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    • 专利摘要:
    The present invention relates to a catalytic system based at least on a conjugated diene monomer preforming, an organometallic compound as cocatalyst, a metallocene of formula {P (Cp1) (Cp2) Y}, Y designating a group comprising a metal atom which is a rare earth, Cp1 and Cp2, which are identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted, P being a group bridging the two groups Cp1 and Cp2, and comprising a silicon or carbon atom. Such a catalytic system has a stability of the catalytic activity improved in time, especially storage.
    公开号:FR3044662A1
    申请号:FR1561770
    申请日:2015-12-03
    公开日:2017-06-09
    发明作者:Vincent Lafaquiere；Julien Thuilliez
    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:

    The present invention relates to a preformed catalytic system based on rare earth metallocenes, particularly useful in the polymerization of monomers such as conjugated dienes, ethylene, α-ffiOoolefins and mixtures thereof. The invention also relates to a process for preparing said catalytic system, as well as its use in the synthesis of polymers.
    The catalytic systems based on rare earth metallocenes are known: they are for example described in patent applications EP 1092 731, WO2004035639 and WO 2007054224 in the name of the Applicants for use in the polymerization of monomers such as conjugated dienes, ethylene and α-monoolefins. They are the reaction product of a lanthanide metallocene and a cocatalyst in a hydrocarbon solvent. These catalytic systems, thus formed, have the disadvantage of having their catalytic activity decrease storage. In order to guarantee the specifications of the polymer to be synthesized, it is then necessary in the polymerization process to compensate for the fluctuations in the catalytic activity of the catalytic system which result from its storage. This compensation passes through the readjustment of the parameters of the polymerization process such as the respective amounts of the monomers and the catalyst system. It follows that a phase of setting the parameters of the polymerization process and a phase of stabilization of the polymerization tool are required before the tool is able to produce the polymer specification. These adjustment and stability phases have the effect of reducing the productivity of the production tool.
    However, some of these catalytic systems are of interest insofar as they allow access to copolymers of ethylene and 1,3-butadiene of original microstructure, because of the formation of cyclic units in the copolymer chain, copolymers of interest for use in rubber formulations for pneumatic application, as described in patent application WO 2014114607 in the name of the Applicants. It is therefore of interest to find a solution for improving the stability over time of the catalytic activity of these catalytic systems, especially storage stability.
    The Applicants, continuing their efforts, have discovered a catalytic system based on a rare earth metallocene having a stability of the catalytic activity improved storage, which solves the problems encountered mentioned above. The catalytic system according to the invention has the particularity of being a catalytic system of "preformed" type.
    Thus, a first subject of the invention is a catalytic system based at least on: a conjugated diene monomer for preforming a metallocene of formula (c) of an organometallic compound as a co-catalyst, {P (Cp1 ) (Cp2) Y} (I) where Y denotes a group comprising a metal atom which is a rare earth, and Cp1 and Cp2, which are identical or different, are chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted, P being a group bridging the two groups Cp1 and Cp2, and comprising a silicon or carbon atom. The invention also relates to a process for preparing the catalytic system according to the invention. The invention also relates to a process for the preparation of a polymer which comprises the polymerization of a monomer in the presence of the catalytic system according to the invention.
    I. DETAILED DESCRIPTION OF THE INVENTION
    In the present description, any range of values designated by the expression "between a and b" represents the range of values greater than "a" and 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 of values from "a" to "b" (i.e. including the strict limits a and b).
    By the term "based on" used to define the constituents of the catalytic system is meant the mixing of these constituents, or the product of the reaction of a part or all of these constituents together.
    In the present application, the term metallocene is understood to mean an organometallic complex whose metal, in this case the rare earth atom, is bonded to a ligand molecule consisting of two Cp1 and Cp2 groups connected to each other by a P bridge. groups Cp1 and Cp2, identical or different, are selected from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, these groups may be substituted or unsubstituted. It is recalled that the rare earths are metals and denote the elements scandium, yttrium and lanthanides whose atomic number varies from 57 to 71.
    The catalytic system according to the invention has the essential characteristic of being a preformed catalyst from a conjugated diene monomer. The conjugated diene pre-forming monomer may be a conjugated diene having from 4 to 8 carbon atoms, preferably a 1,3-diene, more preferably 1,3-butadiene.
