EP2438095A1 - Systeme catalytique pour la polymerisation de dienes conjugues, procede de polymerisation et polymere fonctionnel obtenu - Google Patents

Systeme catalytique pour la polymerisation de dienes conjugues, procede de polymerisation et polymere fonctionnel obtenu

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Publication number
EP2438095A1
EP2438095A1 EP10722954A EP10722954A EP2438095A1 EP 2438095 A1 EP2438095 A1 EP 2438095A1 EP 10722954 A EP10722954 A EP 10722954A EP 10722954 A EP10722954 A EP 10722954A EP 2438095 A1 EP2438095 A1 EP 2438095A1
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EP
European Patent Office
Prior art keywords
catalytic system
formula
rare earth
earth metal
functionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP10722954A
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German (de)
English (en)
French (fr)
Inventor
Guillaume Cortial
Pascal Le Floch
François NIEF
Julien Thuilliez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Compagnie Generale des Etablissements Michelin SCA
Ecole Polytechnique
Michelin Recherche et Technique SA France
Original Assignee
Michelin Recherche et Technique SA Switzerland
Centre National de la Recherche Scientifique CNRS
Ecole Polytechnique
Societe de Technologie Michelin SAS
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Application filed by Michelin Recherche et Technique SA Switzerland, Centre National de la Recherche Scientifique CNRS, Ecole Polytechnique, Societe de Technologie Michelin SAS filed Critical Michelin Recherche et Technique SA Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/463—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from sodium or potassium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/21—Rubbery or elastomeric properties

Definitions

  • the present invention relates to a novel catalytic system based on rare earth, a process for preparing this catalytic system, a process for preparing a functionalized conjugated diene polymer comprising using said catalytic system, and such a polymer.
  • the invention also relates to a novel organometallic compound based on a divalent metal belonging to the 2 nd column of the periodic table used as a cocatalyst in the catalyst system based on rare earth and its preparation process.
  • diene elastomers are obtained by polymerization of the monomers in the presence of a catalytic system based on rare earth, as described in particular in the patent documents EP1355960 A1 or EP 1509557 B1 of the Applicants, functionalization can be envisaged with agents carrying a function adapted to the intended application for the functionalized diene elastomer.
  • a functionalizing agent that can be used for this functionalization step, those used in the prior art for functionalizing diene elastomers can be envisaged. from the anionic polymerization in the presence of a catalyst based on an organic compound of an alkali metal.
  • EP 0692492 A1 and EP 0692493 A1 in the name of the Applicants, is described the functionalization of diene elastomers with an alkoxysilane group, using a functional agent such as an epoxidized alkoxysilane.
  • EP 0778311 A1 discloses diene polymers carrying a silanol function or a polysiloxane block having a silanol end at the end of the chain obtained by reacting, at the end of polymerization, cyclic polysiloxanes on the living polymers.
  • the route of synthesis of functionalized polymers by implementing a catalytic system based on rare earth has the advantage of leading to diene elastomers having end-of-pipe chemical functions of varied structure, depending on the choice of the functional agent used.
  • a disadvantage however is that the synthesis comprises several steps, which can lead to a higher cost during the manufacture of such a polymer on an industrial scale, for example linked to the use of a higher number of reactors. and therefore to a complicated implementation.
  • Another disadvantage is the control of the purity of the functionalizing agent, which may, depending on the case, lead to deactivation or termination reactions of the ends of growing polymer chains, causing a proportion more or less high levels of nonfunctional elastomeric chains.
  • the present invention proposes to solve the above disadvantages by involving a limited number of reaction steps and leading to a proportion of optimal functionalized chains.
  • the inventors have discovered a new catalyst system based on a rare earth metal salt as a cocatalyst comprising an organometallic compound based on a divalent metal belonging to the 2nd or a trivalent metal belonging to the 13th column of the Periodic Table , which makes it possible to limit the steps of synthesis of a functionalized diene elastomer at the end of the chain, while ensuring optimal functionalization, that is to say close to or equal to 100% .
  • the use of this catalytic system for the polymerization more particularly for the preparation of functionalized diene elastomers, makes it possible to dispense with the subsequent reaction step on a functionalization agent.
