Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D277/36—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
  • C07F9/6539—Five-membered rings
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
  • C08K5/47—Thiazoles
• • 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

Definitions

• Rubber composition comprising a thiazole derivative
• the present invention relates to a rubber composition that can be used in particular for the manufacture of tires or semi-finished products for tires such as treads, said composition being based on a diene elastomer, a reinforcing filler and a vulcanization system comprising a particular thiazole compound.
• a relatively complex vulcanization system comprising, in addition to sulfur, a primary vulcanization accelerator, such as sulphonamides with a benzothiazole nucleus, as well as various secondary accelerators or vulcanization activators, in particular zinc such as zinc oxide (ZnO) alone or used with fatty acids.
• a primary vulcanization accelerator such as sulphonamides with a benzothiazole nucleus
• various secondary accelerators or vulcanization activators in particular zinc such as zinc oxide (ZnO) alone or used with fatty acids.
• Benzothiazole ring sulfenamides used as primary vulcanization accelerators are, for example, N-cyclohexyl-2-benzothiazyl sulphenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazole sulphenamide (abbreviated “DCBS”), N-tert-butyl-2-benzothiazyl sulfenamide (abbreviated as "TBBS”), mixtures of these compounds.
• CBS N-cyclohexyl-2-benzothiazyl sulphenamide
• DCBS N-dicyclohexyl-2-benzothiazole sulphenamide
• TBBS N-tert-butyl-2-benzothiazyl sulfenamide
• the rubber compositions must have sufficient crosslinking while maintaining an acceptable compromise between the different rheometric properties.
• the Applicant has discovered a novel rubber composition comprising a thiazole compound as a vulcanization accelerator.
• This new rubber composition makes it possible to obtain a vulcanized composition using accelerators alternative to known accelerators, ideally with a compromise of rheometric properties similar to that obtained with rubber compositions containing vulcanization accelerators conventionally used.
• the invention therefore relates to a rubber composition for the manufacture of tires, based on one or more diene elastomers, one or more reinforcing fillers and a vulcanization system, said vulcanization system comprising one or more thiazole compounds chosen from the compounds of formula (I) below:
• R 1 and R 2 independently represent a hydrogen atom or a C 4 hydrocarbon group; -C 25 selected from linear, branched or cyclic alkyl groups, aralkyl groups, alkyl aryl groups and aryl groups, and optionally interrupted by one or more heteroatoms, Ri and R 2 may together form a non-aromatic ring, but not can not together form an aromatic ring,
• -A is selected from
• R 3 , R 4 and Rs independently represent a C 1 -C 8 hydrocarbon group, optionally interrupted by one or more heteroatoms,
• y is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and most preferably less than or equal to 6; a group
• R 6 is a C1-C18 hydrocarbon group optionally interrupted by one or more heteroatoms; a group in which
• R 7 is a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms; a group
• Y is a hydrocarbon chain C ⁇ -C ⁇ optionally interrupted or substituted by one or more heteroatoms
• Rg is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;
• X is a C1-C12 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms,
• R and Rio independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms, and
• Ru is a hydrogen atom or a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms.
• the invention also relates to a method for preparing a rubber composition for the manufacture of tires as defined above, comprising the following steps:
• the invention relates to the process as defined above, in which between the thermomechanical mixing and the incorporation of the crosslinking system, the whole is cooled to a temperature of less than or equal to 100 ° C.
• the last step is performed on a second mixer.
• the subject of the invention is also the use of a composition according to the invention for the manufacture of a finished article or of a semi-finished product intended for a motor vehicle ground connection system, such as a tire, internal safety support for tire, wheel, rubber spring, elastomeric joint, other suspension and anti-vibration element.
• the composition according to the invention can be used for the manufacture of semi-finished rubber products intended for tires, such as treads, crown reinforcing plies, sidewalls, reinforcing plies. carcases, beads, protectors, underlayments, rubber blocks and other internal rubbers, in particular decoupling erasers, intended to provide the connection or the interface between the aforementioned zones of the tires.
