WO2005028526A1 - Système catalytique pour l'obtention de copolymères diène(s) conjugué(s) / mono-oléfine(s) et ces copolymères - Google Patents

Système catalytique pour l'obtention de copolymères diène(s) conjugué(s) / mono-oléfine(s) et ces copolymères Download PDF

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WO2005028526A1
WO2005028526A1 PCT/EP2004/008336 EP2004008336W WO2005028526A1 WO 2005028526 A1 WO2005028526 A1 WO 2005028526A1 EP 2004008336 W EP2004008336 W EP 2004008336W WO 2005028526 A1 WO2005028526 A1 WO 2005028526A1
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Prior art keywords
copolymer
catalytic system
butadiene
olefin
conjugated diene
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French (fr)
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Christophe Boisson
Vincent Monteil
Roger Spitz
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Total Petrochemicals Research Feluy SA
TotalEnergies Onetech Belgium SA
Michelin Recherche et Technique SA Switzerland
Societe de Technologie Michelin SAS
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Total Petrochemicals Research Feluy SA
Atofina Research SA
Michelin Recherche et Technique SA Switzerland
Societe de Technologie Michelin SAS
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Priority to JP2006522929A priority Critical patent/JP5329040B2/ja
Priority to MXPA06001656A priority patent/MXPA06001656A/es
Priority to EP04763491.0A priority patent/EP1656400B1/fr
Priority to BRPI0413457-5A priority patent/BRPI0413457B1/pt
Priority to KR1020127017251A priority patent/KR101263815B1/ko
Priority to KR1020067002964A priority patent/KR101196236B1/ko
Publication of WO2005028526A1 publication Critical patent/WO2005028526A1/fr
Priority to US11/350,754 priority patent/US7547654B2/en
Anticipated expiration legal-status Critical
Priority to US12/453,333 priority patent/US8039565B2/en
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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
    • 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
    • C08F4/58—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 silicon, germanium, tin, lead, antimony, bismuth or 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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
    • 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
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • Catalytic system for obtaining copoly conjugated diene (s) / mono-olefin (s) and these copolymers.
  • the present invention relates to a catalytic system which can be used for the copolymerization of at least one conjugated diene and at least one mono-olefin, a process for the preparation of this catalytic system, a process for the preparation of a copolymer of at least one conjugated diene and at least one mono-olefin consisting in using said catalytic system, and such a copolymer.
  • the invention applies in particular to the copolymerization of a conjugated diene with an alpha-olefin and / or ethylene.
  • an alpha-olefin ie comprising by definition at least three carbon atoms, unlike ethylene which is not an alpha-olefin
  • a major drawback of these catalytic systems is that they must be prepared at very low temperature (around -70 ° C) and that they lead to the use of an equally low copolymerization temperature, being between -30 ° C and -50 °. C.
  • the use of higher temperatures for the copolymerization leads to deactivation of these catalytic systems and to a reduction in the molecular weights of the copolymers obtained.
  • the German patent document DE-A-270 6118 teaches to use a catalytic system comprising a vanadium dialkoxyhalide and a trialkylaluminum.
  • Non-alternating conjugated diene / alpha-olefin copolymers such as butadiene / propylene or butadiene / ethylene / propylene copolymers, have also been prepared in the past by carrying out the copolymerizations at temperatures above room temperature.
  • European patent document EP-A-891 993 presents a catalytic system for the copolymerization of a mono-olefin having 2 to 12 carbon atoms and of at least one conjugated diene monomer, which comprises the following constituent (a) and at least one compound chosen from the following constituents (b), (c) and (d): (a) a complex of a transition metal corresponding to the choice of one of the following formulas: (Cp 1 -ZY) MX 1 X 2 or else , where M is one of the following metals: Ti, Zr, Hf, Rn, Nd, Sm, Ru, Cp !