    The preformed conjugated diene monomer is preferably used in a molar ratio (monomer conjugated diene preform / metallocene metal) ranging from 5 to 1000, preferably from 10 to 500.
    The metallocene used as a base component in the catalytic system according to the invention corresponds to the formula (I) {P (Cp1) (Cp2) Y} (I) in which - Y denotes a group comprising a metal atom which is a rare earth,
    Cp1 and Cp2, identical or different, are selected from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted, - P is a group bridging the two groups Cp1 and Cp2, and comprising a silicon or carbon atom.
    In the formula (I), the rare earth atom is linked to a ligand molecule consisting of the two groups Cp1 and Cp2 linked together by the bridge P. As substituted cyclopentadienyl, fluorenyl and indenyl groups, mention may be made of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms or by trialkylsilyl radicals such as SiMe3. The choice of radicals is also oriented by accessibility to the corresponding molecules that are cyclopentadienes, fluorenes and substituted indenes, because they are commercially available or easily synthesizable. As substituted fluorenyl groups, there may be mentioned particularly 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl. The positions 2, 3, 6 and 7 respectively designate the position of the carbon atoms of the rings as shown in the diagram below, the position 9 corresponding to the carbon atom to which the P bridge is attached.
    As substituted cyclopentadienyl groups, there may be mentioned particularly those substituted in the 2-position, more particularly the tetramethylcyclopentadienyl group. Position 2 (or 5) denotes the position of the carbon atom which is adjacent to the carbon atom to which bridge P is attached, as shown in the diagram below.
    As substituted indenyl groups, there may be mentioned particularly those substituted in the 2-position, more particularly 2-methylindenyl, 2-phenylindenyl. Position 2 denotes the position of the carbon atom which is adjacent to the carbon atom to which bridge P is attached, as shown in the diagram below.
    According to a preferred embodiment of the invention, Cp1 and Cp2 are identical and are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C13H8.
    The catalytic system according to this preferred embodiment has the particularity of producing copolymers of butadiene and ethylene which additionally comprise monomeric units ethylene and butadiene units of 1,2-cyclohexane cyclic units of the following formula:
    Advantageously, Cp1 and Cp2 are identical and each represents an unsubstituted fluorenyl group of formula C13H8, represented by the symbol Flu.
    According to a preferred embodiment of the invention, the symbol Y represents the group Met-G, with Met denoting a metal atom which is a rare earth and with G denoting a group comprising the borohydride unit BH4 or designating an atom of halogen X selected from the group consisting of chlorine, fluorine, bromine and iodine. Advantageously, G denotes chlorine or the group of formula (II): (ΒΗ4) (ΐ + ν) .ίγ-Νχ (11) in which L represents an alkali metal selected from the group consisting of lithium, sodium and potassium, N represents a molecule of an ether, x, integer or not, is equal to or greater than 0, y, integer, is equal to or greater than 0.
    As ether is suitable any ether which has the power to complex the alkali metal, including diethyl ether and tetrahydrofuran.
    According to any of the embodiments of the invention, the metallocene metal useful in the invention, in this case the rare earth, is preferably a lanthanide whose atomic number ranges from 57 to 71, more preferably neodymium, Nd.
    The bridge P linking the Cp1 and Cp2 groups preferably corresponds to the formula ZR * R2, in which Z represents a silicon or carbon atom, R1 and R2, which may be identical or different, each represent an alkyl group comprising from 1 to 20 atoms carbon, preferably methyl. In the formula ZR * R2, Z preferably denotes a silicon atom, Si.
    According to a particularly preferred embodiment, the metallocene is dimethylsilyl bis-fluorenyl neodymium borohydride of formula (III): [Me 2 Si (Flu) 2 Nd 2 -BH 4) 2 Li (THF) (III) in which Flu represents the group C 13 H 8 .
    Another basic constituent of the catalytic system according to the invention is the cocatalyst capable of activating the metallocene with respect to the polymerization, in particular in the polymerization initiation reaction. The cocatalyst is well known an organometallic compound. Suitable organometallic compounds capable of activating the metallocene, such as organomagnesium, organoaluminum and organolithium compounds.