• the invention further relates to a finished article or semifinished product for a ground connection system of a motor vehicle, in particular tires and semi-finished products for tires, in particular treads, comprising a composition according to the invention.
• the tires according to the invention are in particular for passenger cars, two-wheelers, as well as for industrial vehicles chosen from vans, "heavy goods vehicles” - ie metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles - agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
• the invention further relates to the use as a vulcanization accelerator in a composition . base of one or more diene elastomers, one or more reinforcing fillers and a vulcanization system, of one or more thiazo compounds of formula (I).
• the invention finally relates to a thiazole of formula (F) below:
• Ru and R 2a independently represent a hydrogen atom or a C 1 -C 25 hydrocarbon group selected from linear, branched or cyclic alkyl groups, aralkyl groups, alkyl aryl groups and aryl groups, and optionally interrupted by one or more heteroatoms, R a and R 2a may together form a non-aromatic ring, but can not together form an aromatic ring;
• R a , R 4 a and 3 ⁇ 4 a independently represent a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms,
• y a is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and most preferably less than or equal to 6,
• R and R 2a do not simultaneously denote a methyl or a hydrogen atom; aryl and hydrogen;
• R 6a is a C 1 -C 18 hydrocarbon-based group, optionally interrupted by one or more heteroatoms, chosen from linear, branched, cyclic and aralkyl alkyl groups, optionally substituted with one or more halogens, one or more linear or ri linear or branched alkoxy, hydroxy, nitro,
• R and R2a independently denote a hydrogen atom or an alkyl group; a group
• R 7a is a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms, and with the proviso that R a and R 2a represent methyl respectively; a group
• X a is a C 1 to C 18 hydrocarbon-based chain, optionally interrupted or substituted with one or more heteroatoms, but which can not carry another phosphonate group,
• Ro a and Rj oa independently represent a C1-C16 hydrocarbon group, optionally interrupted by one or more heteroatoms,
• R and R 2a independently represent a hydrogen atom or an alkyl group, a group in which
• R u represents a hydrogen atom or a hydrocarbon group of C ⁇ -C ⁇ %
• R and R 2a are independently an alkyl group having 8 iC i.
• the compounds synthesized as vulcanization accelerators have been characterized by mass spectrometry and NMR with the apparatus and methods indicated below.
• Reactant gas methane / ammonia (85/15) at 2ml / min
• Source temperature 200 ° C
• the structural analysis as well as the determination of the molar purities of the synthesis molecules are carried out by NMR analysis.
• the spectra are acquired on a BRU ER 500 MHz Avance spectrometer equipped with a BBIz-grad 5 mm wideband probe.
• the quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 3 second repetition time between each of the 64 acquisitions.
• the 1 H NMR spectrum coupled to 2D experiments HSQC 1 H / 1 3C and HMBC 1 H / 13C allow the structural determination of the molecules (see allocation tables). Molar quanti fications are made from the quantitative 1 H NMR spectrum.
• 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, ACouple (in dN.m), as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.
• Measurements are processed according to DIN 53529 - Part 2 (March 1983) (with the exception of the conversion rate constant): To is the induction delay, ie the time required at the beginning the vulcanization reaction; T a (for example T99) is the time required to reach a conversion of a%, that is to say a% (for example 99%) of the difference between the minimum and maximum torques.
• composition according to the invention is based on one or more diene elastomers, one or more reinforcing fillers and a vulcanization system.
• composition based on is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with one another, at least partly, during the various phases of manufacture of the composition, in particular during its vulcanization.
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (that is, bounds a and b excluded), while any range of values designated by the expression “from a to b” means the values ranging from a to b (that is to say including the strict limits a and b).
• elastomer or “diene” rubber should be understood in known manner an elastomer derived at least in part (i.e., a homopolymer or a copolymer) of monomers dienes (monomers carrying two carbon-carbon double bonds, conjugated or not ).
• diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
• the term “essentially unsaturated” is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%);
• diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may be especially described as "substantially 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:
• 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.
• conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 ) alkyl-1,3-butadienes, such as, for example, 2,3-Dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• 2,3-Dimethyl-1,3-butadiene 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
• the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
• the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
• the elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion, in emulsion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
• Examples of coupling with carbon black are functional groups comprising a C-Sn bond or amino functional groups such as aminobenzophenone for example; for coupling to 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, US Pat. No.
• alkoxysilane groups as described for example in FR 2,765,882 or US 5,977,238), carboxyl groups (as described for example in WO 01/92402 or US 6 8 15 473, WO 2004 / 096865 or US 2006/0089445) or else polyether groups (as described for example in EP 1 1 27 909, US 6,503,973 WO 2009/000750 or WO 2009/000752).
• functional elastomers include elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
• Suitable are polybutadienes and in particular those having a content (mol%) in units - 1, 2 of between 4% and 80% or those having a content (mol%) of cis -1, 4 of greater than 80%, polyisoprenes. , butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature, measured according to ASTM D3418) between 0 ° C. and -70 ° C. and more particularly between -10 ° C.
• a 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 of between 4% and 75%, a content of (mol%) in trans-1,4 ranges between 10% and 80%, butadiene-isoprene copolymers and in particular those having a soprene content of between 5% and 90% by weight and a Tg of - 40 ° C to -80 ° C, isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a Tg between 5 ° C and - 50 ° C.
• Butadiene-styrene-isoprene copolymers are suitable in particular 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% 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 (mol%) in -1,2 units of the butadiene part.
• the diene elastomer (s) of the composition according to the invention are preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR) and natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• BR polybutadienes
• IR synthetic polyisoprenes
• NR natural rubber
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (B IR), isoprene-styrene copolymers (SIR) and copolymers of isoprene-butadiene-styrene (SBIR).
• SBR butadiene-styrene copolymers
• B IR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR copolymers of isoprene-butadiene-styrene
• the diene elastomer is natural rubber.
• the diene elastomer is predominantly (Le., 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, is used, for example from 35 to 45%, a vinyl content of the butadiene part of between 15% and 70%, a content (mol%) of trans-1,4 bonds of between 15% and 75% and a Tg of 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 copolymers of isoprene and mixtures of these elastomers.
• NR natural rubber
• IR synthetic polyisoprenes
• isoprene copolymers mention will be made in particular of isobutene-isoprene (butyl rubber-IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene copolymers.
• SBIR styrene
• This isoprene elastomer is preferably natural rubber or a 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 can contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (optionally chlorinated or brominated), whether these copolymers are used alone or in a mixture with diene elastomers which are highly unsaturated as mentioned above, in particular NR or IR, BR or SBR.
• the rubber composition comprises a blend of one or more diene elastomers known as "high Tg” having a Tg of between -70 ° C. and 0 ° C. and of a (one or more) diene elastomer called “low Tg” between -1 10 ° C and -80 ° C, more preferably between - 105 ° C and -90 ° C.
• high Tg diene elastomers
• low Tg between -1 10 ° 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 content (mol%) of cis-1,4 preferably greater than 95%), BIR, SIR, SB IR, 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 content (mol%) of cis chains - 1, 4 greater than 90%, with one or more S-SBR or E-SBR (as elastomer (s) high Tg).
• composition according to 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. II-2. Reinforcing charge
• any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tires for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a cutting of these two types of filler, including a cut of carbon black and silica.
• Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
• the reinforcing carbon blacks of the 100, 200 or 300 series for example blacks NI15, N134, N234, N326, N330, N339, N347, N375, or else, according to the targeted applications, the blacks of higher series (for example N660, N683, N772).
• the carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).
• organic fillers other than carbon blacks
• any inorganic or mineral filler e (whatever its color and origin (natural or synthetic), also called “white” filler, “clear” filler “even” non-black filler “(” non-black filler ”) versus carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
• -OH hydroxyl groups
• 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 below.
