Patents by Inventor Julien Thuilliez

Julien Thuilliez has filed for patents to protect the following inventions. This listing includes patent applications that are pending as well as patents that have already been granted by the United States Patent and Trademark Office (USPTO).

  • Publication number: 20240117080
    Abstract: A catalytic system based on at least one rare-earth metallocene and an organomagnesium reagent as co-catalyst of formula RB—(Mg—RA)m—Mg—RB is provided. According to the formula, RB comprises a benzene nucleus substituted with the magnesium atom. One of the carbon atoms of the benzene nucleus ortho to the magnesium is substituted with a methyl, an ethyl or an isopropyl or forms a ring with the carbon atom which is its closest neighbour and which is meta to the magnesium. The other carbon atom of the benzene nucleus ortho to the magnesium is substituted with a methyl, an ethyl or an isopropyl. RA is a divalent aliphatic hydrocarbon-based chain, optionally interrupted with one or more oxygen or sulfur atoms or with one or more arylene groups. The m is a number greater than or equal to 1, preferably 1. The catalytic system allows the synthesis of dienic and/or ethylenic telechelic polymers.
    Type: Application
    Filed: November 19, 2021
    Publication date: April 11, 2024
    Inventors: Robert NGO, Nicolas BAULU, Christophe BOISSON, Franck D'AGOSTO, François JEAN-BAPTISTE-DIT-DOMINIQUE, Julien THUILLIEZ
  • Publication number: 20240043600
    Abstract: A triblock polymer of formula B-A-B is provided. According to the formula, the symbol A represents a “central” block which is a statistical copolymer comprising units of a 1,3-diene and more than 50 mol % of ethylene units. The symbols B each represent an “end” block which is a polyethylene with a melting point of greater than 90° C. and a number-average molar mass of greater than or equal to 2000 g/mol and less than or equal to 10 000 g/mol. The polymer has improved rheological properties relative to a statistical copolymer based on ethylene and 1,3-diene of the same microstructure without changing its mechanical and dynamic or thermal properties.
    Type: Application
    Filed: November 22, 2021
    Publication date: February 8, 2024
    Inventors: Nicolas BAULU, Christophe BOISSON, Franck D'AGOSTO, Damien MONTARNAL, Emma MORESO, Julien THUILLIEZ, François JEAN-BAPTISTE-DIT-DOMINIQUE
  • Publication number: 20240026058
    Abstract: A process for preparing a multiblock polymer by statistical copolymerization of a mixture containing ethylene and a 1,3-diene and subsequent polymerization of ethylene in the presence of a rare-earth metallocene and an organomagnesium reagent RB—(Mg—RA)m—Mg—RB or X—Mg—RA—Mg—X is provided. According to the formula, RA is a divalent aliphatic hydrocarbon-based chain optionally interrupted with one or more oxygen or sulfur atoms or arylene groups, RB comprises a benzene nucleus substituted with the Mg atom, one of the carbon atoms of the benzene nucleus ortho to the Mg is substituted with a methyl, an ethyl or an isopropyl or forms a ring with the carbon atom which is its closest neighbour and which is meta to the Mg. The other carbon atom of the benzene nucleus ortho to the Mg is substituted with a methyl, ethyl or isopropyl, X being a halogen atom, m being greater than or equal to 1.
    Type: Application
    Filed: November 22, 2021
    Publication date: January 25, 2024
    Inventors: Robert NGO, Nicolas BAULU, Christophe BOISSON, Franck D'AGOSTO, François JEAN-BAPTISTE-DIT-DOMINIQUE, Julien THUILLIEZ
  • Publication number: 20240010767
    Abstract: A telechelic polymer of formula Z1-POLY-Z2 is provided. The term “POLY” denotes a polymer chain comprising units of a 1,3-diene, ethylene units and cyclic units, 1,2-cyclohexane units, Z1 and Z2 denoting a group containing a function, Z1 and Z2 being identical. The polymer has a macrostructure defined by a dispersity of less than 1.5 or by a number-average molar mass of greater than 10 000 g/mol.