    The cocatalyst is preferably an organomagnesium compound, that is to say a compound which has at least one C-Mg bond. As organomagnesium compounds, mention may be made of diorganomagnesiums, in particular dialkylmagnesians and organomagnesium halides, in particular alkylmagnesium halides. The diorganomagnesium compound has two C-Mg bonds, in this case C-Mg-C; the organomagnesium halide has a C-Mg bond. More preferably, the cocatalyst is a diorganomagnesian.
    According to a particularly preferred embodiment of the invention, the cocatalyst is an organometallic compound comprising an alkyl group bonded to the metal atom. As a cocatalyst, also known as an alkylating agent, alkyl magnesium (also called alkyl magnesium), especially dialkyl magnesium (also called dialkyl magnesium) or alkyl magnesium halide (also known as alkyl magnesium halide), are particularly suitable. butyloctylmagnesium and butylmagnesium chloride. The cocatalyst is advantageously butyloctylmagnesium.
    The cocatalyst is used in a molar ratio (cocatalyst / metallocene metal) of preferably from 0.5 to 20, more preferably from 1 to 10.
    According to any one of the embodiments of the invention, the catalytic system preferably comprises a hydrocarbon solvent. The catalyst system may be in the form of a solution when it is in the presence of a hydrocarbon solvent. The hydrocarbon solvent may be aliphatic such as methylcyclohexane or aromatic such as toluene. The hydrocarbon solvent is preferably aliphatic, more preferably methylcyclohexane. Generally, the catalyst system is stored as a solution in the hydrocarbon solvent before being used in polymerization. One can speak then of catalytic solution which includes the catalytic system and the hydrocarbon solvent.
    When the catalyst system is in solution, its concentration is defined by the metallocene metal content in the solution. The concentration of metallocene metal has a value ranging preferably from 0.0001 to 0.05 mol / l, more preferably from 0.001 to 0.03 mol / l.
    Another object of the invention is the preparation of the catalytic system described above.
    The process for preparing the catalytic system according to the invention comprises the following steps a) and b): a) reacting the cocatalyst and the metallocene in a hydrocarbon solvent, b) reacting the conjugated diene conjugating monomer with the product. reaction of step a).
    The metallocene used for the preparation of the catalyst system can be in the form of crystallized or non-crystalline powder or in the form of single crystals. The metallocene may be in a monomeric or dimer form, these forms depending on the mode of preparation of the metallocene, as for example that is described in the application WO 2007054224 A2. The metallocene can be prepared in a conventional manner by a method analogous to that described in the documents EPI 092 731, WO 2007054223 and WO 2007054224, in particular by reaction under an inert and anhydrous conditions of the alkali metal salt of the ligand with a sodium salt. rare earth such as a halide or a rare earth borohydride, in a suitable solvent, such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to those skilled in the art. After reaction, the metallocene is separated from the reaction by-products by techniques known to those skilled in the art, such as filtration or precipitation in a second solvent. The metallocene is finally dried and isolated in solid form. Step a) corresponds to the activation step, commonly also called alkylation, of the metallocene by the cocatalyst; step b) corresponds to the preforming step of the catalytic system.
    The hydrocarbon solvent used in the synthesis of the catalytic system is generally of the same chemical nature as the solvent of the catalytic solution defined above, that is to say an aliphatic hydrocarbon solvent such as methylcyclohexane or aromatic such as toluene. Typically, the hydrocarbon solvent in which the catalyst system is in solution comes from the preparation of the catalyst system.
    In step a), the hydrocarbon solvent is generally added the cocatalyst and then the metallocene. Stage a) generally takes place at a temperature ranging from 20 to 80 ° C. The reaction time of step a) is preferably between 5 and 60 minutes, more preferably between 10 and 20 minutes. Step b) is generally carried out at a temperature ranging from 40 to 100 ° C., preferably from 60 to 90 ° C. The reaction time of step b) typically varies from 1 hour to 24 hours, preferably from 5 hours to 12 hours. In step b), the pre-formed conjugated diene monomer is added to the reaction product of step a). Step b) may be followed by a degassing step c) to remove the pre-formed conjugated diene monomer which has not reacted in step b).
    Like any synthesis made in the presence of organometallic compound, the synthesis takes place under anhydrous conditions under an inert atmosphere as well for step a) as for step b) and optionally step c). Typically, the reactions are conducted from anhydrous solvents and monomers under nitrogen or argon anhydrous. Steps a), b) and c) are generally conducted with stirring.
