• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a modified diene elastomer comprising (i) 40 to 80% by weight, relative to the total weight of said modified diene elastomer, of the species functionalized at the end of the chain by an alkylalkoxysilane group, optionally partially or completely hydrolysed to silanol. carrying a primary, secondary or tertiary amine function, and bonded to the elastomer via the silicon atom, (ii) 5 to 45% by weight, based on the total weight of said modified diene elastomer, of the species functionalized in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and whose silicon atom binds the two pieces of the chain, ( iii) 3 to 30% by weight, based on the total weight of said modified diene elastomer, of the three branched star-like species containing a silane functional group, carrying a primary, secondary or tertiary amine function, whose silicon atom links the three branches of the chain. The invention also relates to a process for preparing such a diene elastomer, a composition comprising it, as well as a semi-finished article and a tire comprising this composition.
    公开号:FR3014872A1
    申请号:FR1362870
    申请日:2013-12-18
    公开日:2015-06-19
    发明作者:Charlotte Dire；Jean-Marc Marechal；Margarita Dorato
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The invention relates to a diene elastomer modified with functionalizing agents of di- and trialkoxy silane type bearing amine functional groups. The invention also relates to a process for preparing such a diene elastomer, a composition comprising it, as well as a semi-finished article and a tire comprising this composition.
    [0002] Since fuel savings and the need to preserve the environment have become a priority, it is desirable to produce mixtures with as little hysteresis as possible. This reduction in hysteresis is a permanent objective which must, however, be carried out while maintaining the processability, in particular raw, of the mixtures so that they can be used as rubber compositions for the manufacture of various finished products used in the composition of tire casings, such as, for example, underlays, sidewalls, treads, and to obtain tires having a reduced rolling resistance. To achieve the goal of lower hysteresis, many solutions have already been tested. In particular, mention may be made of the modification of the structure of the diene polymers and copolymers at the end of polymerization by means of functionalization agents or the use of functional initiators, the aim being to obtain a good interaction between the polymer thus modified and the load, be it carbon black or a reinforcing inorganic filler. As an illustration of this prior art, there may be mentioned the use of diene elastomers functionalized with alkoxysilane compounds carrying an amine function. One can quote the patent FR2867477A1 which claims the functionalization at the end of chain with compounds of type (dialkylaminoalkyl) trialkoxysilane and a rubber composition based on silica or carbon black. Mention may also be made of the patents US Pat. No. 8,716,889 and US Pat. No. 8,106,130B2 which respectively claim, for one, the functionalization at the end of the chain with a trialkoxysilane compound bearing a nitrogen-containing group, the nitrogen atom being included in a substituted or unsubstituted aromatic heterocycle, and for the other, with an alkoxysilane carrying an amine function having at least one alkoxysilyl group and at least two tertiary amine groups.
    [0003] In US Pat. No. 7,807,747 B2 it is proposed to improve the processability (mixing aspect after passing over roll tools) of the raw mixtures containing elastomers functionalized with compounds of the aminoalkoxysilane type and synthesized according to a batch process. The strategy consists in adding the aminoalkoxysilane compound, preferably of the (aminoalkyl) trialkoxysilane type, in two stages during the functionalization step: i) the addition in an amount such that the n ((aminoalkyl) trialkoxysilane) / n molar ratio (alkali metal initiator) is between 0.05 and 0.35, ii) and then 2 "in an amount such that the final molar ratio n ((aminoalkyl) trialkoxysilane) / n (alkali metal initiator) is greater than or equal to 0.5 This process makes it possible to obtain a functional diene elastomer mixture comprising 40 to 80% by weight of elastomer functionalized at the end of the chain, 5 to 45% by weight of elastomer functionalized in medium chain and 3 to 30% by weight of star-shaped elastomer (3-star stars) .These functionalized elastomers have been described in the prior art as being effective for reducing hysteresis, however, it turns out that the Mooney viscosity of such elastomers n is not always storage stable, which can lead to problems of industrial robustness. Various strategies have been tried to stabilize the Mooney viscosity in the storage of elastomers carrying alkoxysilane functional groups. By way of illustration, mention may be made of the patent EP0299074B1 claiming the use of particular alkoxysilanes (Si (OR) 'with R = non-hydrolyzable group containing 4 to 20 carbons). Patent EP0801078B1 may also be mentioned, claiming the addition of a carboxylic acid to the elastomer solution, with a molar ratio n (carboxylic acid) / n (anionic polymerization initiator) of between 0.8 and 1.2, before the stripping step in order to neutralize the basicity provided by the anionic polymerization initiator and to minimize the hydrolysis of the alkoxysilane groups. In the patent EP1198506B1, it is proposed to add a compound of the alkylalkoxysilane type (RinSi (OR2) 4_.) In the elastomer solution, before the stripping step, with a molar ratio n (R1'Si (OR2) 4)) / n (Polymer-SiOR ') raised (20/1) in order to promote the reaction between the alkylalkoxysilane and the polymer which is in its hydrolysed form, Polymer-SiOH, by stripping. Finally, mention may be made of the patent EP1237934B1, which claims the addition of a long-chain alcohol in the elastomer solution, before the stripping step, in order to minimize the hydrolysis reactions to the stripping and consequently the formation of Si-O-Si bonds. In view of the state of the art, there is a need to provide a functionalized elastomer for obtaining rubber compositions having a hysteresis / processability compromise of the improved rubber composition, while improving the storage stability of the improved rubber composition. the Mooney viscosity of the functionalized elastomer used in its composition. The object of the present invention is therefore to provide such a composition. One objective is in particular to propose a functionalized elastomer satisfactorily interacting with the reinforcing filler of a rubber composition containing it in order to reduce the hysteresis, while improving the processability and the storage stability of the Mooney viscosity of the elastomer.