• Suitable reinforcing inorganic fillers are mineral fillers of the siliceous type, in particular silica (SiO 2 ), or aluminous type, in particular alumina (Al 2 O 3).
• the silica 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 both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• the silicas Ultrasil 7000 and Ultrasil 7005 from the company Degussa
• the silicas Zeosil 1 1 65MP, 1 1 35MP and 1 1 1 5MP from the company Rhodia
• Hi-Sil silica EZ150G from PPG
• silicas Zeopol 8715, 8745 and 8755 from Huber
• silicas with a high specific surface area as described in application WO 03/16837.
• the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 45 and 400. m / g, more preferably between 60 and 300 m 2 / g.
• the total reinforcing filler content (carbon black and / or reinforcing inorganic filler such as silica) is between 20 and 200 phr, more preferably between 30 and 150 phr, the optimum being in a known manner different according to particular applications targeted: the level of reinforcement expected on a bicycle tire, for example, is of course less than that required on a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for commercial vehicles such as Heavy Duty.
• a reinforcing filler comprising between 30 and 150 phr is used, more preferably between 50 and 120 phr of inorganic filler, particularly of silica, and optionally carbon black; the carbon black, when present, is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 10 phr).
• the reinforcing filler is carbon black.
• a bifunctional coupling agent (or bonding agent) is used in known manner to provide a sufficient chemical and / or physical connection between the inorganic filler. (surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
• Polysulphurized silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are especially used, as described for example in the applications WO03 / 002648 (or US 2005/01 6651) and WO03 / 002649 (or US 2005/01 6650). ).
• polysulphide silanes known as "symmetrical" silanes having the following general formula (III) are suitable in the following non-limiting definition:
• p is an integer of 2 to 8 (preferably 2 to 5);
• D is a divalent hydrocarbon radical (preferably C 1 -C 18 alkyl groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 alkylenes, especially C 1 -C 4 alkylenes, in particular propylene);
• radicals substituted or unsubstituted, identical or different, represent alkyl, Cj-Cig, cycloalkyl C 5 -C 18 aryl or C 6 -C 8 (preferably alkyl groups CJ -C O, cyclohexyl or phenyl, especially alkyl groups, C1-C4 alkyl, more particularly methyl and / or ethyl).
• R22 radicals substituted or unsubstituted, identical or different, represent an alkoxyl group Ci-Cjg or cycloalkoxy C5-C18 (preferably a group selected from alkoxyls Cs and cycloalkoxyls Cs-C 8, more preferably still a group selected from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
• polysulphide silanes examples include polysulfides (in particular disulfides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4 ) silyl-C 1 -C alkyl ), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl).
• bis (3-triethoxysilylpropyl) tetrasulfurc in abbreviated form, is especially used.
• TESPT of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S 2 ] 2 or bis (triethoxysilylpropyl) disulfide, abbreviated to TESPD, of formula [(C 2 H 5 O) 3 Si ( CH) 3 S] 2.
• Preferred polysulfides especially disulfides, trisulphides or tetrasulfides
• bis- (monoalkyl (C 1 -C 4 ) -dialkyl (C 1 -C 4 ) silylpropyl) are also preferred. particularly bis-monoethoxydimethylsilylpropyl tetrasulfide as described in patent application WO 02/083782 (or US 2004/1 32880).
• WO 02/30939 or US Pat. No. 6,774,255
• WO 02/31041 or US 2004/05 1,210
• silanes or POS bearing functional azodicarbonyl groups as described, for example, in the applications of US Pat.
• WO 2006/1 25532, WO 2006/1 25533, WO 2006/25534 silanes or POS bearing functional azodicarbonyl groups
• the content of coupling agent is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.
• the vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• sulfur or a sulfur-donor agent
• a primary vulcanization accelerator To this basic vulcanization system are added, incorporated during the first non-productive phase and / or during the production phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine).
• Sulfur is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr, in particular between 0.5 and 3 phr, when the composition of the invention is intended, according to a method. of the invention, to constitute a tread of a tire.