    Before being used, for example, in polymerization, the catalyst system thus obtained in solution may be stored under an inert atmosphere, for example under nitrogen or argon, in particular at a temperature ranging from -20 ° C. to room temperature (23 ° C.) .
    Another object of the invention is a process for the preparation of a polymer which comprises the polymerization of a monomer M in the presence of the catalytic system according to the invention. The monomer M is to be distinguished from the preforming monomer used in the preparation of the catalytic system in step b): the monomer M may or may not be of the same chemical nature as the monomer used in step b). The monomer M is preferably selected from the group of monomers consisting of conjugated dienes, ethylene, α-monoolefins and mixtures thereof. More preferably, the monomer M is a 1,3-diene preferably having from 4 to 8 carbon atoms, in particular 1,3-butadiene or isoprene, or a mixture of 1,3-butadiene and 'ethylene.
    Depending on the microstructure and the length of the polymer chains prepared by the process according to the invention, the polymer may be an elastomer.
    The polymerization is preferably carried out in solution, continuously or batchwise. The polymerization solvent may be a hydrocarbon, aromatic or aliphatic solvent. As an example of a polymerization solvent, mention may be made of toluene and methylcyclohexane. The monomer charge may be introduced into the reactor containing the polymerization solvent and the catalytic system or conversely the catalytic system may be introduced into the reactor containing the polymerization solvent and the monomer charge. The polymerization is typically conducted under anhydrous conditions and in the absence of oxygen, optionally in the presence of an inert gas. The polymerization temperature generally varies in a range from 40 to 120.degree. C., preferably from 60 to 90.degree.
    The polymerization can be stopped by cooling the polymerization medium. The polymer may be recovered according to conventional techniques known to those skilled in the art, for example by precipitation, by evaporation of the solvent under reduced pressure or by stripping with water vapor.
    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.
    II. EXAMPLES OF CARRYING OUT THE INVENTION 11.1- Preparation of Catalytic Systems in Accordance with the Invention: Examples 1 to 6
    The C1-C6 catalytic systems according to the invention are prepared according to the following procedure.
    In a reactor containing the hydrocarbon solvent methylcyclohexane (MCH) or toluene (Toi), the cocatalyst, butyloctylmagnesium (BOMAG) and then the metallocene [Me2Si (Flu) 2Nd (p-BH4) 2Li (THF)] are added to the The activation time is 10 minutes, the reaction temperature is 20 ° C. (step a)). Then, the pre-formed conjugated diene monomer, 1,3-butadiene, is introduced into the reactor in the proportions indicated in Table I. The preforming reaction proceeds at a temperature indicated in Table I, for a duration also indicated. in Table I. At the end of step b), the reactor is degassed and flushed with nitrogen to remove unconverted 1,3-butadiene. The metallocene may be prepared according to the procedure described in the patent application WO 2007054224. 11.2- Preparation of Catalytic Systems not in Accordance with the Invention: Examples 7,8 and 9
    The catalytic system C7 not according to the invention is prepared according to the method disclosed in the patent application WO 2007054224 and described below:
    In a reactor containing toluene (Toi), the cocatalyst, butyloctylmagnesium (BOMAG) and the metallocene [Me2Si (Flu) 2Nd (p-BH4) 2Li (THF)] are added in the amounts indicated in Table II. The activation time is 10 minutes, the reaction temperature is 20 ° C. Its preparation conditions are shown in Table II.
    The C8 catalytic system not according to the invention is prepared in a similar manner to the C7 catalytic system except for the solvent which is methylcyclohexane.
    The catalytic system C9 not according to the invention is prepared according to the following procedure:
    In a reactor containing the hydrocarbon solvent methylcyclohexane (MCH), the cocatalyst, butyloctylmagnesium (BOMAG) and then the metallocene [Me2Si (Flu) 2Nd (p-BH4) 2Li (THF)] are added in the amounts indicated in the table. II. The activation time is 1 h, the reaction temperature is 60 ° C.
    The catalytic systems C7, C8 and C9 are not in accordance with the invention because of the absence of the preforming step (stage b)). These are catalytic systems known from the state of the art, in particular patent application WO 2007054224. 11.3- Storage conditions for catalytic systems:
    Unless otherwise indicated, the catalytic systems C1 to C6 according to the invention are stored immediately after their preparation in bottles sealed under a nitrogen atmosphere at -20 ° C.