  • Cp 2 are each a cyclopentadienyl, indenyl or fluorenyl group
  • Y is a ligand containing an oxygen, nitrogen, phosphorus or sulfur atom
  • Z represents C, O, B, S, Ge, Si, Sn or a group containing any one of these atoms
  • ⁇ l and X ⁇ each represents an anionic or neutral ligand which is a Lewis base
  • (c) an organoaluminum compound; and (d) an aluminoxane is a compound which reacts with the metal M of (a) to form an ionic complex
  • an organoaluminum compound is an organoaluminum compound
  • an aluminoxane an aluminoxane
  • copolymers obtained in this document EP-A-891 993 comprise a reduced molar level of conjugated diene inserted (less than 10%), and that they always comprise cyclic units (of the cyclopentane and cyclopropane type).
  • Catalytic systems specifically comprising a lanthanide complex and making it possible to copolymerize conjugated dienes and alpha-olefins have also been reported in the literature. Kaulbach. et al described in Angew. Makromol. Chem. 1995, 226, p. 101 butadiene / octene or dodecene copolymerization with a neodymium octoate complex. Visseaux M. et al described in Macromol. Chem. Phys. 2001, 202, p. 2485 alpha-olefin / conjugated diene (butadiene or isoprene) copolymerization with an allylic lanthanide complex.
  • a major drawback of these latter catalytic systems is that the molar level of inserted alpha-olefin is always reduced, being less than 20%.
  • Ln represents a metal of a lanthanide whose atomic number can go from 57 to 71
  • X represents a halogen which can be chlorine, fluorine, bromine or iodine
  • formula A ' are connected to the metal Ln two molecules of ligands Cpi and Cp 2 each consisting of a cyclopentadienyl or fluorenyl group substituted or not
  • formula B ' is linked to metal Ln a ligand molecule, consisting of two cyclopentadienyl or fluorenyl groups Cpi and Cp substituted or not and linked together by a bridge P of formula MR 2
  • M is an element from column IVA of the Mendeleev periodic classification
  • R is an alkyl group comprising from 1 to 20 carbon atoms, and - on the other hand, a co-catalyst chosen in the group comprising an alkyl magnesium, an alkyl lithium, an aluminum aluminum
  • R 2 where M is an element of column IVA of the Mendeleev periodic classification and where R 1 and R 2 , identical or different, each represent alkyl groups having from 1 to 20 carbon atoms or cycloalkyl or phenyl groups having 6 to 20 carbon atoms, where X represents a halogen atom which may be chlorine, fluorine, bromine or iodine, where L comprises an optional complexing molecule, such as an ether, and optionally a molecule substantially less complexing, such as toluene, where p is a natural integer equal to or greater than 1 and x is equal to or greater than 0, and (ii) a co-catalyst belonging to the group consisting of alkyl magnesiums, alkyl lithiums, alkyl aluminum, Grignard reagents and mixtures of these constituents can be used to obtain a copolymer of a conjugated diene and at least one mono-olefin, such as an alpha-olefin and
  • Said organometallic complex is for example represented by the following formula:
  • said organometallic complex is such that p is equal to 2, then being a dimer represented by the following formula:
  • said cyclopentadienyl Cp and fluorenyl FI groups are both unsubstituted in one or the other of the above formulas, corresponding respectively to formulas C 5 H 4 and C 13 H 8 .
  • said bridge P corresponds to the formula SiR R.
  • R and R are each independently alkyl groups, such as methyl groups.
  • said organometallic complex is such that the lanthanide Ln is neodymium.
  • said co-catalyst is an alkyl magnesium such as butyloctyl magnesium, or a mixture of an aluminum alkyl such as diisobutyl aluminum hydride and an alkyl lithium such as butyl lithium which are present in substantially stoichiometric amounts in this mixture.
  • the molar ratio (co-catalyst / organometallic complex) is less than or equal to 5, so that said copolymer obtained can have a number-average molecular mass. Mn greater than 30,000 g / mol.