• the primary vulcanization accelerator must allow crosslinking of the rubber compositions in commercially acceptable times, while maintaining a minimum safety period ("toasting time") during which the compositions can be shaped without the risk of premature vulcanization. (“Roasting").
• the vulcanization system comprises, as a primary vulcanization accelerator, one or more thiolefin compounds chosen from the compounds of formula (I) below:
• R 2 independently represent a hydrogen atom or a C 1 -C 2 hydrocarbon group selected from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by one or more heteroatoms, Ri and R 2 may together form a non-aromatic ring, but can not together form an aromatic ring, -A is selected from
• R 3 , R 5 and R 5 independently represent a C 1 -C 8 hydrocarbon-based group, optionally interrupted by one or more heteroatoms,
• y is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and most preferably less than or equal to 6; a group
• R 6 is a C 1 -C 18 hydrocarbon group optionally interrupted by one or more heteroatoms
• R 7 is a C 1 -C 12 hydrocarbon group ; 8 , optionally interrupted by one or more heteroatoms; a group
• Y is a hydrocarbon chain C iC 18, optionally interrupted or substituted by one or more heteroatoms
• R 8 is a hydrocarbon group-Ci 8, optionally interrupted by one or more heteroatoms; a group
• X is a C 1 -C 18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms;
• R9 and R10 independently represent a C1-C15 hydrocarbon group, optionally interrupted by one or more heteroatoms, and a group
• Ru is a hydrogen atom or a hydrocarbon group in
• cyclic alkyl group is meant an alkyl group consisting of one or more rings.
• hydrocarbon group or chain (e) interrupted (c) by one or more heteroatoms means a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of said group or of said chain, or between an atom carbon of said group or said chain and another heteroatom of said group or said chain or between two other hetero atoms of said group or said chain.
• the heteroatom (s) may be a nitrogen, sulfur or oxygen atom.
• R 1 and R 2 independently represent a hydrogen atom or a methyl group.
• R 1 and R 2 each represent a hydrogen atom.
• R 1 and R 2 each represent a methyl group.
• the compound (s) of formula (I) are advantageously chosen from compounds whose group A is chosen from
• R 3 to R JJ groups may be independently selected from linear, branched or cyclic, aryl groups, aralkyl groups and alkylaryl groups.
• the X and Y groups may be independently selected from linear, branched or cyclic alkylene groups, arylenes and alkyl arylenes.
• R 3 , R and R 5 represent a methyl group.
• R 6 represents a C 1 -C 4 alkyl, more preferably a C 1 -C 3 alkyl and very preferably a methyl group or an ethyl group.
• R 7 represents a C 1 -C 4 alkyl, more preferentially a C 1 -C 3 alkyl and very preferably a methyl group or an ethyl group, or R 7 represents an aralkyl group. as for example a benzyl group.
• Y represents a C 1 -C 4 alkylene, more preferably a C 1 -C 3 alkylene and very preferably a propylene group or an ethylene group and R 8 represents a C 1 -C 4 alkyl, more preferentially a C 1 -C 3 alkyl and very preferably a methyl group or an ethyl group.
• X represents a C 1 -C 4 alkylene, more preferably a C 1 -C 3 alkylene and very preferably a methylene group or an ethylene group
• R 9 and R 10 independently represent a lower alkyl group.
• C 1 -C 4 more preferably a C 1 -C 3 alkyl and very preferably a methyl group or an ethyl group.
• Ru represents a hydrogen atom.
• the compound (s) of formula (I) generally represent from 0.1 to 7 phr, preferably from 0.2 to 7 phr, more preferably from 0.5 to 7 phr, more preferably from 0.5 to 5 phr.
• the vulcanization system of the composition according to the invention may also comprise one or more additional primary accelerators, in particular compounds of the thiuram family, zinc dithiocarbamate derivatives, sulphenamides, guanidines or thiophosphates.
• additional primary accelerators in particular compounds of the thiuram family, zinc dithiocarbamate derivatives, sulphenamides, guanidines or thiophosphates.