    For the study of the stability of the catalytic activity in the storage of a catalytic system according to the invention, bottles hermetically sealed under nitrogen containing the catalytic system C1 are also stored at 4 ° C. or 23 ° C.
    Catalyst systems C7 and C8 not in accordance with the invention are not stored and are used immediately in the polymer synthesis to determine their catalytic activity.
    The catalytic system C9 not according to the invention, if it is not used immediately in the polymer synthesis, is stored immediately after its preparation in bottles sealed under a nitrogen atmosphere at 23 ° C. 11.4- Stability of catalytic activity of catalytic systems: Examples 10 to 14
    Catalyst systems Cl and C9 are used in polymerization without having been stored after their synthesis or after having been stored at ambient temperature (23 ° C.) or at 4 ° C. for varying periods of time. The catalytic activities of the catalytic systems Cl and C9 are determined, according to whether they have been stored or not, under the polymerization conditions described below.
    The polymerization is conducted at 80 ° C and at an initial pressure of 4 bar in a 500 ml glass reactor containing 300 ml of polymerization solvent, methylcyclohexane, catalyst system and monomers, 1,3-butadiene monomers and ethylene being introduced in the form of a gaseous mixture containing 20 mol% of 1,3-butadiene. The polymerization reaction is stopped by cooling and degassing the reactor. The copolymer is recovered by precipitation in methanol and then dried. The weighed mass makes it possible to determine the average catalytic activity of the catalytic system expressed in kilograms of copolymer synthesized per mole of neodymium metal and per hour (kg / mol.h).
    The results of catalytic activity according to the time and storage temperature of the catalyst system in solution are shown in Table III.
    It is observed that the catalytic activity of the catalytic system C1 is the same before or after storage. Even a storage of the catalytic Cl system of more than 45 days at 23 ° C or more than 3 months at 4 ° C does not have the effect of reducing its catalytic activity.
    On the other hand, it is observed that the C9 catalytic system which is not in accordance with the invention does not exhibit a catalytic activity that is as stable at storage at 23 ° C. as Cl. Indeed, the catalytic system C9 exhibits a catalytic decay of more than 20%. % after only 10 days of storage at 23 ° C.
    Maintaining the catalytic activity over a long period makes it possible to use a single production batch of a catalytic system according to the invention over this same period without having to proceed with readjustment phases of the process parameters of the invention. polymerization and stability of the polymerization tool during this period, while ensuring the specifications of the polymer to be synthesized. II.5-Comparison of the Catalytic Activity of the Catalytic Systems According to the Invention with that of the Catalytic Systems of the State of the Art: Examples 10, 13 and PI to P7
    The catalytic systems C1 to C6 in accordance with the invention and the catalytic systems C7 to C9 not in accordance with the invention are each used in the polymerization of a mixture of ethylene and 1,3-butadiene according to the procedure described in below.
    The polymerization is carried out at 80 ° C. and at an initial pressure of 4 bar in a 500 ml glass reactor containing 300 ml of polymerization solvent, methylcyclohexane (Example 10, Example 13, Examples PI to P5 and P7) or the toluene (example P6), the catalyst system and the monomers, 1,3-butadiene monomers and ethylene being introduced in the form of a gas mixture containing 20 mol% of 1,3-butadiene. The polymerization reaction is stopped by cooling and degassing the reactor. The copolymer is recovered by precipitation in methanol and then dried. The weighed mass makes it possible to determine the average catalytic activity of the catalytic system expressed in kilograms of copolymer synthesized per mole of neodymium metal and per hour (kg / mol.h).
    The average catalytic activities calculated for each of the catalyst systems are shown in Tables III and IV. Examples 10, PI to P5 are in accordance with the invention because they implement a catalytic system according to the invention (C1 to C6); Examples 13, P6 and P7 are not in accordance with the invention since they implement a catalytic system of the state of the art (C7, C8 and C9).
    It is noted that for a given hydrocarbon solvent of polymerization, methylcyclohexane, the catalytic activity of the catalytic systems C1 to C6 is at least equal to or greater than that of the catalytic system of the state of the art (C8 or C9). Indeed, the catalytic activity of the catalytic systems according to the invention determined in Examples P1 to P5 is 1.13 to 1.26 times greater than that of C8 determined in Example P7.