  • a process for the preparation according to the invention of said catalytic system comprises: a) the preparation of said organometallic complex comprising: (i) the reaction with an alkyl lithium of a hydrogenated ligand molecule, represented by the following formula (2), to obtain a lithium salt corresponding to the following formula (3):
  • At least one of the following conditions is satisfied: - said alkyl lithium used in a) (i) is butyl lithium, and / or - said complexing solvent used in a) (ii) is tetrahydrofuran, and / or - said substantially less complexing solvent used in a) (iii) is heptane (practically not complexing) or toluene (“moderately” complexing).
  • this process is such that said cyclopentadienyl Cp and fluorenyl FI groups are both unsubstituted, corresponding to the formulas C 5 H 4 and C 13 H 8 respectively .
  • this process is such that said bridge P corresponds to the formula SiR R.
  • R 1 and R 2 are each independently alkyl groups, such as methyl groups.
  • this process is such that said lanthanide Ln is neodymium.
  • this process is such that said co-catalyst is an alkyl magnesium such as butyloctyl magnesium, or a mixture of an aluminum alkyl such as diisobutyl aluminum hydride and an alkyl lithium such as butyl lithium, present in substantially stoichiometric amounts in said mixture. Also preferably in connection with any one of the aforementioned characteristics, this process is such that the molar ratio (number of moles of said co-catalyst / number of moles of said organometallic complex) is less than or equal to 5, the catalytic system being usable so that the copolymer has a molecular weight Mn greater than 30,000 g / mol.
  • this process is such that said molar ratio (co-catalyst / organometallic complex) is less than or equal to 2, the catalytic system being usable so that the copolymer has a molecular mass Mn greater than 60,000 g / mol .
  • a process for the preparation according to the invention of a copolymer of at least one conjugated diene and at least one mono-olefin comprises the reaction of said catalytic system as defined above in an inert hydrocarbon solvent, in the presence of said one or more diene (s) conjugate (s) and said mono-olefin (s).
  • this process is such that said copolymer comprises units originating from a conjugated diene, such as butadiene or isoprene, and units originating from at least one mono-olefin belonging to the group consisting of ethylene, alpha-olefins and vinyl aromatic compounds.
  • this process is such that said copolymer comprises units derived from an alpha-olefin having from 3 to 18 carbon atoms according to a molar ratio equal to or greater than 10%, or although it comprises units derived from ethylene and, according to a molar ratio equal to or greater than 10%, units derived from an alpha-olefin having from 3 to 18 carbon atoms.
  • this process is advantageously such that the units derived from said conjugated diene are present in said copolymer at a molar level greater than 40%, preferably greater than 50%.
  • this process is such that the units obtained from said conjugated diene (s) have a trans-1,4 linkage rate greater than 70%.
  • this process is such that the molar ratio (co-catalyst / organometallic complex) is less than or equal to 5, so that the molecular mass Mn of the copolymer is greater than 30,000 g / mol.
  • this process is such that said molar ratio (co-catalyst / organometallic complex) is less than or equal to 2, so that said copolymer has a molecular weight Mn greater than 60,000 g / mol.
  • a copolymer of at least one conjugated diene and at least one alpha-olefin having 3 to 18 carbon atoms according to the invention is capable of being obtained by a copolymerization process as defined above, and this copolymer according to the invention is preferably such that it satisfies both the following conditions: - the number-average molecular mass of said copolymer is greater than 60,000 g / mol, - said copolymer comprises units derived from said diene (s) conjugate (s) according to a molar ratio greater than 40% and less than or equal to 90%, and units derived from said alpha-olefin (s) according to a molar ratio less than 60% and equal to or greater than 10%, - Said units originating from said conjugated diene (s) have a trans-1,4 linkage rate greater than 70%, and - said copolymer is devoid of cyclic unit.
  • said copolymer consists of a copolymer of a conjugated diene, such as butadiene or isoprene, and d '' an alpha-olefin having 3 to 18 carbon atoms, such as propene, butene, hexene or octene.