    [0004] This object is achieved in that the applicants have surprisingly discovered in the course of their research that a modified diene elastomer comprising (i) 40 to 80% by weight, based on the total weight of said modified diene elastomer, of end-functionalized species with an alkylalkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and bonded to the elastomer via the silicon atom, (ii ) 5 to 45% by weight, relative to the total weight of said modified diene elastomer, of the species functionalized in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary amine functional group or tertiary, and whose silicon atom binds the two pieces of the chain, (iii) 3 to 30% by weight, relative to the total weight of said diene elastomer m of the three-branched star-shaped species containing a silane functional group, carrying a primary, secondary or tertiary amine function, and whose silicon atom links the three branches of the chain, makes it possible to reduce the hysteresis, while improving the processability and storage stability of Mooney viscosity. The subject of the invention is therefore a modified diene elastomer comprising (i) 40 to 80% by weight, relative to the total weight of said modified diene elastomer, of the species functionalized at the end of the chain by an alkylalkoxysilane group, optionally partially or totally hydrolyzed to silanol, bearing a primary, secondary or tertiary amine function, and bonded to the elastomer via the silicon atom, (ii) 5 to 45% by weight, relative to the total weight of said elastomer modified diene, of the species functionalized in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and whose silicon atom binds the two pieces of the chain, (iii) 3 to 30% by weight, based on the total weight of said modified diene elastomer, of the three branched star-shaped species containing a silane functional group, it has a primary, secondary or tertiary amine function, and the silicon atom links the three branches of the chain. The invention also relates to a process for synthesizing said modified diene elastomer.
    [0005] Another object of the invention is a reinforced rubber composition based at least on a reinforcing filler and an elastomeric matrix comprising at least said modified diene elastomer. In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. On the other hand, 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 (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b). It should be noted that it is known to those skilled in the art that when an elastomer is modified by reaction of a functionalizing agent with the living elastomer resulting from an anionic polymerization step, a mixture of modified species of this elastomer whose composition depends in particular on the proportion of reactive sites of the functionalizing agent relative to the number of living chains. This mixture may comprise chain-end functionalized, coupled, starred and / or non-functionalized species. When the elastomeric species has an alkylalkoxysilane functional group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, at one end of the chain, it will be said that the species is end or end functionalized. of chain. The silicon atom of this group is directly bonded to the chain of the diene elastomer and is substituted only by a single alkoxy group, in addition to the alkyl radical and the group comprising the amine function.
    [0006] When the elastomeric species has an alkoxysilane functional group, optionally partially or completely silanol hydrolyzed, carrying a primary, secondary or tertiary amine function, within its elastomeric chain, the silicon atom of this group linking the two pieces of the chain of the diene elastomer, it is said that the elastomer is coupled or functionalized in the middle of the chain, as opposed to the position "at the end of the chain" and although the grouping is not precisely in the middle of the elastomer chain.
    [0007] When a silane functional group bearing a primary, secondary or tertiary amine functional group is central to which three elastomer chains or branches are linked forming a star structure of the elastomer, the species will then be said to be starred. The silicon atom of this group binds the three branches of the diene elastomer modified with one another. By the term "composition-based" 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, less in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization. By diene elastomer, it is to be understood in a known manner (is meant one or more) elastomer derived at least in part (ie, a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not ). More particularly, diene elastomer is any homopolymer obtained by polymerization of a conjugated diene monomer having 4 to 12 carbon atoms, or any copolymer obtained by copolymerization of one or more conjugated dienes with one another or with one or more vinylaromatic compounds. having from 8 to 20 carbon atoms. In the case of copolymers, these contain from 20% to 99% by weight of diene units, and from 1 to 80% by weight of vinylaromatic units.
    [0008] Conjugated dienes which can be used in the process according to the invention are especially suitable for 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 -C 5 alkyl) -1,3 butadiene 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, phenyl-1,3-butadiene, 1,3-pentadiene and 2,4-hexadiene, etc. Particularly suitable vinylaromatic compounds are styrene, ortho-, meta, para-methylstyrene, alpha-methylstyrene, the commercial mixture "vinyltoluene", para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene and vinylnaphthalene, etc. The diene elastomer of the invention is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR) and butadiene copolymers, in particular butadiene copolymers and a vinyl aromatic monomer, isoprene copolymers and mixtures of these elastomers. Such copolymers are more particularly butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-butadiene-styrene copolymers (SBIR). Among these copolymers, butadiene-styrene copolymers (SBR) are particularly preferred. The species (i) functionalized at the end of the chain by an alkylalkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and linked to the elastomer via the atom of silicon, preferably corresponds to the following formula (I): NR; In which: - E denotes the diene elastomer, - R denotes a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl radical, - R 1 'denotes, depending on the degree of hydrolysis, a hydrogen atom or a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl or ethyl radical, R 2 'is a hydrocarbon group divalent aliphatic, saturated or unsaturated, cyclic or not, Ci-Cis, or aromatic C6-C18, preferably linear aliphatic C1-C6, more preferably divalent hydrocarbon radical linear aliphatic saturated C3, - R3 'and R4 , which may be identical or different, represent a hydrogen atom or a linear or branched C 1 -C 18 and preferably C 1 -C 4 alkyl radical, more preferably a methyl or ethyl radical, or else R 3 'and R 4' form with N to which they are attached a heterocycle containing a nitrogen atom and at the m oins a carbon atom, preferably from 2 to 6 carbon atoms. According to advantageous variants of the invention, at least one of the following four characteristics is met and preferably the four: - R represents a methyl radical, - Rr represents a hydrogen atom or a methyl or ethyl radical, preferably an atom of hydrogen, R2 'represents the divalent saturated linear aliphatic hydrocarbon radical C3, - R3' and R4 ', identical or different, preferably identical, represent a methyl or ethyl radical, preferably methyl. The species (ii) functionalized in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and whose silicon atom binds the two pieces of the chain , preferably corresponds to the following formula (II): Rai 4 12 E-Si-E OR1 (II) in which: - E denotes the diene elastomer, - R1 denotes, depending on the degree of hydrolysis, an atom of hydrogen or a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl or ethyl radical, R 2 is a divalent aliphatic hydrocarbon group, saturated or unsaturated, cyclic or otherwise, in Ci-Cis, or C6-C18 aromatic, preferably C1-C6 linear aliphatic, more preferably the divalent divalent linear aliphatic hydrocarbon radical saturated with C3, - R3 and R4, which are identical or different, represent a hydrogen atom or a alkyl radical, linear e or branched, C 1 -C 18, preferably C 1 -C 4, more preferably methyl or ethyl, or R 3 and R 4 form with N to which they are bonded a heterocycle containing a nitrogen atom and at least one atom carbon, preferably 2 to 6 carbon atoms. According to advantageous variants of the invention, at least one of the following three characteristics is met and preferably the three: - R1 represents a hydrogen atom or a methyl or ethyl radical, preferably a hydrogen atom, - R2 represents the divalent linear aliphatic hydrocarbon radical saturated with C3, - R3 and R4, identical or different, preferably identical, represent a methyl or ethyl radical, preferably methyl.
