terms of functional group ensuring the binding to the inorganic filler (isomolar silicon level).
• 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 firing (approximately 25 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
• composition C2 according to the invention comprising a coupling agent of formula (Ia), compared with the control composition C1 comprising the coupling agent TESPT, exhibits significantly improved properties concerning the reinforcement of the composition (MA300 / MA100) and also the hysteresis (values of tan (ô) max significantly reduced), while maintaining properties that are almost similar in terms of properties at break (stress and elongation at breaking).
• composition C3 not in accordance with the invention comprising another coupling agent of formula with a rate corresponding to the composition C2 according to the invention, to an identical number of functions ensuring the connection. with the load, has both degraded elongation and degradation properties and degraded reinforcement (in particular the MA300 module is not measurable).
• the object of this test is to demonstrate the improved properties of a rubber composition according to the invention comprising the novel coupling agent in a blend with another coupling agent conventionally used in tire tread rubber compositions having silica as a reinforcing filler, compared to a control composition comprising this coupling agent traditionally used alone as well as to a composition comprising a coupling of two coupling agents traditionally used.
• compositions based on a diene elastomer (natural rubber, R) reinforced with a highly dispersible silica (HDS) are prepared for this purpose, these compositions essentially differing from the following technical characteristics:
• composition C l is identical to the composition C1 of the test 1 with the exception of the level of the coupling agent TESPT,
• composition C4 is a composition in accordance with the invention comprising, as coupling agent, a blend consisting of 50% of TESPT compound relative to the level of TESPT in composition C 1, and of azosilane compound of formula (I-a ) with an isomolar silicon content with respect to these 50% of TESPT,
• the composition C5 is a second control composition comprising, as coupling agent, a cross-section consisting of 50% of TESPT compound relative to the level of TESPT in the composition C 1 and an azosilane compound of formula (III) with a rate of isomolar with respect to the amount of coupling agent of formula (I-a) of the composition C4 according to the invention, in terms of functional group ensuring the binding to the inorganic filler (isomolar silicon level),
• Tables 3 and 4 give the formulation of the various compositions (Table 3 - levels of the various products expressed in phr or parts by weight per hundred parts of elastomer) as well as their properties after curing (approximately 25 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
• composition C4 comprising as a coupling agent a coupling agent coupling of formula (Ia) and of TESPT compound, compared to the control composition C 1 comprising the agent TESPT alone coupling as well as composition C5 comprising a cleavage of azosilane compound of formula (III) and TESPT compound, present:
• Test 3 This test is intended to demonstrate the improved properties of rubber compositions according to the invention comprising a novel coupling agent compared to a control composition using a coupling agent traditionally used in rubber compositions for treads of tires. having silica as a reinforcing filler.
• compositions based on a diene elastomer (natural rubber, R) reinforced with a highly dispersible silica (HDS) are prepared, these compositions essentially differing from the following technical characteristics:
• composition C l is a composition identical to the composition C 1 of the test 2, containing the coupling agent TESPT,
• composition C6 is a composition in accordance with the invention comprising the azosilane compound of formula (I-b) as a coupling agent with a number of moles identical to that of the TESPT of the first control composition (isomolar rate in silicon),
• the composition C7 is a composition in accordance with the invention comprising the azosilane compound of formula (Ic) as coupling agent with a number of moles identical to that of the TESPT of the first control composition (isomolar rate in silicon), Tables 5 and 6 give the formulation of the various compositions (Table 5 - levels of the various products expressed in phr or parts by weight per hundred parts of elastomer) as well as their properties after firing (approximately 25 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
• Table 6 shows that the compositions C6 and C7 in accordance with the invention, comprising as coupling agent respectively a coupling agent of formula (Ib) and a coupling agent of formula (Ic), compared to the reference composition.
• C l comprising the coupling agent TESTP, have very significantly improved properties concerning the reinforcement of the composition (MA300 / MA100) but also concerning the hysteresis (values of tan (ô) max significantly diminished).
• composition according to the invention comprising as coupling agent an azosilane compound of formula (I) alone or in a blend, in particular with another coupling agent traditionally used in tire compositions, makes it possible to obtain improved properties (strengthening, hysteresis) compared to the control compositions.
• silica "ZEOSIL 1165 MP” from Rhodia in the form of microbeads BET and CTAB: about 150-160 m2 / g

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