  • said copolymer according to the invention comprises the units derived from said conjugated diene (s) in a molar ratio greater than 60% and less or equal to 80%, and the units obtained from said alpha-olefin (s) in a molar ratio of less than 40% and equal to or greater than 20%.
  • said copolymer consists of a terpolymer of a conjugated diene, such as butadiene or isoprene, ethylene and an alpha-olefin of 3 to 18 atoms carbon, such as propene, butene, hexene or octene.
  • said copolymer is such that each unit derived from said alpha-olefin (s) is inserted in the chain of said copolymer between two units derived from said or each conjugated diene, so that all of the units of said copolymer have a regular distribution of practically alternating type (also called “pseudo-alternating” by those skilled in the art).
  • a “BRUKER DRX” 400 spectrometer was used, at frequencies of 400 MHz for the 1 H NMR technique and 100, 6 MHz for the 13 C NMR technique. See the attached appendix for a detailed description of these techniques.
  • the glass transition temperatures were measured by DSC (Differential Scanning Calorimetry) on a “Setaram DSC 131” device.
  • the temperature program used corresponds to a temperature rise from -120 ° C to 150 ° C at the speed of 10 ° C / min.
  • the molecular weights Mn and the polymolecularity indices were determined by size exclusion chromatography using the apparatus and the analysis conditions described below. The molecular weight values indicated in the following examples are expressed in polystyrene equivalent.
  • the structure of the salt obtained is [Me 2 Si (C 5 H 4 ) (C 13 H 8 )] Li 2 (OC 4 H 8 ) 2.
  • - synthesis of the organometallic complex [Me 2 Si (C 5 H 4 ) (C 1 3Hs)] NdCl (OC4H8) x : 0.58 g (2.3 mmol) of NdCl 3 are stirred for 1 night at reflux in 50 ml of THF.
  • To the suspension obtained is added at -20 ° C a solution of 0.82 g of the salt [Me 2 Si (C 5 H 4 ) (C 13 H 8 )] Li2 (OC 4 H 8 ) 2 in
  • Example 2 Copolymerization of butadiene and ethylene using the organometallic complex of Example 1 and various co-catalysts.
  • the internal pressure of the reactor was maintained at 4 bars when the butadiene fraction y allows it.
  • the temperature of the polymerization reactor was maintained at 80 ° C during the polymerization. After a reaction time t (min.), The polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying, a mass m (g) of copolymer is obtained comprising units derived from butadiene in a molar fraction z (%).
  • BMAG butyllithium
  • HDiBA diisobutylaluminum hydride
  • Examples 3 Copolymerization of butadiene and octene using the organometallic complex of Example 1 and various co-catalysts.
  • the temperature of the polymerization reactor was brought to 80 °
  • a solution composed of 10 ml of toluene, 100 ml of octene, 37 mg of said complex prepared in Example 1 and 20 molar equivalents relative to the neodymium of a co-catalyst is successively introduced into an argon reactor. "BOMAG", then 25 ml of butadiene.
  • the temperature of the polymerization reactor was brought to 80 ° C. After 15 h of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 13.3 g.
  • the glass transition temperature is - 65.4 ° C.
  • Example 3-3 A solution composed of 10 ml of toluene, 100 ml of octene, 37 mg of said complex prepared in Example 1 and 5 molar equivalents relative to the neodymium of a co-catalyst is successively introduced into an argon reactor. "BOMAG", then 25 ml of butadiene. The temperature of the polymerization reactor was brought to 80 ° C. After 15 h of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 13.1 g.
  • the glass transition temperature is - 69.0 ° C.
  • Example 3-4 A solution composed of 10 ml of toluene, 100 ml of octene, 33 mg of said complex prepared in Example 1 and 2 molar equivalents relative to the neodymium of a co-catalyst is successively introduced into an argon reactor. "BOMAG", then 25 ml of butadiene. The temperature of the polymerization reactor was brought to 80 ° C. After 15 h of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 6.8 g.
  • the glass transition temperature is - 69.6 ° C.