  • the functionalized diene elastomers thus obtained have a high degree of functionalization, up to 100%, and can be advantageously used in rubber compositions comprising a reinforcing filler and intended for pneumatic application.
  • a first object of the present invention is a catalytic system based on a metal salt of rare earth and an organometallic compound based on a metal belonging to the 2 nd or 13 th column of the periodic table.
  • Another object of the invention is a process for preparing said catalytic system based on a rare earth metal salt.
  • the invention also relates to a process for preparing a functionalized diene elastomer by polymerizing at least one conjugated diene monomer in the presence of said catalytic system based on a rare earth metal salt.
  • Another subject of the invention is a functionalized diene elastomer that can be obtained by polymerizing at least one conjugated diene monomer in the presence of said catalytic system based on a rare earth metal salt.
  • the subject of the invention is also a family of novel compounds that can be used as cocatalyst in said catalytic system based on a rare earth metal salt.
  • the invention also relates to a process for preparing these novel compounds.
  • 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).
  • the term "functionalized polymer” means a polymer carrying a functional group at the chain end.
  • a first object of the invention is a catalytic system based on a metal salt of rare earth and an organometallic ⁇ mposé based on a metal belonging to 2 ⁇ 8 or 13 th column of the classification periodic, the latter compound corresponding to formula (I):
  • M is a metal belonging to the 2 ⁇ 6 or 13 th column of the periodic table
  • R1, R2, R3, R4, identical or different are hydrogen atoms or alkyl substituents, linear or branched, or aryls, substituted or unsubstituted, optionally bonded to one another (R 1 is then bonded to R, +1 ) to form at least one ring composed of 5 or 6 atoms, or at least one aromatic ring;
  • A is an alkyl radical based on C, H or Si atoms
  • X is a chemical function bonded to (CH 2 ) m by a hetero atom
  • L is a Lewis base
  • x is an integer which is 0, 1, 2, 3 or 4
  • n and m independently of each other, are each an integer equal to or greater than
  • M is preferably magnesium or aluminum
  • R 1, R 2, R 3 or R 4 denotes an alkyl substituent, that is preferably C 1 -C 12 , and even more preferably Ci-C
  • R1, R2, R3 or R4 refers to an aryl substituent that is preferably Ce-Ci 2, and still more preferably C 6 -C 0
  • the unit obtained is preferably composed of 2 to 4 conjugated aromatic rings, and more preferably of 2 to 3 aromatic rings.
  • R1, R2, R3 and R4 are hydrogen atoms.
  • A is more particularly a radical comprising 1 to 8 carbon atoms, preferably 2 to 8 carbon atoms.
  • A is an ethyl, n-butyl, i-butyl, n-hexyl, n-octyl, -CH 2 -Si (CH 3 ) 3 or -CH- [Si (CH 3 ) 3 ] 2 radical.
  • X is preferably chosen from the groups -OR and the groups - NRR 1 with R, R 'denoting alkyl substituents, linear or branched, or aromatic, substituted or unsubstituted, identical or different from each other;
  • n is an integer equal to or greater than 0, preferably equal to or greater than 1 and less than 3, more particularly equal to 1
  • m is an integer equal to or greater than 0, preferably equal to or greater than 0 and less than 3, more preferably equal to 0 or 1
  • m is more preferably equal to 1.
  • y is a non-zero integer from 1 to z, y is preferably 2 or 3.
  • L is a Lewis base.
  • the Lewis base is particularly selected from amines or ethers.
  • the Lewis base is pyridine or tetrahydrofuran (THF).
  • the compound according to the invention corresponding to formula (I) may also be in the form of an aggregate of aluminum salts of similar composition.
  • organometallic compounds of formula (I) and of their preparation process can be found in the scientific literature and in particular in Marcel Schreuder Groetheijt et al., Journal of Organometallic Chemistry, 1997, 1-5, 527 or Peter R. Markies et al., Journal of Organometallic Chemistry, 1991, 289-312, 402.
  • These compounds of formula (I) act as alkylating agents in catalytic systems based on a rare earth metal salt according to the invention.
  • the preferred compounds according to the invention are those of formula (I) based on an element of the 2nd column of the Periodic Table.