    [0009] The species (iii) stellate three branches containing a silane functional group, carrying a primary, secondary or tertiary amine function, and whose silicon atom binds the three branches of the chain, preferably corresponds to the formula (III ): R3N / R4 2 E wherein R2, R3 and R4 are as defined above.
    [0010] The various aspects, preferential or not, which precede are combinable between them. The modified diene elastomer according to the invention may be prepared according to a process that includes modifying the elastomer by reacting a living diene elastomer with two suitable functionalization agents. Such a method is also the subject of the invention. Thus, according to the invention, the modified diene elastomer is obtained by the process comprising the following steps: 1) anionic polymerization of at least one conjugated diene in the presence of a polymerization initiator to form a living diene elastomer, and then 2 ) addition to the living diene elastomer obtained in step 1) of a trialkoxysilane compound bearing a protected primary or protected secondary or tertiary amine function, the trialkoxysilane molar ratio carrying a protected, secondary secondary amine protected or tertiary / polymerization initiator varying from 0.05 to 0.35, then 3) adding to the elastomer solution obtained at the end of step 2) an alkyl dialkoxysilane compound bearing a protected primary amine function, secondary protected or tertiary, the alkyldialcoxysilane molar ratio carrying a primary protected, secondary protected or tertiary amine function / polymerization initiator used se in step 1) being greater than or equal to 0.8.
    [0011] The polymerization of diene monomers is initiated by an initiator. As a polymerization initiator, any known monofunctional anionic initiator can be used. However, an initiator containing an alkali metal such as lithium is used in a preferred manner.
    [0012] Suitable organolithium initiators include those having a carbon-lithium or nitrogen-lithium bond. Representative compounds are aliphatic organoliths such as ethyllithium, n-butyllithium (n-BuLi), isobutyl lithium, and the like; lithium amides obtained from a secondary amine and more particularly those obtained from a cyclic secondary amine, such as pyrrolidine or hexamethyleneimine. The polymerization is preferably carried out in the presence of an inert hydrocarbon solvent which may be for example an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane or a hydrocarbon aromatic such as benzene, toluene, xylene. The polymerization can be carried out continuously or discontinuously. The polymerization is generally carried out at a temperature of between 20 ° C. and 150 ° C. and preferably in the region of 30 ° C. to 110 ° C. The second step of the process according to the invention consists of the modification of the living diene elastomer, obtained at the end of the anionic polymerization step, according to operating conditions favoring the star-branching and coupling reactions of the elastomer diene with a functionalisation agent of the trialkoxysilane type bearing a primary protected, secondary protected or tertiary amine function This trialkoxysilane compound carrying a primary protected, secondary protected or tertiary amine function preferably corresponds to the following formula (IV): R 5 In which - the linear or branched R 1 "radicals, which are identical to or different from each other, represent a C 1 -C 10 alkyl group, preferably a C 1 -C 4 alkyl group, more preferably a C 1 -C 4 alkyl radical; methyl or ethyl, R2 is a divalent aliphatic hydrocarbon group, saturated or unsaturated, cyclic or non-cyclic, C 1 -C 18, or aromatic C 6 -C 18, preferably C 1 -C 6 linear aliphatic more preferably, the divalent divalent linear aliphatic hydrocarbon radical saturated with C3, R5 and R6, which may be identical or different, represent a trialkyl silyl radical, the alkyl groups, which may be identical or different, having from 1 to 4 carbon atoms, or an alkyl radical, linear or branched, C 1 -C 18, preferably C 1 -C 4, more preferably methyl or ethyl, or R 5 and R 6 form with N to which they are bonded a heterocycle containing a nitrogen atom and at least one atom carbon, preferably 2 to 6 carbon atoms. Mention may be made, as functionalizing agent, of (N, N-dialkylaminopropyl) trialkoxysilanes, (N-alkylaminopropyl) trialkoxysilanes, the secondary amine function of which is protected by a trialkyl silyl group and aminopropyltrialkoxysilanes, the primary amine function of which is protected by two trialkyl silyl groups. According to variants, the functionalizing agent may be chosen from 3- (N, N-dimethylaminopropyl) trimethoxysilane, 3- (N, N-dimethylaminopropyl) triethoxysilane, 3 - (N, N-diethylaminopropyl) trimethoxysilane, 3 - (N, N-diethylaminopropyl) triethoxysilane, 3 - (N, N-dipropylaminopropyl) triethoxysilane, 3 - (N, N-dibutylaminopropyl) trimethoxysilane, 3 - (N, N-diethylaminopropyl) triethoxysilane; (N, N-dibutylaminopropyl) triethoxysilane, 3 - (N, N-dipentylaminopropyl) triethoxysilane, 3 - (N, N-dihexylaminopropyl) trimethoxysilane, 3 - (N N, N-dihexylaminopropyl) triethoxysilane, 3- (hexamethyleneaminopropyl) trimethoxy silane, 3- (hexamethyleneaminopropyl) triethoxysilane, 3- (morpholinopropyl) trimethoxy silane, 3- (morpholinopropyl) triethoxysilane, 3- (piperi dinopropyl) trimethoxy silane 3- (piperidinopropyl) triethoxy silane. Preferably, the coupling agent is then 3- (N, N-dimethylaminopropyl) trimethoxysilane. According to other variants, the functionalizing agent may be chosen from 3- (N, N-methyltrimethylsilylaminopropyl) trimethoxysilane, 3 - (N, N-methyltrimethylsilylaminopropyl) triethoxysilane, 3 - (N, N-ethyltrimethyl) silylaminopropyl) trimethoxy silane, 3 - (N, N-ethyltrimethylsilylaminopropyl) triethoxy silane, 3 - (N, N -propyltrimethylsilylaminopropyl) trimethoxysilane, 3 - (N, N-propyltrimethylsilyl aminopropyl) triethyloxy silane. Preferably, the coupling agent is then 3- (N, N-methyltrimethylsilylaminopropyl) trimethoxy silane. According to still other variants, the functionalising agent may be chosen from 3- (N, N-bistrimethylsilylaminopropyl) trimethoxysilane and 3- (N, N-bistrimethylsilylaminopropyl) triethoxysilane. Preferably, the coupling agent is then 3- (N, N-bi-strimethylsilylaminopropyl) trimethoxy silane. The mixing of the living diene polymer and the trialkoxysilane compound carrying a protected primary, protected secondary or tertiary amine function can be carried out by any appropriate means. The reaction time between the living diene polymer and aminotrialkoxysilane compound may be between 10 seconds and 2 hours.