    In addition, the activity of the catalytic systems C1 to C6 used for a polymerization in methylcyclohexane is comparable to or even greater than that of the catalytic system of the state of the art C7 for a polymerization in toluene, determined in the example P6.
    The preformation of the catalytic system according to the invention also makes it possible to improve the productivity of the catalytic systems for the copolymerization of olefin and conjugated diene in an aliphatic hydrocarbon solvent and to obtain aliphatic hydrocarbon solvent productivity similar to that obtained in aromatic hydrocarbon solvent with the catalytic systems of the state of the art, or even higher.
    Finally, the catalyst systems according to the invention can be synthesized as well as aromatic solvent (toluene, Examples 2 and 3) in aliphatic solvent without affecting their catalytic activity. Indeed, the catalytic activity of C2 and C3 (Examples PI and P2) is comparable to that of Cl and C4 to C6 synthesized in an aliphatic hydrocarbon solvent, methylcyclohexane (Examples 10 and P3 to P5).
    Table I Table II
    Table III Table IV
    权利要求:
    Claims (27)
    [1" id="c-fr-0001]
    claims
    1. Catalytic system based at least on: • a pre-formed conjugated diene monomer • a metallocene of formula (I) • an organometallic compound as cocatalyst, {P (Cp1) (Cp2) Y } (I) Y denoting a group comprising a metal atom which is a rare earth, Cp1 and Cp2, which are identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted, P being a group bridging the two groups Cp1 and Cp2, and comprising a silicon or carbon atom.
    [2" id="c-fr-0002]
    2. Catalyst system according to claim 1 wherein the cocatalyst is an organomagnesium, preferably a diorganomagnesian.
    [3" id="c-fr-0003]
    3. Catalyst system according to any one of claims 1 to 2 wherein the cocatalyst is an organometallic compound having an alkyl group bonded to the metal atom.
    [4" id="c-fr-0004]
    4. Catalyst system according to any one of claims 1 to 3 wherein the cocatalyst is a dialkylmagnesian or an alkylmagnesium halide, preferably butyloctylmagnesium or butylmagnesium chloride, more preferably butyloctylmagnesium.
    [5" id="c-fr-0005]
    5. Catalyst system according to any one of claims 1 to 4 wherein Cp1 and Cp2 are identical and are selected from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C13H8.
    [6" id="c-fr-0006]
    6. Catalyst system according to any one of claims 1 to 5 wherein Cp1 and Cp2 each represent an unsubstituted fluorenyl group of formula C13H8.
    [7" id="c-fr-0007]
    7. Catalyst system according to any one of claims 1 to 6, wherein the symbol Y represents the group Met-G, with Met denoting a metal atom which is a rare earth and G denoting a group comprising the borohydride unit BH4 or designating a halogen atom X selected from the group consisting of chlorine, fluorine, bromine and iodine.
    [8" id="c-fr-0008]
    The catalyst system of claim 7 wherein G denotes chlorine or the group of formula (II) (BH4) (i + y) -Ly-Nx (II) wherein L represents an alkali metal selected from the group consisting of lithium, sodium and potassium, N represents a molecule of an ether, preferably diethyl ether or tetrahydrofuran, x, integer or not, is equal to or greater than 0, y, integer, is equal to or greater than 0.
    [9" id="c-fr-0009]
    9. Catalyst system according to any one of claims 1 to 8 wherein the rare earth is a lanthanide whose atomic number varies from 57 to 71.
    [10" id="c-fr-0010]
    10. Catalyst system according to any one of claims 1 to 9 wherein the rare earth is neodymium, Nd.
    [11" id="c-fr-0011]
    11. Catalyst system according to any one of claims 1 to 10 wherein the bridge P has the formula ZRXR2, Z representing a silicon or carbon atom, R1 and R2, identical or different, each representing an alkyl group comprising 1 to 20 carbon atoms, preferably methyl.
    [12" id="c-fr-0012]
    The catalyst system of claim 11 wherein Z is Si.
    [13" id="c-fr-0013]
    13. Catalyst system according to any one of claims 1 to 12 wherein the metallocene is neodymium dimethylsilyl bis-fluorenyl borohydride of formula (III): [Me2Si (Flu) 2Nd (p-BH4) 2Li (THF)] ( III) Flu representing the group C13H8.