    Type: Application
    Filed: November 19, 2021
    Publication date: January 11, 2024
    Inventors: Robert NGO, Nicolas BAULU, Christophe BOISSON, Franck D'AGOSTO, François JEAN-BAPTISTE-DIT-DOMINIQUE, Julien THUILLIEZ
  • Publication number: 20230406966
    Abstract: A catalytic system based on at least one rare-earth metallocene and as co-catalyst an organomagnesium reagent of formula X—Mg—RA—Mg—X is provided. In the formula, RA is a divalent aliphatic hydrocarbon-based chain, optionally interrupted with an oxygen atom, a sulfur atom or with an arylene group, and X is a halogen atom. The catalytic system allows the synthesis of dienic and/or ethylenic telechelic polymers.
    Type: Application
    Filed: November 19, 2021
    Publication date: December 21, 2023
    Inventors: Nicolas BAULU, Christophe BOISSON, Franck D'AGOSTO, Robert NGO, Julien THUILLIEZ, François JEAN-BAPTISTE-DIT-DOMINIQUE
  • Publication number: 20230357462
    Abstract: A catalytic system based on at least one metallocene and on a diorganomagnesium compound of formula RB—Mg—RA is provided, RB being different from RA and comprising a benzene nucleus substituted with a magnesium atom, one of the carbon atoms of the benzene nucleus ortho to the magnesium being substituted with a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its closest neighbour and which is meta to the magnesium, the other carbon atom of the benzene nucleus ortho to the magnesium being substituted with a methyl, an ethyl or an isopropyl, RA being an alkyl, a cycloalkyl or a benzyl, which may be substituted or unsubstituted. The catalytic system makes it possible to increase the functional group content in the synthesis of a functional polymer.
    Type: Application
    Filed: December 14, 2020
    Publication date: November 9, 2023
    Inventors: Julien Thuilliez, Robert Ngo, François Jean-Baptiste-Dit-Dominique
  • Publication number: 20230145123
    Abstract: The invention relates to a diorganomagnesium compound of formula RB—Mg—RA, RA being different from R8, RA being a polymer chain containing units of a monomer chosen from the group of monomers consisting of 1,3-dienes, aromatic ?-monoolefins and mixtures thereof, RB comprising a benzene nucleus substituted with a magnesium atom, one of the carbon atoms of the benzene nucleus ortho to the magnesium being substituted with a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its closest neighbour and which is meta to the magnesium, the other carbon atom of the benzene nucleus ortho to the magnesium being substituted with a methyl, an ethyl or an isopropyl, on condition that if one of the two ortho carbon atoms is substituted with an isopropyl, the second ortho carbon atom is not substituted with an isopropyl.
    Type: Application
    Filed: December 14, 2020
    Publication date: May 11, 2023
    Inventors: Julien Thuilliez, Robert Ngo, François Jean-Baptiste-Dit-Dominique
  • Publication number: 20230047483
    Abstract: The invention relates to a diorganomagnesium compound of formula RB—Mg—RA, RB being different from RA, RB comprising a benzene nucleus substituted with a magnesium atom, one of the carbon atoms of the benzene nucleus ortho to the magnesium being substituted with a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its closest neighbour and which is meta to the magnesium, the other carbon atom of the benzene nucleus ortho to the magnesium being substituted with a methyl, an ethyl or an isopropyl, RA being an alkyl, a cycloalkyl or a benzyl, which may be substituted or unsubstituted, which diorganomagnesium compound is other than n-butylmesitylmagnesium. When used as co-catalyst of a metallocene, it makes it possible to increase the functional group content in the synthesis of a functional polymer.
    Type: Application
    Filed: December 14, 2020
    Publication date: February 16, 2023
    Inventors: Julien Thuilliez, Robert Ngo, François Jean-Baptiste-Dit-Dominique
  • Patent number: 11498985
    Abstract: A process for the synthesis of an ethylene/butadiene copolymer is provided. The process is continuous and comprises the following steps: a. feeding at least one stirred polymerization reactor with a mixture of ethylene, butadiene, hydrocarbon-based solvent and catalytic system allowing the formation of cyclic trans-1,2-cyclohexane units in the polymer chain with a mole ratio of ethylene to the sum of the ethylene and butadiene monomers ranging from 0.5 to 0.99; the concentration of ethylene and butadiene monomers in the polymerization reaction medium being less than 15% by weight; the operating pressure of the reactor is greater than or equal to the saturated vapour pressure of the polymerization reaction medium; and the polymerization temperature is greater than 90° C.; b.