    [0013] The second step of the process according to the invention leads to the formation of the species (ii) functionalized in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and whose silicon atom binds the two pieces of the chain, and of the species (iii) stellate three branches containing a silane functional group, carrying a primary, secondary or tertiary amine function, and whose atom of silicon binds the three branches of the chain.
    [0014] The third step of the process according to the invention consists in modifying the living diene elastomer according to operating conditions that favor an end-functionalization reaction of the diene elastomer with an alkyldialcoxysilane functionalization agent bearing a functional function. primary amine protected, secondary protected or tertiary. This alkyldialkoxysilane compound carrying a protected primary, protected secondary or tertiary amine function has the following formula (V): ## STR2 ## in which R represents a radical alkyl, linear or branched, C 1 -C 10, preferably C 1 -C 4, more preferably a methyl radical, - radicals R '", identical or different from each other, represent a linear or branched alkyl radical, C 1 -C 4 C 10, preferably C 1 -C 4, more preferably a methyl or ethyl radical, - R 2 'is a divalent aliphatic hydrocarbon group, saturated or unsaturated, cyclic or non-cyclic, C 1 -C 18, or aromatic C 6 -C 18, preferably C1-C6 linear aliphatic, more preferably the divalent divalent linear aliphatic hydrocarbon radical saturated with C3, - R7 and R8, identical or different, represent a trialkyl silyl radical, the alkyl groups, identical or different, having from 1 to 4 carbon atoms; carbon, or a radical (V) alkyl, linear or branched, C 1 -C 18, preferably C 1 -C 4, more preferably a methyl or ethyl radical, or R 7 and R 8 form with N to which they are bonded a heterocycle containing a nitrogen atom and at least a carbon atom, preferably from 2 to 6 carbon atoms. The (N, N-di-alkylaminopropyl) (alkyl) dialkoxysilane s (N-alkylaminopropyl) (alkyl) dialkoxysilanes, the secondary amine function of which is protected by a grouping, may be mentioned as functionalizing agents. trialkyl silyl and (aminopropyl) (alkyl) dialkoxysilanes whose primary amine function is protected by two trialkyl silyl groups. According to variants, the functionalising agent may be chosen from 3- (N, N-dimethylaminopropyl) (methyl) dimethoxysilane, 3 - (N, N-dimethylaminopropyl) (methyl) diethoxysilane and 3- (N, N-dimethylaminopropyl) (methyl) dimethoxysilane. diethylaminopropyl) (methyl) dimethoxysilane, 3 - (N, N-diethylaminopropyl) (methyl) diethoxysilane, 3 - (N, N-dipropylaminopropyl) (methyl) dimethoxysilane, 3 - (N, N-dipropylaminopropyl) (methyl) diethoxysilane, 3 - (N, N-dibutylaminopropyl) (methyl) dimethoxysilane, 3 - (N, N-dibutylaminopropyl) (methyl) diethoxysilane, 3 - (N, N-dipentylaminopropyl) (methyl) dimethoxysilane, 3 - (N, N-dipentylaminopropyl) (methyl) diethoxysilane, 3 - (N, N-dihexylaminopropyl) (methyl) dimethoxysilane, 3- (N, N-dihexylaminopropyl) (methyl) diethoxysilane, 3- (hexamethyleneaminopropyl) (methyl) ) dimethoxysilane, 3- (hexamethyleneaminopropyl) (methyl) diethoxy silane, 3- (morpholinopropyl) (methyl) dimethoxysilane, 3- (morpholinopropyl) (methyl) diethoxysilane, 3- (piperidinopropyl) (methyl) dimethoxysilane, 3- (piperidinopropyl) (methyl) diethoxysilane. Preferably, the coupling agent is then 3- (N, N-dimethylaminopropyl) (methyl) dimethoxysilane.
    [0015] According to other variants, the functionalizing agent may be chosen from 3- (N, N-methyltrimethylsilylaminopropyl) (methyl) dimethoxysilane, 3- (N, N-methyltrimethylsilylaminopropyl) (methyl) diethoxysilane, 3- (N, N) ethyltrimethylsilylaminopropyl) (methyl) dimethoxysilane, 3- (N, N-ethyltrimethylsilylaminopropyl) (methyl) diethoxysilane, 3- (N, N-propyltrimethylsilylaminopropyl) (methyl) dimethoxy silane, 3- (N, N-propyltrimethylsilylaminopropyl) (methyl) ) diethoxysilane. Preferably, the coupling agent is then 3 - (N, N-methyltrimethylsilylaminopropyl) (methyl) dimethoxysilane. According to still other variants, the functionalizing agent may be chosen from 3- (N, N-bistrimethylsilylaminopropyl) (methyl) dimethoxysilane and 3- (N, N -istrimethylsilylaminopropyl) (methyl) diethoxysilane.
    [0016] Preferably, the coupling agent is then 3- (N, N-bistrimethylsilylaminopropyl) (methyl) dimethoxysilane.The third step of the process according to the invention leads to the formation of the species (i) functionalized at the end of the chain by an alkylalkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and bonded to the elastomer via the silicon atom. The method of synthesis of the modified diene elastomer according to the invention can be continued in a manner known per se by the recovery steps of the modified elastomer. According to variants of this process, these steps comprise a stripping step in order to recover the elastomer from the previous steps in dry form. This stripping step may in particular have the effect of hydrolyzing all or part of the hydrolyzable alkoxysilane functions of the modified diene elastomer to transform them into silanol functions. According to other variants of this process, these steps comprise a specific hydrolysis step dedicated to the hydrolysis of all or part of the hydrolyzable alkoxysilane functional groups of the modified diene elastomer to convert them into silanol functions. This total or partial hydrolysis step may be carried out in a manner known per se, before a possible stripping step, by adding an acidic or basic compound. Such hydrolysis steps are described, for example, in EP 2 266 819 A1. According to other variants of this process, these steps comprise a specific step of deprotection of the primary amine or of the secondary amine when at least one of the two functionalization agents used carries a protected primary or secondary amine function. This step is carried out after the two functionalization steps, before a possible stripping step. By way of example, it is possible to react the functionalized chains with the protected amine group with an acid, a base, a fluorinated derivative such as tetrabutylammonium fluoride, a silver salt such as silver nitrate, etc. to deprotect this or these function (s) amine. These various methods are described in the book "Protective Groups in Organic Synthesis, W. W. Green, P.GM Wuts, Third Edition, 1999". This deprotection step may have the effect of hydrolyzing all or part of the hydrolyzable alkoxysilane functions of the modified diene elastomer to transform them into silanol functions. Because of the recognized effect of its functions on the hysteresis and the processability of reinforced rubber compositions, the modified diene elastomer according to the invention is advantageously used in reinforced rubber compositions, in particular intended for the manufacture of tires. Thus, another subject of the invention is a reinforced rubber composition based on at least one reinforcing filler and an elastomeric matrix comprising at least one modified diene elastomer as described above. It should be understood that the rubber composition may comprise one or more of these modified diene elastomers according to the invention.