  • the compounds of formula (I) in which M denotes magnesium and y is 2 are particularly preferred. Among these, there may be mentioned, for example, magnesium di (ortho-N, N'-alkylaminoalkylbenzyl) and magnesium bisfortho- methoxybenzyl).
  • rare earth metal is meant according to the invention any element of the family of lanthanides, or yttrium or scandium.
  • the rare earth element is chosen from yttrium, neodymium, gadolinium or samarium elements, more preferentially neodymium or gadolinium.
  • the rare earth metal salt according to the invention can be represented by the formula Ln (A 1 J 3 (B) n , in which Ln is the rare earth element, A 1 is chosen from halides, carboxylates , the organophosphates, the alcoholates, the amides, the alkyls or the borohydrides and B is one or more solvent molecules complexed on the rare earth metal, n is an integer between 0 and 3.
  • the term complexed solvent is understood to include ethers, amines, phosphates and thioethers.
  • amine there may be mentioned the family of trialkylamines and aromatic amines such as pyridine or piperazine and its derivatives.
  • phosphate mention may be made, for example, of tri-n-butyl phosphate.
  • thioether mention may be made of the family of dialkyl sulphides such as dimethyl sulphide.
  • ether As ether, mention may be made, for example, of diethyl ether, 1,2-diethoxyethane, 1,2-di-n-propoxyethane, 1,2-di-n-butoxyethane, tetrahydrofuran, dioxane and tetrahydropyran. More particularly B is an ether, preferably tetrahydrofuran (THF). When A 1 is a halide, it is preferably a chloride. B is then preferably a THF molecule and n is 2.
  • THF tetrahydrofuran
  • a ' is a carboxylate, it is chosen from linear or branched aliphatic carboxylic acid esters having 6 to 16 carbon atoms in the linear chain, and esters of aromatic carboxylic acids having between 6 and 12 carbon atoms, substituted or unsubstituted.
  • neodecanoate versatate
  • octoate hexanoate
  • linear or branched or naphthenate
  • a ' is preferably 2-ethylhexanoate, naphthenate or rare earth neodecanoate.
  • a ' is chosen from organophosphates, it comprises phosphoric acid diesters of general formula (R 1 O) (RO) PO (OH), in which R 1 and R ", which may be identical or different, represent a radical alkyl, aryl or alkylaryl, Among these phosphoric acid diesters, R 'and R ", which are identical or different, are preferably an n-butyl radical, isobutyl, pentyl, amyl, isopentyl, 2,2-dimethylhexyl, 1-ethylhexyl, 2-ethylhexyl, tolyl, nonaphenoxyl.
  • the salt is more preferably rare earth bis (2-ethylhexyl) phosphate.
  • a 1 is chosen from alcoholates
  • neopentanolate may be mentioned.
  • a ' is chosen from the amide family, it comprises in particular dialkylamides, N, N-bis (dialkylsilyl) amides and N, N-bis (trialkylsilyl) amides, the alkyl groups having between 1 and 5 atoms. of carbons.
  • a 1 is chosen from dialkylamides
  • B is preferably THF and n is preferably 1 to 1. Then is preferably diisopropylamide and dimethylamide.
  • n is preferably 0.
  • a 1 is then preferably N, N-bis (trimethylsilyl) amide of formula -N [Si (CH 3 ) 3 ].
  • a ' is selected from N, N-bis (dialkylsilyl) amides
  • B is preferably THF and n is preferably 2 or 3. Then is N 1 N-bis (dimethylsilyl) ) amide of the formula -N [SiH (CH 3 J 2 ].
  • A' is preferably a (trialkylsilyl) alkyl, such as (trimethylsilyl) methyl or bis (trimethylsilyl) methyl.
  • a ' is selected from borohydrides, A' is preferably tetrahydroborate, B is preferably THF and n is preferably 2 or 3.
  • the rare earth metal salt is chosen from rare earth organophosphates, amides, alkyls or borohydrides. More particularly, the rare earth metal salt is chosen from rare earth tris [di (2-ethylhexyl) phosphate], rare earth tri [N, N-bis (trimethylsilyl) amide] or tris (borohydride) from rare earth.
  • the rare earth metal salt may be a salt of a mixture of rare earth metals or a mixture of several salts of one or more rare earth metals.
