公开(公告)号：EP2424902A1

公开(公告)日：2012-03-07

申请号：EP10717618.2

申请日：2010-04-27

申请人： Société de Technologie MICHELIN ,  MICHELIN Recherche et Technique S.A. ,  Centre National de la Recherche Scientifique ,  University Claude Bernard Lyon I

发明人： BOISSON, Christophe ,  ROLLAND, Olivier ,  THUILLIEZ, Julien

IPC分类号： C08F4/54 ,  C08F36/06 ,  C08F36/08

CPC分类号： C08F4/545 ,  C08F36/04

摘要： The present invention relates to a multi-component catalytic system which can be used for 1,4-cis stereospecific polymerisation of conjugated dienes. The system is made up of (i) a rare earth complex with formula (II) Ln(A)
3 (B)
n , in which Ln is a rare earth metal, A is a ligand, B is a Lewis base or a molecule of solvent and n is a number from 0 to 3; (ii) an alkylating agent, (iii) a compound made up of an aromatic ring having at least two hetero atoms, selected from the elements O, N, S, P, and having the formula (III), wherein the R groupings each designate hydrogen, an alkyl radical possibly comprising one or more hetero atoms (N, O, P, S, Si) or one or more halogen atoms, a halogen atom, a grouping made up of one or more hetero atoms (N, O, P, S, Si); x and y are integers from 0 to 6; D is a grouping having a chemical function in which one of the atoms has a non-binding doublet; L being an atom from the first column of the periodic table.

公开(公告)号：EP1954705A2

公开(公告)日：2008-08-13

申请号：EP06818328.4

申请日：2006-10-31

申请人： Société de Technologie Michelin ,  Michelin Recherche et Technique S.A. ,  Total Petrochemicals France ,  Centre National de la Recherche Scientifique ,  Ecole Superieure de Chimie Physique Electronique de Lyon

发明人： THUILLIEZ, Julien ,  BOISSON, Christophe ,  SPITZ, Roger

IPC分类号： C07F17/00 ,  C08F4/52 ,  C08F210/12

CPC分类号： C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

摘要： The invention relates to a borohydride metallocene complex of a lanthanide, the preparation method thereof, a catalytic system including said borohydride metallocene complex, a method for the copolymerisation of olefins using said catalytic system and an ethylene/butadiene copolymer obtained using said method, having butadiene units with 1,2-cyclohexane or 1,2 and 1,4-cyclohexane chains. The inventive complex has one of the following formulas (A and B), wherein, in formula A, two molecules of ligands Cp1 and Cp2 are linked to the lanthanide Ln, such as Nd, said ligand molecules each consisting of a fluorenyl group, and, in formula B, a ligand molecule is linked to the lanthanide Ln, said ligand molecule consisting of two fluorenyl groups Cp1 and Cp2 which are interlinked by means of a bridge P having formula MR1R2, in which M is an element from column IVA, such as Si, and R1 and R2, which may be identical or different, represent an alkyl group having between 1 and 20 carbon atoms. According to the invention, L represents an alkali metal, such as Li, N represents a molecule of a complexing solvent, such as THF, x is an integer or a non-integer which is greater than 0 and p is an integer which is equal to or greater than 1.

公开(公告)号：EP1954705B1

公开(公告)日：2012-03-07

申请号：EP06818328.4

申请日：2006-10-31

申请人： Société de Technologie Michelin ,  Michelin Recherche et Technique S.A. ,  Total Petrochemicals France ,  Centre National de la Recherche Scientifique ,  Ecole Superieure de Chimie Physique Electronique de Lyon

发明人： THUILLIEZ, Julien ,  BOISSON, Christophe ,  SPITZ, Roger

IPC分类号： C07F17/00 ,  C08F4/52 ,  C08F210/12

CPC分类号： C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

摘要： The invention relates to a borohydride metallocene complex of a lanthanide, the preparation method thereof, a catalytic system including said borohydride metallocene complex, a method for the copolymerisation of olefins using said catalytic system and an ethylene/butadiene copolymer obtained using said method, having butadiene units with 1,2-cyclohexane or 1,2 and 1,4-cyclohexane chains. The inventive complex has one of the following formulas (A and B), wherein, in formula A, two molecules of ligands Cp1 and Cp2 are linked to the lanthanide Ln, such as Nd, said ligand molecules each consisting of a fluorenyl group, and, in formula B, a ligand molecule is linked to the lanthanide Ln, said ligand molecule consisting of two fluorenyl groups Cp1 and Cp2 which are interlinked by means of a bridge P having formula MR1R2, in which M is an element from column IVA, such as Si, and R1 and R2, which may be identical or different, represent an alkyl group having between 1 and 20 carbon atoms. According to the invention, L represents an alkali metal, such as Li, N represents a molecule of a complexing solvent, such as THF, x is an integer or a non-integer which is greater than 0 and p is an integer which is equal to or greater than 1.