    [0017] The reinforced rubber composition according to the invention may be in the crosslinked state or in the uncrosslinked state, that is to say crosslinkable. The diene elastomer modified according to the invention can be, according to different variants, used alone in the composition or in blending with at least one other conventional diene elastomer, whether star-shaped, coupled, functionalized or not. Preferentially, this other diene elastomer used in the invention is chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, copolymers of isoprene and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers. butadiene-styrene (SBIR). It is also possible to cut with any synthetic elastomer other than diene, or with any other polymer other than elastomer, for example a thermoplastic polymer.
    [0018] It will be noted that the improvement in the properties of the composition according to the invention will be all the greater as the proportion of the elastomer (s) different from the modified diene elastomers of the invention in this composition will be reduced. Thus, preferably, the elastomer matrix comprises predominantly the modified diene elastomer according to the invention. When the conventional elastomer used in cutting is natural rubber and / or one or more diene polymers such as polybutadienes, polyisoprenes, butadiene-styrene or butadiene-styrene-isoprene copolymers, this elastomer or these elastomers, modified or otherwise can then be present from 1 to 70 parts by weight per 100 parts of modified diene elastomer according to the invention. More preferably, the elastomeric matrix consists solely of the modified diene elastomer according to the invention.
    [0019] The rubber composition of the invention comprises, in addition to at least one elastomeric matrix as described above, at least one reinforcing filler. It is possible to use any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tire treads, for example carbon black, a reinforcing inorganic filler such as silica with which it is associated with known manner a coupling agent, or a mixture of these two types of load.
    [0020] The rubber composition according to the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, such as, for example, pigments, non-reinforcing fillers, coupling activators, agents and the like. for covering the fillers or, more generally, agents for assisting the processing, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, plasticizers, resins reinforcing or plasticizing, acceptors (for example phenolic novolac 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 donors of sulfur and / or peroxide and / or bismaleimides, vulcanization accelerators, vulcanization activators.
    [0021] The rubber composition according to the invention can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile that can be used as a semi-finished rubber product for the tire. .
    [0022] The invention also relates to a semi-finished rubber article for a tire, comprising a rubber composition according to the invention, crosslinkable or crosslinked or consisting of such a composition.
    [0023] Due to the improvement of the hysteresis / processability compromise of a reinforced rubber composition according to the invention and the storage stability of the Mooney viscosity of the elastomer which enters into its composition, it will be noted that such a composition can constitute any semi-finished product of the tire and especially the tread. The invention therefore finally relates to a tire comprising a semi-finished article according to the invention, in particular a tread.
    [0024] The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation.
    [0025] Examples Measurements and tests used High resolution steric exclusion chromatography The high resolution SEC technique is used to determine the mass percentages of the different chain populations present in a polymer sample.
    [0026] There is no particular treatment of the polymer sample before analysis. This is simply solubilized in the eluting solvent at a concentration of about 1 g / L. Then the solution is filtered on a porosity filter 0.45 i.tm before injection. The equipment used is a chromatographic chain "WATERS alliance 2695". The elution solvent is tetrahydrofuran, the flow rate 0.2 ml.min-1, the system temperature 35 ° C. A set of three identical columns in series is used (Shodex, length 300 mm, diameter 8 mm). The number of theoretical plates in the set of columns is greater than 22,000. The injected volume of the solution of the polymer sample is 50 μl. The detector is a differential refractometer "WATERS 2414" and the chromatographic data exploitation software. is the "WATERS EMPOWER" system. The calculated molar masses relate to a calibration curve produced for SBRs of microstructure as follows: 25% by weight of styrene type units, 23% by mass of 1,2 type units and 50% by mass of 1,4-trans type units. Mooney Viscosity The Mooney viscosities ML (i + 4) 100 ° C elastomers are measured according to ASTM D-1646. An oscillatory consistometer is used as described in ASTM D-1646. The Mooney plasticity measurement is carried out according to the following principle: the elastomer is molded in a cylindrical chamber heated to 100 ° C. After one minute preheating, the rotor rotates within the specimen at 2 rpm and the torque needed to maintain this movement after 4 minutes of rotation is measured. The Mooney plasticity ML (i + 4) is expressed in "Mooney unit" (UM, with 1 UM = 0.83 Nm). Differential calorimetry The glass transition temperatures (Tg) of the elastomers are determined using a differential scanning calorimeter. Near Infrared Spectroscopy (NIR) The microstructure of elastomers is characterized by the technique of near infrared spectroscopy (NIR).
    [0027] Near-infrared spectroscopy (NIR) is used to quantitatively determine the mass content of styrene in the elastomer as well as its microstructure (relative distribution of 1,2-butadiene 1,4-trans and 1,4-cis units). The principle of the method is based on the Beer-Lambert law generalized to a multicomponent system. The method being indirect, it uses a multivariate calibration [Vilmin, F .; Dussap, C .; Coste, N. Applied Spectroscopy 2006, 60, 619-29] carried out using standard elastomers of composition determined by 13C NMR. The styrene content and the microstructure are then calculated from the NIR spectrum of an elastomer film about 730 μm thick. The acquisition of the spectrum is carried out in transmission mode between 4000 and 6200 cm-1 with a resolution of 2 cm-1, using a Bruker Tensor 37 Fourier transform infrared near-infrared spectrometer equipped with a cooled InGaAs detector. by Peltier effect. Examples of Preparation of Modified Elastomers Preparation of Polymer A-Polymer According to the Invention In a 90-liter reactor, maintained under a nitrogen pressure of about 2 bars, containing 45.5 kg of methylcyclohexane, are injected 2.0 kg of styrene and 4.7 kg of butadiene and 318 ml of a solution of tetrahydrofurfuryl ether at 0.0708 mol.L-1 in methylcyclohexane. After neutralization of the impurities in the solution to be polymerized by addition of n-butyllithium, 644 ml of 0.059 mol.L -1 n-butyllithium in methylcyclohexane are added. The polymerization is conducted at 40 ° C.