  • the catalytic system may comprise at least one additional compound of alkylaluminium or alkylaluminium halide type, then acting as an alkylating agent and / or halogen donors.
  • alkylaluminium or alkylaluminium halide type then acting as an alkylating agent and / or halogen donors.
  • trialkylaluminiums the alkyl radical being C ⁇ -C ⁇ , for example triethylaluminium, triisobutylaluminium, or trioctylaluminium; dialkylaluminum hydrides, the alkyl radical being C 2 -C 4 , for example diisobutylaluminum hydride;
  • the alkylaluminium halides the alkyl radical being C 2 -C 4 and the halogen being chlorine or bromine, for example diethylaluminum chloride, diethylaluminum bromide, ethylaluminium dichloride or sodium sesquichloride; ethylaluminum.
  • this alkylaluminum agent is preferably constituted by diisobutylaluminum hydride or triisobutylaluminum hydride. It is associated with a catalytic system comprising an organometallic compound of formula (II), it will be noted that this alkylating agent is preferably a mixture consisting of an alkylaluminium and an alkylaluminium halide, for example hydride of diisobutylaluminum or tri-isobutylaluminum and diethylaluminum chloride.
  • the catalytic system according to the invention may also comprise a conjugated pre-forming diene.
  • conjugated diene that can be used to preform the catalytic system according to the invention, mention may be made of 2-methyl-1,3-butadiene (or isoprene), 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, and 2-butadiene; methyl-3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, or any other conjugated diene having 4 to 8 carbon atoms; -butadiene being used on a preferential basis.
  • Another embodiment of the invention consists of the combination of these two embodiments.
  • the molar ratio (organometallic compound of formula (I) / rare earth metal) can have a value ranging from 1.5 to 20 (limits included), more preferably from 2 to 12.
  • the molar ratio (alkylating agent / rare earth metal) can have a value ranging from 2 to 20 (limits included). more preferably from 2 to 6.
  • the molar ratio (halogen / rare earth metal) may a value ranging from 2 to 3.5, to observe a satisfactory catalytic activity, more preferably 2.6 to 3.
  • the molar ratio may have a value ranging from 10 to 70, to observe a better catalytic activity and a reduced molecular weight distribution, more preferably 30 to 70.
  • the catalytic system according to the invention comprises a rare earth metal concentration equal to or greater than 0.002 mol / l and, preferably, ranging from 0.010 mol / l to 0.1 mol / l and more advantageously, ranging from 0.015 to 0.06 mol / L.
  • Another object of the invention is a process for the preparation of the catalytic system described above.
  • different catalytic constituents including the pre-formed conjugated diene, are brought into contact in an inert hydrocarbon solvent for a period of time. a duration between 0 and 30 minutes at a temperature possibly greater than ambient temperature, generally between 10 0 C and 80 0 C, followed by aging of the catalytic constituents, in the presence of said conjugated pre-forming diene.
  • inert hydrocarbon solvents are, for example, an aromatic solvent, such as toluene, or an aliphatic or alicyclic solvent, such as pentanes, n-pentane, iso-pentane, a mixture of hexanes, n-pentane and the like.
  • aromatic solvent such as toluene
  • aliphatic or alicyclic solvent such as pentanes, n-pentane, iso-pentane, a mixture of hexanes, n-pentane and the like.
  • hexane, cyclohexane, methylcyclohexane, a mixture of heptanes or n-heptane are, for example, an aromatic solvent, such as toluene, or an aliphatic or alicyclic solvent, such as pentanes, n-pentane, iso-pentane, a mixture of hexanes,
  • said catalytic system is advantageously prepared by carrying out a premixing for 0 to 30 minutes at a temperature ranging from 10 0 C to 80 0 C, introducing into a hydrocarbon solvent inert as defined above, the compound of formula (I) and optionally the alkylating agent and / or the halogenating agent, and then adding the metal salt of rare earth to this premix.
  • the catalytic system is specifically formed in situ, that is to say that all the catalytic constituents, the solvent, the rare earth metal salt, the compound of formula ( I), the monomer to be polymerized and optionally the alkylating agent and / or the halogenating agent, are introduced into the reactor just before polymerization in an indifferent order.