• the rubber composition according to the invention may also comprise all or part of the usual additives conventionally used in elastomer compositions intended for the manufacture of tires, in particular treads, such as, for example, plasticizers or lubricating oils. extension, whether aromatic or non-aromatic, pigments, protective agents such as anti-ozone waxes (such as C32 ST Ozone wax), chemical antiozonants, anti-oxidants (such as 6-paraphenylenediamine), anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M) as described for example in application WO 02/1 0269.
• protective agents such as anti-ozone waxes (such as C32 ST Ozone wax), chemical antiozonants, anti-oxidants (such as 6-paraphenylenediamine), anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3
• the composition according to the invention comprises, as preferred non-aromatic or very weakly aromatic plasticizer, at least one compound selected from the group consisting of naphthenic, paraffinic, MES, TDAE oils, esters (in particular trioleates) of glycerol, the hydrocarbon plasticizing resins having a high Tg preferably greater than 30 ° C, and mixtures of such compounds.
• composition according to the invention may also contain, in addition to the coupling agents, activators for coupling the reinforcing inorganic filler or, more generally, medium-useful assisting agents, in a known manner, by means of an improvement of the dispersion of the inorganic filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement 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 hydrolysable POSs, for example ⁇ , ⁇ -dihydroxy-polyorganosiloxanes (especially ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes), fatty acids such as, for example, stearic acid. II-5. Fabricat
• the rubber composition according to the invention is manufactured in suitable mixers, generally using two successive preparation phases according to a general procedure well known to those skilled in the art: a first working phase or thermomechanical mixing (sometimes referred to as "non-productive" phase) at a high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 115 ° C. and 150 ° C. and more preferably still between 1 ° and 15 ° C. C. and 140 ° C., followed by a second phase of mechanical work (sometimes referred to as a "productive" phase) at a lower temperature, typically below 110 ° C., for example between 40 ° C.
• a first working phase or thermomechanical mixing (sometimes referred to as "non-productive" phase) at a high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 115 ° C. and 150 ° C. and more preferably still between 1 ° and 15 ° C. C. and 140
• all the basic constituents of the composition of the invention with the exception of the vulcanization system, namely the reinforcing filler or fillers, the coupling agent, where appropriate, are intimately incorporated, by kneading, with the diene elastomer or the diene elastomers during the so-called non-productive first phase, that is to say that it is introduced into the mixer and kneaded.
• the two phases can be carried out consecutively on the same mixer or be separated by a cooling step at a temperature below 100 ° C., the last step then being carried out on a second mixer.
• the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible setting agents, are introduced into a suitable mixer such as a conventional internal mixer.
• a suitable mixer such as a conventional internal mixer.
• the total mixing time, in this non-productive phase is preferably between 1 and 15 min.
• 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.
• 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 strip of tire rolling for passenger vehicle.
• II-6. Special thiazole compounds
• the subject of the invention is also a thiazole compound of formula ( ⁇ ):
• R i a and R 2a independently represent a hydrogen atom or a C 1 -C 25 hydrocarbon group selected from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by a or more heteroatoms, R la and R 2a may together form a non-aromatic ring, but can not together form an aromatic ring,
• R 3a , R 4a and R J a independently represent a C 1 -C 8 hydrocarbon group, optionally interrupted by one or more heteroatoms,
• y a is an integer greater than or equal to 1, preferably less than or equal to 1 0, more preferably less than or equal to 8 and most preferably less than or equal to 6, with the proviso that the R and R 2a do not simultaneously denote a methyl or a hydrogen atom; aryl and hydrogen; a group
• R 6a is a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms, chosen from linear, branched, cyclic, aralkyl, alkyl groups optionally substituted by one or more halogens, one or more linear or branched alkyl groups; linear or branched alkoxy, hydroxy, nitro,
• R a and R 2a independently denote a hydrogen atom or an alkyl group; a group
• R 7a is a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms,
• R a and R 2a represent methyl respectively; a group
• X a is a C1-C1 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms, but which can not carry another phosphonate group,
• R.9 and has RIOA independently represent a hydrocarbon group-Cig, optionally interrupted by one or more heteroatoms, and
• R a and R 2a independently represent a hydrogen atom or an alkyl group; and a group
• Riia is a hydrogen atom or a hydrocarbon group-Cig, provided that R a and R 2a independently represent an alkyl group Ci-Cjg.