    Type: Grant
    Filed: April 16, 2018
    Date of Patent: November 15, 2022
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Julien Thuilliez, Nuno Pacheco
  • Publication number: 20220332878
    Abstract: A diblock polymer composed of a first block and a second block is provided. The first block is a statistical copolymer comprising units of a 1,3-diene and more than 50 mol % of ethylene units. The second block is a polyethylene with a melting point above 90° C. and a number-average molar mass greater than or equal to 2000 g/mol and less than or equal to 10 000 g/mol. Such a diblock polymer has improved rheology compared to a statistical copolymer of the same microstructure and of the same macrostructure as the first block of the diblock polymer.
    Type: Application
    Filed: July 27, 2020
    Publication date: October 20, 2022
    Inventors: Emma Moreso, Julien Thuilliez, François Jean-Baptiste-Dit-Dominique, Christophe Boisson, Franck D'Agosto, Nicolas Baulu, Damien Montarnal
  • Publication number: 20220135717
    Abstract: A process for the synthesis of an ethylene/butadiene copolymer is provided. The process is continuous and comprises the following steps: a. feeding at least one stirred polymerization reactor with a mixture of ethylene, butadiene, hydrocarbon-based solvent and catalytic system allowing the formation of cyclic trans-1,2-cyclohexane units in the polymer chain with a mole ratio of ethylene to the sum of the ethylene and butadiene monomers ranging from 0.5 to 0.99; the concentration of ethylene and butadiene monomers in the polymerization reaction medium being less than 15% by weight; the operating pressure of the reactor is greater than or equal to the saturated vapour pressure of the polymerization reaction medium; and the polymerization temperature is greater than 90° C.; b.
    Type: Application
    Filed: April 16, 2018
    Publication date: May 5, 2022
    Applicant: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Julien THUILLIEZ, Nuno PACHECO
  • Publication number: 20220056175
    Abstract: A terpolymer of ethylene, of 1,3-butadiene and of an aromatic ?-monoolefin is provided. The terpolymer contains more than 60 mol %, preferably at least 70 mol %, and preferably at most 90 mol % of ethylene units, at most 10 mol % of aromatic ?-monoolefin units and 1,2-cyclohexanediyl units. Such a diene terpolymer rich in ethylene units has the advantage of exhibiting a reduced, or even zero, crystallinity.
    Type: Application
    Filed: December 2, 2019
    Publication date: February 24, 2022
    Applicant: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Emma MORESO, Vincent LAFAQUIERE, Julien THUILLIEZ
  • Patent number: 11155656
    Abstract: An ethylene/1,3-butadiene copolymer containing ethylene units, butadiene units and UD units of cyclic, 1,2-cyclohexanediyl structure, and bearing, at one of its chain ends, an alkoxysilyl or silanol function, functional group F1 is provided.
    Type: Grant
    Filed: June 6, 2018
    Date of Patent: October 26, 2021
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Julien Thuilliez, Vincent Lafaquiere, Leyla Pehlivan, Benoît MacQueron, Christophe Boisson, Franck D'Agosto
  • Patent number: 11136422
    Abstract: A process for the synthesis of an ethylene/butadiene copolymer is provided. The process is continuous and comprises: a. feeding at least one stirred polymerization reactor with a mixture of ethylene, butadiene, hydrocarbon-based solvent and catalytic system allowing the formation of cyclic trans-1,2-cyclohexane units in the polymer chain with a mole ratio of ethylene to the sum of the ethylene and butadiene monomers ranging from 0.5 to 0.99; the concentration of ethylene and butadiene monomers in the polymerization reaction medium being at least 10% by weight relative to the total weight; the operating pressure of the reactor is greater than or equal to the saturated vapour pressure of the polymerization reaction medium; b. recovering the ethylene/butadiene copolymer, this copolymer comprising, statistically distributed, ethylene units, butadiene units and trans-1,2-cyclohexane units, the molar fraction of ethylene units in the copolymer being greater than or equal to 50%.