  • Another subject of the invention is a process for preparing a functionalized diene elastomer by polymerizing at least one conjugated diene monomer in the presence of said catalytic system based on a metal salt of rare earth (s).
  • said polymerization reaction can be carried out at a temperature preferably ranging from 0 to 100 ° C., in an inert hydrocarbon polymerization solvent, such as pentane, n-pentane, iso-pentane, a mixture of hexanes, n-hexane, cyclohexane, methylcyclohexane, a mixture of heptanes or n-heptane, or in bulk.
  • an inert hydrocarbon polymerization solvent such as pentane, n-pentane, iso-pentane, a mixture of hexanes, n-hexane, cyclohexane, methylcyclohexane, a mixture of heptanes or n-heptane, or in bulk.
  • the weight ratio solvent / monomer (s) before the polymerization reaction is advantageously from 1 to 10 and preferably from 4 to 7.
  • the polymerization process can be carried out in a continuous or batch process.
  • said catalytic system is present in the reaction medium in a concentration of between 5 and 5000 ⁇ mol per 100 grams of monomer to be polymerized, preferably between 50 and 500 ⁇ mol per 100 grams of monomer. to polymerize.
  • diene elastomer that can be prepared by the process according to the invention, mention may be made of any homopolymer or copolymer obtained by homopolymerization or copolymerization of at least one conjugated diene monomer having from 4 to 12 carbon atoms, optionally with a compound vinylaromatic.
  • 1,3-butadiene, isoprene, 2,3-di (C 1 -C 8) 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.
  • Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, 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 may be for example block, statistic, sequence, micro-block, and they may be coupled and / or star with a coupling agent and / or starring.
  • said diene elastomer is chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR) and synthetic polyisoprenes (IR).
  • the catalytic system used in the process according to the invention makes it possible in particular to obtain diene elastomers functionalized at the end of the chain by an aromatic polar function, originating from the organometallic compound of formula (I), without having to involve a step additional reaction on a functionalizing agent.
  • the degree of functionalization of the diene elastomer is high. It can reach values ranging from 75% to 100%, preferably from 90% to 100%, and even substantially equal to 100%.
  • catalytic systems used in the process according to the invention advantageously make it possible to obtain conjugated diene polymers, for example polybutadiene, having a polydispersity index of a value ranging from 1 to 3. More particularly, catalytic systems used in the process according to the invention advantageously make it possible to obtain homopolymers of butadiene having both a polydispersity index of a value ranging from 1 to 2.5, preferably a polydispersity index of a value ranging from 1 to 1, 5 (measured by size exclusion chromatography technique SEC, see annex 2 attached), and a high functionalization rate which can reach values ranging from 75%, or even 90%, to 100%, and even substantially equal to 100%.
  • Functionalized diene elastomers obtained by polymerization of at least one conjugated diene in the presence of a catalytic system according to the invention are also the subject of the invention.
  • the invention more particularly relates to functionalized diene elastomers carrying at the end of the chain an aromatic polar function.
  • elastomers are characterized in that they comprise at least one chain end a polar function originating from the organometallic compound of formula (I), which can be represented by formula (II):
  • R1, R2, R3, R4, n, m and X being as defined above in formula (I).
  • 75% to 100% of chains of the elastomer are functionalized at the end of the chain, even more preferably 90% to 100%, or even substantially 100%, of the elastomeric chains are functionalized.
  • the functionalized diene elastomers according to the invention can advantageously be used in reinforced rubber compositions in which they improve the hysteresis properties by promoting interaction with respect to the filler.
  • the choice of the functional group can be made judiciously depending on the type of reinforcing filler used.
  • Such rubber compositions are then particularly suitable for application in a tire for a motor vehicle with a view to reducing the rolling resistance.
  • Such reinforced rubber compositions are also the subject of the invention.
  • These rubber compositions comprise at least one functionalized diene elastomer obtained by polymerization of at least one conjugated diene in the presence of the system. catalytic converter according to the invention.
  • This elastomer may optionally be used in a blend with at least one or more elastomers conventionally used in tire rubber compositions and chosen from natural rubber, synthetic diene elastomers, optionally coupled and / or star-shaped and / or partially or fully functionalized. , synthetic elastomers other than diene, or polymers other than elastomers.