• cyclic alkyl group is meant an alkyl group consisting of one or more rings.
• group or hydrocarbon chain (e) interrupted by one or more heteroatoms is meant a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of said group or said chain, or between an atom carbon of said group or said chain and another heteroatom of said group or said chain or between two other hetero atoms of said group or said chain.
• the heteroatom (s) may be a nitrogen, sulfur or oxygen atom.
• the R and R 2a independently represent a hydrogen atom or a group rnéthyle.
• R] a and R 2a each represents a hydrogen atom.
• the R and R 2a each represents a rnéthyle group.
• the thiazole compound of formula ( ⁇ ) is such that Aa is chosen from
• R 3a to R a being as defined above.
• the groups R 3a to R 7 a and R a to R lla may be independently selected from linear, branched or cyclic, aryl groups, aralkyl groups and alkaryl groups, subject to any conditions explained above for each of these groupings.
• the group X may be independently selected from linear alkylene, branched or cyclic arylene groups and alkylarylene groups.
• R 3 a , R 4 a and R 5 a represent a methyl group.
• R 7a represents a C 1 -C 4 alkyl, more preferably a C 1 -C 3 alkyl and very preferably a methyl group or an ethyl group, or R 7a represents an aralkyl group such as as for example a benzyl group.
• X is an alkylene C 1 - C4 alkyl, more preferably a C 1 -C 3 alkylene and very preferably a methylene group or an ethylene group and R a and Rio are independently alkyl C 1 -C 4, more preferably a C 1 -C 3 alkyl and very preferably a methyl group or an ethyl group.
• thiazole compounds of general formula (I) when the group A represents a hydrogen atom, in which case the thiazoles are substituted by a thiol.
• This thiol can be salified by techniques known to those skilled in the art to obtain the thiolate compounds.
• the compound can be prepared by an oxidative coupling.
• an organic or inorganic oxidizing agent for example diisopropylazodicarboxylate or ammonium persulfate, or alternatively iodine or a solution of sodium hypochlorite.
• organic or inorganic oxidizing agent for example diisopropylazodicarboxylate or ammonium persulfate, or alternatively iodine or a solution of sodium hypochlorite.
• Birch describes the oxidative coupling of methyl mercaptan with tertbutyl mercaptan in the presence of potassium hexacy noferrate III (Birch et al., Journal of the Institute of Petroleum, 1953, vol 39, p.206-210).
• this compound may be prepared according to a thioesterification reaction between the thiol or its corresponding thiolate with a carboxylic acid or its derivatives (acid chloride, anhydride) bearing the radical R 6 or R (, B.
• this compound may be prepared by elimination addition reaction between the thiol and an alkyl chloroformate carrying the radical R 7 or R 7a which may itself be commercially available or prepared by reaction between a alcohol and phosgene or a derivative thereof.
• An organic or inorganic base can be added to trap the hydrochloric acid formed.
• Another synthetic route is to react the thiol or its thiolate with phosgene (Chen, H.W. et al., Journal of the American Chemical Society 1978, vol. 1 00, p. 2370-2375) or a derivative thereof such as triphosgene (WO2008 / 0381 75) optionally in the presence of an inorganic or organic base such as a tertiary amine for example to form the chlorothioformate intermediate.
• This intermediate can then react with an alcohol in the presence of an organic base such as a tertiary amine to form the thiocarbonate compound.
• This approach is for example described in Organic Syntheses, Coll. Flight. 5, p. 166 (1973); Flight. 44, p.20 (1964).
• radical A represents a group
• this compound may be prepared by nucleophilic substitution between the thiol or its thiolate and an ester substituted with a halogenated group and bearing the radicals Y and R g such as, for example, bromoethylacetate or 4-bromomethylbutyrate.