    [14" id="c-fr-0014]
    14. Catalyst system according to any one of claims 1 to 13 wherein the preformed conjugated diene monomer is a 1,3-diene.
    [15" id="c-fr-0015]
    The catalyst system of claim 14 wherein the conjugated diene pre-forming monomer is 1,3-butadiene.
    [16" id="c-fr-0016]
    16. Catalyst system according to any one of claims 1 to 15 wherein the molar ratio of the preformed conjugated diene monomer on the metallocene metal has a value ranging from 5 to 1000, preferably from 10 to 500.
    [17" id="c-fr-0017]
    17. Catalyst system according to any one of claims 1 to 16 wherein the molar ratio of cocatalyst on the metallocene metal has a value ranging from 0.5 to 20, preferably from 1 to 10.
    [18" id="c-fr-0018]
    18. Catalyst system according to any one of claims 1 to 17, which catalytic system comprises a hydrocarbon solvent, preferably is in solution in said hydrocarbon solvent.
    [19" id="c-fr-0019]
    19. Catalyst system according to claim 18 wherein the hydrocarbon solvent is aromatic or aliphatic, preferably aliphatic, more preferably methylcyclohexane.
    [20" id="c-fr-0020]
    20. Catalyst system according to any one of claims 18 to 19 wherein the molar concentration of metallocene metal in the catalyst system has a value ranging from 0.0001 to 0.05 mol / l, preferably from 0.001 to 0.03. mol / l.
    [21" id="c-fr-0021]
    21. Process for the preparation of a catalytic system defined in any one of claims 1 to 20 which comprises the following steps a) and b): a) reacting in a hydrocarbon solvent the cocatalyst and the metallocene, b) reacting the preformed conjugated diene monomer with the reaction product of step a).
    [22" id="c-fr-0022]
    22. The method of claim 21 wherein step a) takes place at a temperature ranging from 20 to 80 ° C, and step b) is carried out at a temperature ranging from 40 to 100 ° C, preferably from 60 to 100 ° C. 90 ° C.
    [23" id="c-fr-0023]
    23. A process for the preparation of a polymer which comprises the polymerization of a monomer M in the presence of a catalytic system defined in any one of claims 1 to 20.
    [24" id="c-fr-0024]
    24. The method of claim 23 wherein the monomer M is selected from the group of monomers consisting of conjugated dienes, ethylene, α-monoolefins and mixtures thereof.
    [25" id="c-fr-0025]
    25. The method of claim 23 wherein the monomer M is a 1,3-diene, preferably 1,3-butadiene, isoprene or a mixture thereof.
    [26" id="c-fr-0026]
    26. The method of claim 23 wherein the monomer M is 1,3-butadiene or a mixture of 1,3-butadiene and ethylene.
    [27" id="c-fr-0027]
    27. The method of any one of claims 23 to 26 wherein the polymer is an elastomer.
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    同族专利:
    公开号 | 公开日
    FR3044662B1|2017-12-08|
    WO2017093654A1|2017-06-08|
    JP2018536074A|2018-12-06|
    US10752712B2|2020-08-25|
    EP3383928A1|2018-10-10|
    US20180355083A1|2018-12-13|
    CN108290981B|2021-06-18|
    SG11201803919SA|2018-06-28|
    EP3383928B1|2021-09-08|
    CN108290981A|2018-07-17|
    JP6903660B2|2021-07-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3794604A|1971-09-24|1974-02-26|Goodyear Tire & Rubber|Diolefin polymerization catalyst composition|
    EP1092731A1|1999-10-12|2001-04-18|Société de Technologie Michelin|Catalytic system, process for its preparation and that of an ethylene-conjugated diene copolymer|
    WO2007054224A2|2005-11-09|2007-05-18|Societe De Technologie Michelin|Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method|
    WO2007054223A2|2005-11-09|2007-05-18|Societe De Technologie Michelin|Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method|