  • the reinforcing filler present in the rubber composition is selected from inorganic fillers, such as silica, organic fillers, such as carbon black, or mixtures of these fillers.
  • compositions may furthermore comprise various additives usually present in rubber compositions, in particular intended for motor vehicle tires.
  • additives usually present in rubber compositions, in particular intended for motor vehicle tires.
  • gum / filler binding agents non-reinforcing fillers, various processing agents or other stabilizers, plasticizers, pigments, antioxidants, anti-fatigue agents, anti-ozonating waxes, adhesion promoters, reinforcing or plasticizing resins
  • a crosslinking system based on either sulfur and / or peroxide and / or bismaleimides
  • crosslinking activators comprising zinc monoxide and stearic acid, derivatives thereof, guanidics, extension oils, one or more silica overcoating agents.
  • organometallic syntheses were performed under an argon inert atmosphere, using either Schlenk techniques or a glove box. All solvents used in these syntheses are dry according to conventional techniques (distillation on sodium or molecular sieve) and stored under an inert atmosphere. For example, pentane and THF are freshly distilled on sodium / benzophenone. All the reagents come from Sigma-Aldrich, Acros Organics, Strem and Fluka.
  • Nd (BH 4) 3 (THF) 3 was prepared according to a procedure described in the literature S. Cendrowski-Guillaume, M. Nierlich, M. Lance, M. Ephritikhine, Organometallics, 1998, 17, 786.
  • a bottle “Steinie” previously washed and dried and equipped with a capsule and a seal to air and moisture is used.
  • the polymerization reactions of butadiene are carried out at a temperature of between 50 and 60 ° C and under an inert atmosphere (nitrogen).
  • methylcyclohexane is introduced into said bottle as a polymerization solvent. This methylcyclohexane is bubbled with nitrogen for 10 minutes to remove volatile impurities.
  • a mass ratio "polymerization solvent (methylcyclohexane) / monomer (butadiene)" of between 5 and 7 is used (this weight ratio is called S / M hereinafter).
  • the neodymium-based precursor i.e. the neodymium tris (borohydride), and the functional cocatalyst are air-sensitive compounds. For this reason, they are introduced through sealed glass ampules, which are then broken at the beginning of the polymerization reaction.
  • the amount of neodymium catalytic base and the amount of alkylating agent are expressed in ⁇ mol and ⁇ Mcm ( ⁇ mol per 100 grams of monomer). Methanol (1 ml) or acetylacetone (used in excess) are used to stop the polymerization reactions.
  • N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD) and I ⁇ O2246 are used as protective agent for the polymeric solutions obtained (according to a mass of 0.2 g of each per 100 g of elastomer) .
  • the polybutadienes are then extracted from the polymer solutions thus obtained, either by stripping with water vapor in the presence of calcium tamolate and either drying on rolls at 100 ° C., ie drying in an oven at 60 ° C. under vacuum with a slight nitrogen stream, either by devolatilization under partial vacuum with nitrogen sweep at 50 ° C. Sample test
  • BOMAG butyloctylmagnesium
  • Mg (RN) 2 bis (ortho-N, N-dimethylaminobenzyl) magnesium
  • b Mn and Ip are determined by steric exclusion chromatography (Appendix 1)
  • c The microstructure is determined by a near infra-red method ( Annex 2)
  • d The proportion of chains functionalized by the dimethylamino-benzyl group is determined by 1 H NMR and 13 C (see Annex 3)
  • e na means "does not apply"
  • Size Exclusion Chromatography is used to separate macromolecules in solution by size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, the larger ones being eluted first.
  • the SEC allows to apprehend the distribution of the molar masses of a polymer.
  • the apparatus used is a "WATERS alliance" chromatograph.
  • the elution solvent is (tetrahydrofuran + 1% vol diisopropylamine + 1% vol triethylamine), the flow rate 0.7 ml / min, the temperature of the system 35 ° C and the duration of analysis of 90 min.
  • a set of four WATERS columns in series, trade names "STYRAGEL HMW7", “STYRAGEL HMW6E” and two “STYRAGEL HT6E" are used.