公开(公告)号：EP1957506A2

公开(公告)日：2008-08-20

申请号：EP06818327.6

申请日：2006-10-31

申请人： Société de Technologie Michelin ,  Michelin Recherche et Technique S.A. ,  Total Petrochemicals France ,  Centre National de la Recherche Scientifique ,  Ecole Superieure de Chimie Physique Electronique de Lyon

发明人： THUILLIEZ, Julien ,  BOISSON, Christophe ,  SPITZ, Roger

IPC分类号： C07F17/00 ,  C08F4/52 ,  C08F210/12

CPC分类号： C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

摘要： The invention relates to a borohydride metallocene complex of a lanthanide, the preparation method thereof, a catalytic system including said borohydride metallocene complex and a method for the copolymerisation of olefins using said catalytic system. The inventive complex has one of the following formulas (A and B), wherein, in formula A, two ligands Cp1 and Cp2 are linked to the lanthanide Ln, such as Nd, said ligands each consisting of a cyclopentadienyl group, and, in formula B, a ligand molecule is linked to the lanthanide Ln, said ligand molecule consisting of two cyclopentadienyl groups Cp1 and Cp2 which are interlinked by means of a bridge P having formula MR1R2, in which M is an element from column IVA, such as Si, and R1 and R2, which may be identical or different, represent an alkyl group having between 1 and 20 carbon atoms. According to the invention, L represents an alkali metal, such as Li, N represents a molecule of a complexing solvent, such as THF, x is an integer or a non-integer which is greater than 0, p is an integer which is equal to or greater than 1 and y is an integer which is equal to or greater than 0.

摘要翻译： 本发明涉及镧系元素的硼氢化物金属茂配合物，其制备方法，包括所述硼氢化物金属茂配合物的催化体系以及使用所述催化体系进行烯烃共聚的方法。 本发明的配合物具有下式（A和B）之一，其中在式A中，两个配体Cp1和Cp2连接至镧系元素Ln，例如Nd，所述配体各自由环戊二烯基组成，并且在式 B，配体分子与镧系元素Ln连接，所述配体分子由两个环戊二烯基Cp1和Cp2组成，它们通过具有式MR1R2的桥P相互连接，其中M是来自IVA列的元素，例如Si， 并且R1和R2可以相同或不同，表示具有1至20个碳原子的烷基。 根据本发明，L表示碱金属如Li，N表示配位溶剂例如THF的分子，x是大于0的整数或非整数，p是相等的整数 等于或大于1，并且y是等于或大于0的整数。

公开(公告)号：EP1957506B1

公开(公告)日：2014-10-22

申请号：EP06818327.6

申请日：2006-10-31

申请人： COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN ,  Michelin Recherche et Technique S.A. ,  Total Petrochemicals France ,  Centre National de la Recherche Scientifique ,  Ecole Superieure de Chimie Physique Electronique de Lyon

发明人： THUILLIEZ, Julien ,  BOISSON, Christophe ,  SPITZ, Roger

IPC分类号： C07F17/00 ,  C08F4/52 ,  C08F210/12

CPC分类号： C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

公开(公告)号：EP2424902B1

公开(公告)日：2013-08-14

申请号：EP10717618.2

申请日：2010-04-27

申请人： COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN ,  MICHELIN Recherche et Technique S.A. ,  Centre National de la Recherche Scientifique ,  Université Claude Bernard Lyon I

发明人： BOISSON, Christophe ,  ROLLAND, Olivier ,  THUILLIEZ, Julien

IPC分类号： C08F4/54 ,  C08F36/06 ,  C08F36/08

CPC分类号： C08F4/545 ,  C08F36/04

公开(公告)号：EP3230292A1

公开(公告)日：2017-10-18

申请号：EP15818014.1

申请日：2015-12-11

申请人： Compagnie Générale des Etablissements Michelin ,  Michelin Recherche et Technique S.A. ,  Université Claude Bernard Lyon 1 ,  Centre National de la Recherche Scientifique ,  CPE Lyon Formation Continue et Recherche

发明人： CORTIAL, Guillaume ,  THUILLIEZ, Julien ,  BOISSON, Christophe ,  D'AGOSTO, Franck ,  NORSIC, Sébastien

IPC分类号： C07F7/08

CPC分类号： C07F7/0816 ,  C07F7/081 ,  C08F10/02

摘要： The present invention relates to a compound of formula (II) and its use in the preparation of a functional or telechelic polyolefin: Y((CH
2 )
P -B')
m (II) m = 2 or 3; Y being and alkaline earth or zinc when m = 2, Y being aluminium when m = 3; B' being selected from the group comprising N(SiMe
3 )
2 ; N(SiMe
2 CH
2 CH
2 SiMe
2 ); C
6 F
5 ; C
3 F
7 ; C
6 F
13 ; para-C
6 H
4 -NMe
2 ; para-C
6 H
4 -0-Me; para-C
6 H
4 -N(SiMe
3 )
2 ; and CH(OCH
2 CH
2 0); p being an integer between 0 and 50.