  • Example 3-5 A solution composed of 200 ml of toluene, 50 ml of octene, 30 mg of said complex prepared in Example 1 and 20 molar equivalents relative to the neodymium of a co-catalyst is successively introduced into an argon reactor. "BOMAG", then 30 ml of butadiene. The temperature of the polymerization reactor was brought to 80 ° C. After 22 h of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 7.6 g. The molecular weight Mn of the copolymer is
  • tests 3-3 and 3-4 advantageously lead to octene / butadiene copolymers of relatively high molecular weight Mn (greater than 30,000 and 60,000 g / mol respectively), due to the molar ratio (co-catalyst / organometallic complex) very reduced which was used (ratio equal to 5 and 2 for these tests 3-3 and 3-4, respectively).
  • Example 4 Copolymerization of butadiene and hexene using the organometallic complex of Example 1 and a co-catalyst.
  • the temperature of the polymerization reactor was brought to 80 ° C. After 17 h of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol.
  • Example 5 Copolymerization of butadiene and butene using the organometallic complex of Example 1 and a co-catalyst.
  • a solution composed of 100 ml of toluene, 37 mg of said complex prepared in Example 1 and 20 molar equivalents relative to the neodymium of a co-catalyst consisting of a “BuLi” mixture is successively introduced into an argon reactor.
  • the temperature of the polymerization reactor was brought to 80 ° C. After 7 hours of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol.
  • Example 7 Copolymerization of butadiene and propene using the organometallic complex of Example 1 and a co-catalyst.
  • BuLi / HDiBA with neodymium /
  • the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 7.3 g.
  • the molecular weight Mn of the copolymer is
  • Example 8 Copolymerization of butadiene and styrene using the organometallic complex of Example 1 and a co-catalyst.
  • a solution composed of 50 ml of toluene, 50 ml of styrene, 30 mg of said complex prepared in Example 1 and 20 molar equivalents relative to the neodymium of a co-catalyst is successively introduced into an argon reactor. BOMAG ", then 25 ml of butadiene.
  • the temperature of the polymerization reactor was brought to 80 ° C. After 14 hours of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 46.4 g.
  • the glass transition temperature is + 16 ° C.
  • Example 9 Terpolymerization of butadiene, ethylene and octene using the organometallic complex of Example 1 and a co-catalyst.
  • the polymerization is stopped by cooling and degassing of the reactor, then the terpolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 25.7 g.
  • the glass transition temperature is - 78 ° C.
  • Comparative Examples 10 Butadiene / hexene copolymerization and ethylene / butadiene / hexene terpolymerization using a known organometallic complex and a co-catalyst.
  • the catalytic system used is one of those described in the aforementioned patent document EP-Al 092 731, as being usable for the copolymerization of ethylene and butadiene.
  • This catalytic system comprises an organometallic complex of formula [Me 2 Si (Me 3 SiC 5 H) 2 jNdCl, where Me denotes a methyl group, and a BuLi / HDiBA co-catalyst. It will be noted that this organometallic complex comprises two substituted cyclopentadienyl groups, unlike the organometallic complex according to the invention which specifically comprises a cyclopentadienyl group and a fluorenyl group.
  • Example 10-1 (Butadiene / hexene copolymerization).
  • a solution composed of 10 ml of toluene, 100 ml of hexene, 42.3 mg of this known complex of formula [Me 2 Si (Me 3 SiC 5 H 3 ) 2 ] is successively introduced into an argon reactor.
  • NdCl and 20 molar equivalents relative to the neodymium of the co-catalyst consisting of a “BuLi / HDiBA” mixture with neodymium / BuLi / HDiBA 1/10/10, then 30 ml of butadiene.
  • Example 10 (copolymerization with the organometallic complex according to Example 1) had a much higher molar rate of units from hexene (29.8% compared to 11.6% only in this example 10-1), and that the yield of the copolymerization relating to this example 4 (18.9 g) was much higher than that of this comparative example 10-1.
  • Example 10-2 (ethylene / butadiene / hexene terpolymerization).