  • the injected volume of the solution of the polymer sample is 100 ⁇ l.
  • the detector is a differential refractometer "WATERS 2410" and the chromatographic data exploitation software is the “WATERS EMPOWER” system.
  • the calculated average molar masses relate to a calibration curve made for polybutadienes with the following microstructure: 11% by mass of type-1-2 units and 48% by mass of type 1-4 trans units.
  • NIR near infra-red spectroscopy
  • NIR near infrared
  • the polymers are analyzed by 1 H NMR and 13 C NMR using a Bruker AV500 spectrometer equipped with a BBI 1 HX 5 mm probe.
  • the solvent used for the analysis is a mixture of CS 2 and C 6 D 12 .
  • Calibration is performed from the protonated CS2 impurity with a chemical shift of 7.12 ppm.
  • the quantification of the number of functional chains is carried out either from the aromatic proton signal at 6.80 ppm, which integrates for a proton or from the solid mass between 2.7 and 2.3 ppm (-N (CH 3 groups ) 2 and CH 2 in alpha of the aromatic nucleus), which integrates for 8 protons.
  • These values are related to the integration of the characteristic signals of the 1,4-cis, 1,4-trans and 1,2 units of the polybutadiene. The two calculation methods lead to statistically identical values between them.

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EP10722954A 2009-06-02 2010-06-01 Systeme catalytique pour la polymerisation de dienes conjugues, procede de polymerisation et polymere fonctionnel obtenu Ceased EP2438095A1 (fr)

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FR2946048B1 (fr) * 2009-06-02 2012-12-28 Michelin Soc Tech Systeme catalytique pour la polymerisation de dienes conjugues,procede de polymerisation et polymere fonctionnel obtenu
JP5965169B2 (ja) * 2012-03-16 2016-08-03 株式会社ブリヂストン 重合触媒組成物、及び重合体組成物の製造方法
WO2016080764A1 (ko) * 2014-11-20 2016-05-26 주식회사 엘지화학 공액 디엔의 중합용 촉매 조성물
FR3029918B1 (fr) 2014-12-12 2018-01-26 Universite Claude Bernard Lyon 1 Agent de transfert pour la preparation d'une polyolefine fonctionnelle ou telechelique
FR3029920B1 (fr) 2014-12-12 2016-12-09 Univ Claude Bernard Lyon Polyolefine fonctionnelle ou telechelique, ses derives, et son procede de preparation
KR101899636B1 (ko) 2015-06-24 2018-09-17 주식회사 엘지화학 공액 디엔계 중합체 제조용 촉매 조성물 및 이를 이용하여 제조된 공액 디엔계 중합체
FR3044664B1 (fr) * 2015-12-08 2017-12-29 Michelin & Cie Copolymere monofonctionnel ou telechelique de 1,3-diene et d'ethylene ou d'alpha-monoolefine.
FR3044663B1 (fr) * 2015-12-08 2017-12-29 Michelin & Cie Copolymere monofonctionnel ou telechelique de 1,3-butadiene et d'ethylene.
FR3061181B1 (fr) 2016-12-22 2019-07-05 Universite Claude Bernard Lyon 1 Copolymere d'ethylene et de derive styrenique, sa preparation et son utilisation
FR3068973B1 (fr) 2017-07-11 2020-08-28 Centre Nat Rech Scient Procede de fonctionnalisation d'un polydiene stereo-regulier
KR102193437B1 (ko) 2017-10-30 2020-12-21 주식회사 엘지화학 공액디엔 중합용 촉매의 제조방법, 촉매 및 이를 이용한 공액디엔계 중합체의 제조방법
EP3720889B1 (fr) 2017-12-05 2025-08-06 Compagnie Générale des Etablissements Michelin Procede continu de preparation d'un elastomere dienique

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CN102449002A (zh) 2012-05-09
WO2010139449A1 (fr) 2010-12-09
BRPI1011131A2 (pt) 2018-02-06
KR101706925B1 (ko) 2017-02-15
CN102449002B (zh) 2014-09-24
US20130274407A1 (en) 2013-10-17
JP5623514B2 (ja) 2014-11-12
FR2946048A1 (fr) 2010-12-03
US9315590B2 (en) 2016-04-19

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