摘要翻译： 本发明涉及式（II）化合物及其在制备官能或遥爪聚烯烃中的用途：Y（（CH 2）P-B'）m（II）m = 2或3; 当m = 2时Y为碱土或锌，当m = 3时Y为铝; B'选自N（SiMe 3）2; N（SiMe 2 CH 2 CH 2 SiMe 2）; C 6F 5; C 3F 7; C 6F 13; 对-C 6H 4 -NMe 2; 对-C 6H 4-0-Me; 对-C 6H 4 -N（SiMe 3）2; 和CH（OCH 2 CH 20）; p是0到50之间的整数。

公开(公告)号：EP1656400A1

公开(公告)日：2006-05-17

申请号：EP04763491.0

申请日：2004-07-26

申请人： Société de Technologie Michelin ,  MICHELIN RECHERCHE ET TECHNIQUE S.A. ,  TOTAL PETROCHEMICALS RESEARCH FELUY

发明人： BOISSON, Christophe ,  MONTEIL, Vincent ,  SPITZ, Roger

IPC分类号： C08F210/02 ,  C08F4/62

CPC分类号： C08F210/00 ,  C08F210/02 ,  C08F210/06 ,  C08F210/14 ,  C08F210/16 ,  C08F236/04 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

摘要： The invention relates to a catalytic system for the copolymerisation of a conjugated diene and at least one mono-olefin, a method for production of said catalytic system, a method for production of a copolymer of a conjugated diene and at least one mono-olefin, using said catalytic system and said copolymer. The catalytic system comprises (i) an organometallic complex, represented by the following generic formula (1) {[P(Cp)(F1)Ln(X)(Lx)}p, where Ln is a lanthanide atom to which is bonded a ligand molecule with cyclopentadienyl (Cp) and fluorenyl (F1) groups, bonded to each other by means of a bridge (P) of formula MR1R2, where M is an element of the IVA group and where R1 and R2, independently = an alkyl group with 1 to 20 C atoms, or cycloalkyl or phenyl groups with 6 to 20 C atoms, where X = a halogen which can be chlorine, fluorine, bromine, or iodine, where L comprises an optional complexing molecule such as an ether and, optionally a substantially less complexing molecule such as toluene, where p is a whole natural number equal to or greater than 1 and x is equal to or greater than 0 and (ii) a co-catalyst belonging to the group of alkyl magnesiums, alkyl lithiums, alkyl aluminiums, Grignard reagents and mixtures of said components.

公开(公告)号：EP1554321A1

公开(公告)日：2005-07-20

申请号：EP03776864.5

申请日：2003-10-13

申请人： Société de Technologie Michelin ,  MICHELIN RECHERCHE ET TECHNIQUE S.A. ,  TOTAL PETROCHEMICALS RESEARCH FELUY

发明人： Monteil, Vincent ,  SPITZ, Roger ,  BOISSON, Christophe

IPC分类号： C08F210/12 ,  C08F236/06

CPC分类号： C08F10/00 ,  C08F210/02 ,  C08F236/06 ,  C08F4/52 ,  C08F232/00 ,  C08F2500/01

摘要： The invention relates, in particular, to ethylene and butadiene copolymers and to a catalytic system which can be used for the synthesis of said copolymers. The inventive copolymers comprise a molar ratio of units derived from butatdiene which is greater than or equal to 8 %, said units comprising trans-1,2 cyclohexane chain formations, and have an average molecular mass Mn which is greater than or equal to 40 000 g/mol. According to the invention, the catalytic system consists of (i) an organometallic complex which is represented by either formula A or B , wherein: Ln represents a lanthanide and X represents a halogen. In formula A , two ligand molecules Cp1 and Cp2, which are each formed by a fluorenyl group, are linked to Ln. In formula B , a ligand molecule is linked to Ln, said molecule being formed by two fluorenyl groups Cp1 and Cp2 which are interconnected by a bridge P having formula MR2, wherein M is an element from column IVA and R is an alkyl with between 1 and 20 carbon atoms. The catalytic system also consists of (ii) a co-catalyst belonging to the group comprising a magnesium alkyl, a lithium alkyl, an aluminium alkyl, a Grignard reagent or a mixture of said components. Said catalytic system is such that the molar ratio (co-catalyst/organometallic complex) lies between 1 and 8.

公开(公告)号：EP4251659A1

公开(公告)日：2023-10-04

申请号：EP21823967.1

申请日：2021-11-19

申请人： COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN ,  Centre National de la Recherche Scientifique ,  Ecole Superieure de Chimie, Physique, Electronique de Lyon ,  Université Claude Bernard Lyon 1

发明人： BAULU, Nicolas ,  BOISSON, Christophe ,  D'AGOSTO, Franck ,  NGO, Robert ,  THUILLIEZ, Julien ,  JEAN-BAPTISTE-DIT-DOMINIQUE, François

IPC分类号： C08F10/02 ,  C08F4/54