    [0028] After 70 minutes, the conversion rate of the monomers reaches 90%. This level is determined by weighing a dried extract at 140 ° C., under the reduced pressure of 200 mmHg. 147 ml of a solution of 3- (N, N-dimethylaminopropyl) trimethoxysilane at 0.0516 mol.L-1 in methylcyclohexane are added to the living polymer solution.
    [0029] After 15 minutes of reaction at 40 ° C., 190 ml of a solution of 3- (N, N-dimethylaminopropyl) (methyl) dimethoxy silane at 0.08 mol.L -1 in methylcyclohexane are then added to this solution of polymer. After 15 minutes of reaction at 40 ° C., the solution is antioxidized by the addition of 0.8 part per hundred parts of elastomer (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0 2 parts per hundred parts elastomer (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-pphenylenediamine. The copolymer thus treated is separated from its solution by devolatilization.
    [0030] The mass percentage of chains functionalized at the end of the chain, determined by the high-resolution SEC technique, is 50%, that of the functionalized chains in the middle of the chain is 20% and that of the 3-pointed star chains is 30%. The Mooney viscosity of polymer A is 70.
    [0031] The microstructure of this copolymer is determined by the NIR method: the mass ratio of 1,4-trans units is 22%, that of 1,4-cis units is 19% and that of 1,2 units is 59%. , each of these three rates pertaining to the butadiene units. The mass content of styrene is 27%.
    [0032] The glass transition temperature of this copolymer is -23 ° C. Preparation of polymer B - Polymer not according to the invention In a reactor of 90 liters, maintained under a nitrogen pressure of about 2 bars, containing 45.3 kg of methylcyclohexane, are injected 2.0 kg of styrene and 4 , 7 kg of butadiene and 354 ml of a solution of tetrahydrofurfuryl ether at 0.0695 mol.L-1 in methylcyclohexane. After neutralization of the impurities in the solution to be polymerized by addition of n-butyllithium, 644 ml of 0.059 mol.L -1 n-butyllithium in methylcyclohexane are added. The polymerization is conducted at 40 ° C.
    [0033] After 70 minutes, the conversion rate of the monomers reaches 90%. This level is determined by weighing a dried extract at 140 ° C., under the reduced pressure of 200 mmHg. 147 ml of a solution of 3- (N, N-dimethylaminopropyl) trimethoxysilane at 0.0516 mol.L-1 in methylcyclohexane are added to the living polymer solution. After 15 minutes of reaction at 40 ° C., 294 ml of a solution of 3- (N, N-dimethylaminopropyl) trimethoxysilane at 0.0516 mol.L -1 in methylcyclohexane are then added to this polymer solution. After 15 minutes of reaction at 40 ° C., the solution is antioxidized by the addition of 0.8 parts per hundred parts of elastomer (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0 , 2 part per hundred parts elastomer (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. The copolymer thus treated is separated from its solution by devolatilization.
    [0034] The mass percentage of chains functionalized at the end of the chain, determined by the high-resolution SEC technique, is 50%, that of the functionalized chains in the middle of the chain is 20% and that of the 3-pointed star chains is 30%. The Mooney viscosity of polymer B is 72.
    [0035] The microstructure of this copolymer is determined by the NIR method: the mass ratio of 1,4-trans units is 21%, that of 1,4-cis units is 19% and that of 1,2 units is 60%. , each of these three rates pertaining to the butadiene units. The mass content of styrene is 28%.
    [0036] The glass transition temperature of this copolymer is -22 ° C. Results The evolution of the Mooney viscosity over time of these polymers was evaluated during storage under usual conditions.
    [0037] Samples of polymers A and B were wrapped in air permeable polyethylene film and stored at a temperature of 25 ° C at atmospheric pressure and protected from light. Mooney viscosity measurements were made at time intervals as shown in Table 1 below. Table 1 Mooney time (j) Polymer A Polymer B 0 70 72 4 70 79 7 70 84 11 70 89 15 70 94 19 70 98 30 71/60 74 / In Table 1, "I" means that no Mooney measurement has not been performed (unreliable measured values beyond 100). It is found that the polymer A, diene elastomer modified according to the invention undergoes no change in Mooney viscosity during the storage period spanning 60 days, unlike the control polymer B which sees its Mooney viscosity increase by 26 Mooney units. after 19 days of storage.
    权利要求:
    Claims (17)
    [0001]
    REVENDICATIONS1. A modified diene elastomer comprising (i) 40 to 80% by weight, relative to the total weight of said modified diene elastomer, of the species functionalized at the end of the chain by an alkylalkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and bonded to the elastomer via the silicon atom, (ii) 5 to 45% by weight, based on the total weight of said modified diene elastomer, of the functionalized species in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and whose silicon atom binds the two pieces of the chain, (iii) 3 to 30 % by weight, relative to the total weight of said modified diene elastomer, of the three-branched star-containing species containing a silane functional group carrying a primary amine function re, secondary or tertiary, and whose silicon atom links the three branches of the chain.
    [0002]
    2. Modified diene elastomer according to claim 1, characterized in that the species (i) functionalized at the end of the chain by an alkylalkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary, secondary or tertiary amine function, and linked to the elastomer via the silicon atom, corresponds to the following formula (I): NR 4 R; In which: - E denotes the diene elastomer, - R denotes a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl radical, R 1 'denotes, according to the degree of hydrolysis, a hydrogen atom or a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl or ethyl radical; is an aliphatic divalent hydrocarbon group, whether saturated or unsaturated, cyclic or non-cyclic, C 1 -C 18 aromatic or C 6 -C 18 aromatic, preferably C 1 -C 6 linear aliphatic, more preferably the divalent linear aliphatic hydrocarbon radical saturated with C 3, R 3 'and R 4', which are identical or different, represent a hydrogen atom or a linear or branched C 1 -C 18 and preferably C 1 -C 4 alkyl radical, more preferably a methyl or ethyl radical, or else R 3 and R4 'form with N to which they are bonded a heterocycle containing a nitrogen atom and at least one carbon atom, preferably 2 to 6 carbon atoms.