• this compound can be prepared by nucleophilic substitution between the thiol or thiolate and a halogenated derivative of a phosphonate or phosphonic acid bearing the radicals X, R 9 and io or X a, R a and R oa and more particularly with a bromo or chloro alkyl phosphonate.
• This reaction is described, for example, for the reaction between diethyl- (2-bromoethyl) phosphonate and sodium rethanethiolate in an ether (Mikolajczyk, Mari, Costisella, Burkhard, Grzej szczak, Slawomir, Tetrahedron, 1983, vol 39 # 7, pp. 89-1,193).
• this compound may be prepared by nucleophilic substitution between the thiol or its thiolate and an allyl halide carrying the radical Rn or R u, and for example between the thiol and allyl bromide.
• ABCR ABCR
• the precipitate formed of the residual salts is filtered and washed on the filter with 5 ml of acetone.
• the filtrate is concentrated under reduced pressure (5-6 mbar, 23 ° C.) to obtain a constant mass.
• reaction crude is dissolved in petroleum ether (500 mL) and this solution is washed with a solution of triethylamine (3.0 g, 0.030 mol) in water (150 mL).
• the biphasic mixture is stirred vigorously for 2 hours at room temperature.
• the organic phase is separated and washed with water (3 x 50 mL).
• the separated and combined organic phases are concentrated under reduced pressure (32 ° C., 3-4 mbar).
• the precipitate is filtered on the filter with 10 ml of acetone.
• the filtrate was concentrated under reduced pressure (9- 1 0 mbar, 24 ° C) until obtaining a constant weight.
• the molar purity is greater than 99% ( 1 H NMR).
• the aqueous phase is washed with heptane (4 times on 25 ml).
• the combined organic phases are washed with water (twice with 50 ml), dried over sodium sulphate, filtered and concentrated under reduced pressure (Tbain 35 ° C., 7 mbar).
• the molecular purity is greater than 99% (1H NMR).
• composition C 1 The purpose of this example is to compare the properties of a rubber composition comprising carbon black and silica, usable for the manufacture of a tire tread, including the MBTS as the primary accelerator of vulcanization (composition C 1), with the properties of a rubber composition according to the invention comprising compound F (composition C2), compound B (composition C3) or compound E (composition C4) as primary accelerator vulcanization.
• compositions according to the invention show that the compounds F, B and E can be used as a vulcanization accelerator in rubber compositions comprising one or more reinforcing fillers.
• composition C l a rubber composition comprising carbon black, usable for the manufacture of a tire tread, including the MBTS as a primary vulcanization accelerator
• composition C1 a rubber composition comprising compound F (composition C2), compound B (composition C3) or compound E (composition C4) as a primary vulcanization accelerator.
• compositions according to the invention show that compounds F, B and E can be used as a vulcanization accelerator in rubber compositions comprising one or more reinforcing fillers.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Thiazole And Isothizaole Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=45976938

Family Applications (1)

Country Status (8)

Families Citing this family (5)

Family Cites Families (40)

• 2011
  • 2011-04-14 FR FR1101169A patent/FR2974096A1/fr not_active Withdrawn
• 2012
  • 2012-04-16 RU RU2013150518/05A patent/RU2013150518A/ru not_active Application Discontinuation
  • 2012-04-16 CN CN201280029114.8A patent/CN103917584B/zh active Active
  • 2012-04-16 WO PCT/EP2012/056912 patent/WO2012140258A2/fr not_active Ceased
  • 2012-04-16 US US14/111,613 patent/US9688852B2/en not_active Expired - Fee Related
  • 2012-04-16 EP EP12715381.5A patent/EP2697301A2/fr not_active Withdrawn
  • 2012-04-16 JP JP2014504357A patent/JP5997759B2/ja not_active Expired - Fee Related
  • 2012-04-16 BR BR112013026506A patent/BR112013026506A2/pt not_active IP Right Cessation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events