  • the internal pressure of the reactor is then maintained at 4 bars. After 2 hours of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the terpolymer is obtained by precipitation in methanol. After drying under reduced pressure at 70 ° C, the yield is 6.4 g.
  • Comparative Example 11 Butadiene / hexene copolymerization using another known organometallic complex and a co-catalyst.
  • the catalytic system used here is one of those described in the aforementioned patent document EP-A-1 092 731, as being usable for the copolymerization of ethylene and butadiene.
  • This catalytic system comprises an organometallic complex of formula [Me 2 Si (C 13 H 8 ) 2 ] NdCl, where Me denotes a methyl group, and a co-catalyst BuLi / HDiBA. It will be noted that this organometallic complex comprises two fluorenyl groups, unlike the organometallic complex according to the invention.
  • a solution composed of 10 ml of toluene, 100 ml of hexene, 28 mg of this known complex of formula [Me 2 Si (C 13 H 8 ) 2 ] NdCl and 20 is successively introduced into an argon reactor.
  • molar equivalents relative to the neodymium of the cocatalyst consisting of a mixture "BuLi / HDiBA" with neodymium / BuLi / HDiBA 1/10/10, then 25 ml of butadiene.
  • the temperature of the polymerization reactor was brought to 80 ° C. After 18 hours of reaction, the polymerization is stopped by cooling and degassing of the reactor, then the copolymer is obtained by precipitation in methanol.
  • the apparatus used for these analyzes is a Bruker DRX 400 spectrometer operating at the frequency of 400 MHz in proton and 100.6 MHz in carbon.
  • the analysis solvent is a mixture of deuterated tetrachlorethylene (TCE) and benzene (CD 6 ).
  • the spectra production temperature is 90 ° C.
  • H of an ⁇ -olefin and butadiene copolymer provides access to the composition of the copolymer (butadiene and ⁇ -olefin content) and to the ratio between the insertion 1.2 and 1.4 of butadiene without distinguish between 1,4-trans and 1,4-cis insertions.
  • the spectra were divided into 5 regions (S 0 -S 4 ) which correspond to lines characteristic of the different protons belonging to the ⁇ -olefin (denoted Ol), to the butadiene inserted in 1,2 (V) or in 1, 4 (L) (see Table 1).
  • composition of the copolymer can easily be deduced from the quantities of butadiene and ⁇ -olefin calculated above.
  • Table 2 Calculated and observed chemical shifts of the lines characteristic of a THT sequence.
  • B / (B + L) 2A 7 / (2A 7 + A 3 + A 6 + A 5 + A 8 )
  • L 1.4 butadiene
  • B / (B + Bu) 2A 7 / (2A 7 + (l / (l- ⁇ )) (A 3 + A 6 + A 5 + A 8 ))

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PCT/EP2004/008336 2003-08-13 2004-07-26 Système catalytique pour l'obtention de copolymères diène(s) conjugué(s) / mono-oléfine(s) et ces copolymères Ceased WO2005028526A1 (fr)

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JP2006522929A JP5329040B2 (ja) 2003-08-13 2004-07-26 共役ジエン／モノオレフィンコポリマーを得るための触媒およびこれらのコポリマー
MXPA06001656A MXPA06001656A (es) 2003-08-13 2004-07-26 Sistema catalitico para obtencion de copolimeros de dieno conjugado/monoolefina y estos copolimeros.