    [0003]
    3. Modified diene elastomer according to claim 2 characterized in that R1 'represents a hydrogen atom or a methyl or ethyl radical, preferably a hydrogen atom.
    [0004]
    4. Modified diene elastomer according to claim 2 or 3 characterized in that R2 'represents the divalent linear aliphatic hydrocarbon radical saturated with C3.
    [0005]
    5. modified diene elastomer according to any one of claims 2 to 4 characterized in that R3 'and R4', identical or different, preferably identical, represent a methyl or ethyl radical, preferably methyl.
    [0006]
    6. Modified diene elastomer according to any one of the preceding claims, characterized in that the species (ii) functionalized in the middle of the chain by an alkoxysilane group, optionally partially or completely hydrolysed to silanol, carrying a primary amine function, secondary or tertiary, and whose silicon atom binds the two pieces of the chain, corresponds to the following formula (II): Rai 4 12 E-Si-E OR1 (II) in which: - E denotes the diene elastomer, R 1 denotes, according to the degree of hydrolysis, a hydrogen atom or a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl or ethyl radical, - R 2 is a divalent aliphatic hydrocarbon group, saturated or unsaturated, cyclic or non-cyclic, C 1 -C 18, or aromatic C 6 -C 18, preferably C 1 -C 6 linear aliphatic, more preferably the divalent linear aliphatic hydrocarbon radical saturated with C 3, - R 3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C18, preferably C1-C4, alkyl radical, more preferably a methyl or ethyl radical, or else R3 and R4 form with N to which they are attached a heterocycle containing a nitrogen atom and at least one carbon atom, preferably from 2 to 6 carbon atoms.
    [0007]
    7. modified diene elastomer according to claim 6 characterized in that R1 represents a hydrogen atom or a methyl or ethyl radical, preferably a hydrogen atom.
    [0008]
    8. modified diene elastomer according to claim 6 or 7 characterized in that R2 represents the divalent linear aliphatic hydrocarbon radical saturated with C3.
    [0009]
    9. modified diene elastomer according to any one of claims 6 to 8 characterized in that R3 and R4, identical or different, preferably identical, represent a methyl or ethyl radical, preferably methyl.
    [0010]
    10. modified diene elastomer according to any one of claims 6 to 9 characterized in that the species (iii) stellate three branches containing a silane functional group bearing a primary, secondary or tertiary amine function, and whose silicon atom binds the three branches of the chain, corresponds to the following formula (III): R3N / R4 2 E
    [0011]
    11. Modified diene elastomer according to any one of the preceding claims, characterized in that the diene elastomer is a copolymer of butadiene and a vinylaromatic monomer, in particular an SBR.
    [0012]
    12. Process for preparing a modified diene elastomer as defined in any one of the preceding claims, characterized in that it comprises the following steps: 1) anionic polymerization of at least one conjugated diene in the presence of a polymerization initiator to form a living diene elastomer and then 2) addition to the living diene elastomer obtained in step 1) of a trialkoxysilane compound carrying a protected primary or protected secondary or tertiary amine function, the trialkoxysilane molar ratio carrier of a primary protected, secondary protected or tertiary amine / polymerization initiator function varying from 0.05 to 0.35, then 3) addition to the elastomer solution obtained at the end of step 2); an alkyl dialkoxysilane compound bearing a protected primary or protected secondary or tertiary amine function, the alkyldialkoxysilane molar ratio carrying a protected primary amine function e, secondary protected or tertiary / polymerization initiator used in step 1) being greater than or equal to 0.8.
    [0013]
    13. Preparation process according to claim 12, characterized in that the polymerization initiator is selected from the alkyl lithium compounds.
    [0014]
    14. Preparation process according to claim 12 or 13, characterized in that the trialkoxysilane compound carrying a primary protected, secondary protected or tertiary amine function has the formula R5 N / R6 R2 R "1 Si -OR" i OR "(IV) in which - the linear or branched R 1" radicals, which are identical to or different from one another, represent a C 1 -C 10, preferably C 1 -C 4, alkyl group, better still a methyl or ethyl radical, - R 2 is a divalent aliphatic hydrocarbon group, whether saturated or unsaturated, cyclic or non-cyclic, C 1 -C 18 aromatic or C 6 -C 18 aromatic, preferably linear C 1 -C 6 aliphatic, more preferably the divalent linear aliphatic hydrocarbon radical saturated with C 3 and R 5; and R6, which may be identical or different, represent a trialkyl silyl radical, alkyl groups, which may be identical or different, having from 1 to 4 carbon atoms, or a linear or branched C 1 -C 18 and preferably C 1 -C 4 alkyl radical; , preferably a methyl or ethyl radical, or else R5 and R6 form with N to which they are bonded a heterocycle containing a nitrogen atom and at least one carbon atom, preferably from 2 to 6 carbon atoms.
    [0015]
    15. Preparation process according to any one of claims 12 to 14, characterized in that the alkyldialcoxysilane compound bearing a primary protected, secondary protected or tertiary amine function has the following formula (V): R7 / R8 ( In which R denotes a linear or branched C1-C10, preferably C1-C4, alkyl radical, more preferably a methyl radical, the radicals R1 '. ", identical or different from each other, represent a linear or branched C 1 -C 10, preferably C 1 -C 4, alkyl radical, more preferably a methyl or ethyl radical; R 2 'is a divalent aliphatic hydrocarbon group, saturated or No, cyclic or non-cyclic, C 1 -C 18 or aromatic C 6 -C 18, preferably C 1 -C 6 linear aliphatic, more preferably the linear aliphatic divalent hydrocarbon radical saturated with C 3, R 7 and R 8, which may be identical or different, represent a trialkyl radical silyl, the alkyl groups, which may be identical or different, having from 1 to 4 carbon atoms, or a linear or branched C 1 -C 18 and preferably C 1 -C 4 alkyl radical, more preferably a methyl or ethyl radical, or else R 7 and R8 together with N to which they are attached a heterocycle containing a nitrogen atom and at least one carbon atom, preferably 2 to 6 carbon atoms.
    [0016]
    16. Reinforced rubber composition based on at least one reinforcing filler and an elastomeric matrix comprising at least one modified diene elastomer as defined in any one of Claims 1 to 11.