    FR3054221A1|2016-07-25|2018-01-26|Compagnie Generale Des Etablissements Michelin|PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE|
    FR3085683B1|2018-09-11|2020-10-23|Michelin & Cie|PNEUMATIC|
    FR3085684B1|2018-09-11|2021-06-04|Michelin & Cie|RUBBER COMPOSITION|
    FR3086945B1|2018-10-04|2020-12-04|Michelin & Cie|SYNTHESIS OF ETHYLENE AND MYRCENE COPOLYMER|
    FR3086944B1|2018-10-04|2020-12-04|Michelin & Cie|METHOD FOR SYNTHESIS OF ETHYLENE AND 1,3-DIENE COPOLYMER|
    FR3086943B1|2018-10-08|2020-12-04|Michelin & Cie|ETHYLENE AND BETA-FARNESENE COPOLYMER|
    FR3086949B1|2018-10-09|2020-12-04|Michelin & Cie|RUBBER COMPOSITION|
    FR3086948B1|2018-10-09|2020-12-04|Michelin & Cie|RUBBER COMPOSITION|
    FR3087443B3|2018-10-23|2020-10-23|Michelin & Cie|RUBBER COMPOSITION|
    FR3090659A3|2018-12-21|2020-06-26|Michelin & Cie|Tire tread|
    FR3090663A3|2018-12-21|2020-06-26|Michelin & Cie|Tire tread|
    FR3090661A3|2018-12-21|2020-06-26|Michelin & Cie|Tire tread|
    FR3090654A3|2018-12-21|2020-06-26|Michelin & Cie|Rubber composition|
    FR3090656A3|2018-12-21|2020-06-26|Michelin & Cie|Tire tread|
    FR3099766B1|2019-08-07|2021-07-30|Michelin & Cie|Ethylene-rich diene block polymer having a statistical block and a polyethylene block.|
    FR3100811B1|2019-09-18|2021-09-03|Michelin & Cie|Functional ethylene and 1,3-diene copolymers|
    FR3100810B1|2019-09-18|2021-09-03|Michelin & Cie|Ethylene 1,3-diene terpolymer|
    FR3100815B1|2019-09-18|2022-01-28|Michelin & Cie|rubber composition|
    FR3100812B1|2019-09-18|2021-09-03|Michelin & Cie|Functional ethylene and 1,3-diene copolymers|
    FR3104597B1|2019-12-16|2021-11-12|Michelin & Cie|RUBBER COMPOSITION|
    FR3104584B1|2019-12-17|2021-12-03|Michelin & Cie|Asymmetric diorganomagnesium compound|
    FR3104487B1|2019-12-17|2021-11-05|Michelin & Cie|ELASTOMERIC LAMINATE|
    FR3104585B1|2019-12-17|2021-12-03|Michelin & Cie|Catalytic system based on a metallocene and a diorganomagnesium|
    FR3104596B1|2019-12-17|2021-11-12|Michelin & Cie|RUBBER COMPOSITION|
    FR3104595B1|2019-12-17|2021-11-12|Michelin & Cie|PNEUMATIC WITH A TREAD CONTAINING REINFORCING ELEMENTS|
    FR3105225B1|2019-12-18|2021-12-03|Michelin & Cie|Copolymer of ethylene and a 1,3-diene|
    FR3108117A1|2020-03-10|2021-09-17|Compagnie Generale Des Etablissements Michelin|A method of making a rubber composition.|
    FR3111352A1|2020-06-11|2021-12-17|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION WITH IMPROVED AGGRESSION RESISTANCE|
    法律状态:
    2016-12-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-09| PLSC| Publication of the preliminary search report|Effective date: 20170609 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1561770A|FR3044662B1|2015-12-03|2015-12-03|PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE|FR1561770A| FR3044662B1|2015-12-03|2015-12-03|PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE|
    PCT/FR2016/053137| WO2017093654A1|2015-12-03|2016-11-30|Catalytic preform system comprising a rare earth metallocene|
    CN201680070128.2A| CN108290981B|2015-12-03|2016-11-30|Preformed catalytic systems comprising rare earth metallocenes|
    US15/780,233| US10752712B2|2015-12-03|2016-11-30|Catalytic preform system comprising a rare earth metallocene|
    EP16819134.4A| EP3383928B1|2015-12-03|2016-11-30|Catalytic preform system comprising a rare earth metallocene|
    SG11201803919SA| SG11201803919SA|2015-12-03|2016-11-30|Catalytic preform system comprising a rare earth metallocene|
    JP2018528653A| JP6903660B2|2015-12-03|2016-11-30|Catalyst preformation system containing rare earth metallocenes|
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