EP04763491.0A EP1656400B1 (fr) 2003-08-13 2004-07-26 Systeme catalytique pour l'obtention de copolymères diène(s) conjugué(s) / mono-oléfine(s) et ces copolymères
BRPI0413457-5A BRPI0413457B1 (pt) 2003-08-13 2004-07-26 Sistema catalítico, processos de preparação de um sistema catalítico e de um copolímero, e, copolímero
KR1020127017251A KR101263815B1 (ko) 2003-08-13 2004-07-26 공액 디엔/모노올레핀 공중합체를 제조하기 위한 방법 및 공액 디엔/모노올레핀 공중합체
KR1020067002964A KR101196236B1 (ko) 2003-08-13 2004-07-26 공액 디엔/모노올레핀 공중합체를 제조하기 위한 촉매시스템 및 공액 디엔/모노올레핀 공중합체
US11/350,754 US7547654B2 (en) 2003-08-13 2006-02-10 Catalytic system for obtaining conjugated diene/monoolefin copolymers and these copolymers
US12/453,333 US8039565B2 (en) 2003-08-13 2009-05-07 Catalytic system for obtaining conjugated diene/mono-olefin copolymers and these copolymers

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EP1957506B1 (fr) * 2005-11-09 2014-10-22 Compagnie Generale Des Etablissements Michelin Complexe metallocene borohydrure d un lanthanide, systeme catalytique l incorporant, procede de polymerisation l utilisant et copolymere ethylene/butadiene obtenu par ce procede
US8071700B2 (en) 2005-11-09 2011-12-06 Michelin Recherche Et Technique S.A Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerization method using same and ethylene/butadiene copolymer obtained using said method
US8492573B2 (en) 2005-11-09 2013-07-23 Michelin Recherche Et Technique S.A. Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerization method using same and ethylene/butadiene copolymer obtained using said method
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US10513150B2 (en) 2015-06-19 2019-12-24 Compagnie Generale Des Etablissements Michelin Diene rubber/polypropylene thermoplastic elastomer copolymer, compositions containing same, and preparation method
WO2017097829A1 (fr) 2015-12-08 2017-06-15 Compagnie Generale Des Etablissements Michelin Copolymère monofonctionnel ou téléchélique de 1,3-diène et d'éthylène ou d'alpha-monooléfine
US10844149B2 (en) 2015-12-17 2020-11-24 Compagnie Generale Des Etablissements Michelin Ethylene and butadiene copolymer having a homogeneous microstructure
US10723814B2 (en) 2015-12-22 2020-07-28 Compagnie Generale Des Etablissements Michelin Tire comprising a rubber composition including a substituted diene elastomer
WO2018109312A1 (fr) 2016-12-15 2018-06-21 Compagnie Generale Des Etablissements Michelin Pneumatique comportant une composition de caoutchouc comprenant un polymere porteur d'un groupement diene conjugue reticule par un dienophile
WO2018109397A1 (fr) 2016-12-15 2018-06-21 Compagnie Generale Des Etablissements Michelin Élastomère diénique portant des groupes pendants anthracényles
WO2018115703A1 (fr) 2016-12-19 2018-06-28 Compagnie Generale Des Etablissements Michelin Procede de preparation d'un elastomere dienique modifie par un compose 1,3-dipolaire par extrusion reactive
WO2018115704A1 (fr) 2016-12-19 2018-06-28 Compagnie Generale Des Etablissements Michelin Procede de preparation d'un elastomere dienique modifie par un compose 1,3-dipolaire
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US11685803B2 (en) 2017-07-28 2023-06-27 Compagnie Generale Des Etablissements Michelin Resin-extended elastomer
WO2019102126A1 (fr) 2017-11-21 2019-05-31 Compagnie Generale Des Etablissements Michelin Polymère diénique modifié par un groupe époxyde
WO2019102132A1 (fr) 2017-11-21 2019-05-31 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
WO2019102128A1 (fr) 2017-11-21 2019-05-31 Compagnie Generale Des Etablissements Michelin Composé 1,3-dipolaire comportant un groupe époxyde
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CN1835978A (zh) 2006-09-20
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US20060160969A1 (en) 2006-07-20
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FR2858817A1 (fr) 2005-02-18
BRPI0413457A (pt) 2006-10-17
EP1656400A1 (fr) 2006-05-17
KR101196236B1 (ko) 2012-11-05
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EP1656400B1 (fr) 2019-05-29
US8039565B2 (en) 2011-10-18
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US20090270578A1 (en) 2009-10-29
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