    [0017]
    17. A rubber composition according to claim 16, characterized in that the elastomer matrix comprises predominantly the modified diene elastomer as defined in any one of claims 1 to 11.3019. A rubber semi-finished article for a tire, characterized in that it comprises a cross-linkable or cross-linked rubber composition according to any one of claims 16 to 18. 20. A tire characterized in that it comprises a semi-finished article as defined in claim 19.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3030589B1|2018-06-13|Diene elastomer modified, synthesis method for same and rubber composition comprising it
    FR3014872A1|2015-06-19|MODIFIED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME
    EP3359396B1|2019-12-04|Diene elastomer having a function in the middle of the chain and rubber composition containing the same
    EP3030588B1|2018-03-28|Diene elastomer modified by coupling having silanol functions, synthesis method for same and rubber composition comprising it
    EP3030587B1|2021-02-24|Continuous synthesis method for a modified diene elastomer, facility for implementing same
    FR3009557A1|2015-02-13|MODIFIED DIENOUS ELASTOMER COMPRISING A DIAMOND ELASTOMER COUPLED BY AN AMINOALCOXYSILANE COMPOUND AND FUNCTIONALIZED AMINE IN CHAIN END AND RUBBER COMPOSITION COMPRISING SAME
    EP3063179B1|2019-12-04|Modified diene elastomer mostly comprising a diene elastomer coupled by an alkoxysilane compound bearing an amine-functionalised epoxide group at the end of the chain
    EP3030586A1|2016-06-15|Coupled diene elastomer having a silanol function in the middle of the chain and having an amine function at the chain end, and rubber composition comprising same
    WO2016001372A1|2016-01-07|Diene elastomer with a reduced pi having a silanol function at the chain end and composition containing same
    FR3011241A1|2015-04-03|DIAMOND ELASTOMER TRIBLOC WHOSE CENTRAL BLOCK IS A BLOCK POLYETHER AND FUNCTIONALIZED AMINE IN END OF CHAIN
    EP3558704A1|2019-10-30|Rubber composition comprising a modified diene elastomer
    EP3317122B1|2019-05-08|Modified diene elastomer of reduced polydispersity index, and rubber composition containing same
    WO2017060396A1|2017-04-13|Rubber composition containing a diene elastomer having a function in the middle of the chain
    EP3317123B1|2019-05-08|Modified diene elastomer of reduced polydispersity index, and rubber composition containing same
    EP3317121B1|2019-05-08|Modified diene elastomer with reduced pdi and composition containing same
    WO2018115168A1|2018-06-28|Method for continuous polymerisation of modified diene elastomer with lithium amide initiator
    同族专利:
    公开号 | 公开日
    FR3014872B1|2017-03-10|
    US20160319045A1|2016-11-03|
    JP6709157B2|2020-06-10|
    WO2015091855A1|2015-06-25|
    JP2017502138A|2017-01-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2915202A1|2007-04-18|2008-10-24|Michelin Soc Tech|MONOMODAL COUPLED DIENIC ELASTOMER HAVING CHAIN SILANOL FUNCTION, PROCESS FOR OBTAINING THE SAME, AND RUBBER COMPOSITION CONTAINING SAME.|
    FR2930554A1|2008-04-29|2009-10-30|Michelin Soc Tech|ELASTOMERIC MIXTURE COMPRISING MAJORITARILY A DIAGNOSTIC ELASTOMER COUPLED BY AN AMINO-ALCOXYSILANE GROUP, RUBBER COMPOSITION COMPRISING SAME AND METHODS OF OBTAINING SAME|
    FR2951178A1|2009-10-08|2011-04-15|Michelin Soc Tech|FUNCTIONALIZED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME.|
    FR2967679A1|2010-11-23|2012-05-25|Michelin Soc Tech|LOW-FUNCTIONAL IP DIENIC ELASTOMER WITH IMPROVED COLD-FLOWING AND RUBBER COMPOSITION CONTAINING SAME|WO2017001685A1|2015-07-02|2017-01-05|Compagnie Generale Des Etablissements Michelin|Modified diene elastomer of reduced polydispersity index, and rubber composition containing same|
    WO2017001684A1|2015-07-02|2017-01-05|Compagnie Generale Des Etablissements Michelin|Modified diene elastomer of reduced polydispersity index, and rubber composition containing same|
    EP3150401A1|2015-09-29|2017-04-05|Continental Reifen Deutschland GmbH|Rubber composition and vehicle tyre|
    EP3150402A1|2015-09-29|2017-04-05|Continental Reifen Deutschland GmbH|Rubber composition and vehicle tyre|
    EP3150403A1|2015-09-29|2017-04-05|Continental Reifen Deutschland GmbH|Rubber composition and vehicle tyre|US7807747B2|2007-06-22|2010-10-05|Sumitomo Chemical Company, Limited|Conjugated diene polymer, method for producing conjugated diene polymer, and conjugated diene polymer composition|
    JP6101459B2|2012-09-13|2017-03-22|日本エラストマー株式会社|Modified conjugated diene polymer, modified conjugated diene polymer composition and method for producing the same|
    FR3009559A1|2013-08-08|2015-02-13|Michelin & Cie|MODIFIED DIENIC ELASTOMER, PROCESS FOR THE SYNTHESIS, AND RUBBER COMPOSITION COMPRISING SAME|US20200001650A1|2017-01-31|2020-01-02|Compagnie Generale Des Etablissements Michelin|A tire comprising a rubber composition|
    WO2018182042A1|2017-03-31|2018-10-04|Compagnie Generale Des Etablissements Michelin|A tire comprising a tread|
    FR3067355A1|2017-06-08|2018-12-14|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION|
    EP3431511A1|2017-07-19|2019-01-23|ARLANXEO Deutschland GmbH|Star-branched diene rubber|
    CN108598481B|2018-04-18|2021-03-16|广东工业大学|Organic electrode material, preparation method and application thereof|
    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-22| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362870A|FR3014872B1|2013-12-18|2013-12-18|MODIFIED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME|FR1362870A| FR3014872B1|2013-12-18|2013-12-18|MODIFIED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME|
    JP2016541403A| JP6709157B2|2013-12-18|2014-12-18|Modified diene elastomer and rubber composition containing the same|
    US15/105,181| US20160319045A1|2013-12-18|2014-12-18|Modified diene elastomer and rubber composition containing same|
    PCT/EP2014/078557| WO2015091855A1|2013-12-18|2014-12-18|Modified diene elastomer and rubber composition containing same|
    [返回顶部]