    Type: Grant
    Filed: April 16, 2018
    Date of Patent: October 5, 2021
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Julien Thuilliez, Nuno Pacheco
  • Patent number: 11130826
    Abstract: A catalytic system based at least on a preformation monomer selected from the group consisting of 1,3-dienes, ethylene, ?-olefins and their mixtures, on a metallocene of formula {P(Cp)(Flu)LnG} and on an organometallic compound as cocatalyst is provided. In the formula, Ln denotes a metal atom which is a rare earth metal, G denotes a group comprising the borohydride BH4 unit or denotes a halogen atom X selected from the group consisting of chlorine, fluorine, bromine and iodine, Cp denotes a cyclopentadienyl group of formula C5H4, Flu denotes a fluorenyl group of formula C13H8, P being a group bridging the two Cp and Flu groups and comprising a silicon or carbon atom. Such a catalytic system exhibits an improved stability of the catalytic activity over time, in particular on storage.
    Type: Grant
    Filed: November 28, 2017
    Date of Patent: September 28, 2021
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Vincent Lafaquiere, Julien Thuilliez
  • Patent number: 11104755
    Abstract: A copolymer of a 1,3-diene and of an olefin selected from the group consisting of ?-monoolefins, ethylene and mixtures thereof is provided. The copolymer bears, at one of its chain ends, an alkoxysilyl or silanol function, functional group F1, and the copolymer is different from a copolymer of a 1,3-diene and a vinylaromatic monomer.
    Type: Grant
    Filed: June 6, 2018
    Date of Patent: August 31, 2021
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Julien Thuilliez, Vincent Lafaquiere, Leyla Pehlivan, Benoît Macqueron, Christophe Boisson, Franck D'Agosto
  • Publication number: 20210230325
    Abstract: A copolymer of ethylene and of isoprene, which comprises from 10 to 35 mol % of isoprene units, at least 70% of which are in the 3,4 configuration and a portion of which is in the 1,2 configuration is provided. A copolymer of this type with a reduced crystallinity is synthesized with a much higher productivity than its homologues of ethylene and of butadiene, and also confers improved curing properties on rubber compositions.
    Type: Application
    Filed: May 27, 2019
    Publication date: July 29, 2021
    Applicant: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: José-Carlos ARAUJO DA SILVA, Vincent LAFAQUIERE, Emma MORESO, Julien THUILLIEZ, Aurélie TRIGUEL
  • Publication number: 20210079135
    Abstract: A rubber composition which comprises at least one reinforcing inorganic filler and a highly saturated elastomer comprising 1,3-diene units and ethylene units and bearing, at the chain end, a functional group F1 which is a silanol or alkoxysilane function is provided. The ethylene units represent more than 50 mol % of all the monomer units of the elastomer. The rubber composition has an improved hysteresis/stiffness compromise.
    Type: Application
    Filed: June 6, 2018
    Publication date: March 18, 2021
    Applicant: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Julien THUILLIEZ, Emma MORESO, Vincent LAFAQUIERE
  • Patent number: 10934377
    Abstract: A catalytic system based at least on a preformation monomer which is ethylene or a mixture of ethylene and of a conjugated diene, on a metallocene of formula {P(Cp1)(Cp2)Y} or Cp3Cp4Y and on an organometallic compound as cocatalyst, Y denoting a group comprising a metal atom which is a rare earth metal, the Cp1, Cp2, Cp3 and Cp4 groups, which are identical or different, being selected from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted, and P being a group bridging the two Cp1 and Cp2 groups and comprising a silicon or carbon atom, is provided. Such a catalytic system exhibits an improved stability of the catalytic activity over time, in particular on storage.
    Type: Grant
    Filed: July 24, 2017
    Date of Patent: March 2, 2021
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Vincent Lafaquiere, Julien Thuilliez
  • Patent number: 10844149
    Abstract: An ethylene/butadiene copolymer comprising statistically distributed ethylene units and butadiene unit is provided. The molar fraction of the ethylene units in the copolymer is greater than or equal to 50%, relative to the total number of moles of ethylene and butadiene units. The microstructure of the copolymer is homogeneous. A process for preparing such a copolymer and also the uses of this copolymer, in particular in rubber compositions for tires is also provided.
    Type: Grant
    Filed: December 16, 2016
    Date of Patent: November 24, 2020
    Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
    Inventors: Nuno Pacheco, Julien Thuilliez