公开(公告)号：US20090182104A1

公开(公告)日：2009-07-16

申请号：US12084809

申请日：2006-10-31

Applicant: Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

Inventor： Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

IPC: C07F17/00 ,  C08F4/52 ,  B01J31/12

CPC classification number: C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

Abstract: A borohydride metallocene complex of a lanthanide, its process of preparation, a catalytic system incorporating a borohydride metallocene complex and a process for the copolymerization of olefins employing this catalytic system. Such a complex corresponds to one or other of the following formulae A and B: where, in the formula A, two ligands Cp1 and Cp2, each composed of a cyclopentadienyl group, are connected to the lanthanide Ln, such as Nd, and where, in the formula B, a ligand molecule, composed of two cyclopentadienyl groups Cp1 and Cp2 which are connected to one another via a bridge P of formula MR1R2, where M is an element from group IVa, such as Si, and where R1 and R2, which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to the lanthanide Ln, where L represents an alkali metal, such as Li, where N represents a molecule of a complexing solvent, such as THF, where x is an integral or non-integral number greater than 0, where p is an integer equal to or greater than 1 and where y is an integer which is equal to or greater than 0.

Abstract translation: 镧系元素的硼氢化物茂金属络合物，其制备方法，掺入硼氢化物茂金属络合物的催化体系和使用该催化体系的烯烃共聚方法。 这样的复合物对应于下式A和B中的一种或其中之一：其中，在式A中，每个由环戊二烯基组成的两个配体Cp1和Cp2连接到镧系元素Ln如Nd， 在式B中，配体分子由两个环戊二烯基Cp1和Cp2组成，它们通过式MR1R2的桥P相互连接，其中M是Ⅳa族元素，如Si，其中R1和R2， 其相同或不同，表示含有1至20个碳原子的烷基，连接到镧系元素Ln，其中L表示碱金属，例如Li，其中N表示络合溶剂如THF的分子， 其中x是大于0的整数或非整数，其中p是等于或大于1的整数，其中y是等于或大于0的整数。

公开(公告)号：US20090042720A1

公开(公告)日：2009-02-12

申请号：US10587058

申请日：2006-07-21

Applicant: Floran Prades ,  Christophe Boisson ,  Roger Spitz ,  Abbas Razavi

Inventor： Floran Prades ,  Christophe Boisson ,  Roger Spitz ,  Abbas Razavi

IPC: B01J31/12 ,  C01B7/19 ,  C01B33/10 ,  B32B5/16

CPC classification number: C08F10/00 ,  C08F4/65912 ,  C08F4/65927 ,  C08F110/02 ,  C08F110/06 ,  C08F210/16 ,  Y10S526/902 ,  Y10S526/907 ,  Y10S526/943 ,  Y10T428/2982 ,  C08F4/65916 ,  C08F4/025 ,  C08F2500/15 ,  C08F2500/12 ,  C08F2500/18 ,  C08F210/14

Abstract: The present invention relates to a process for preparing an activating support for metallocene complexes in the polymerisation of olefins comprising the steps of: I) providing a support prepared consisting in particles formed from at least one porous mineral oxide; II) optionally fixing the rate of silanols on the surface of the support; III) functionalising the support with a solution containing a fluorinated functionalising agent; IV) heating the functionalised and fluorinated support of step c) under an inert gas and then under oxygen; V) retrieving an active fluorinated support. That activating support is used to activate a metallocene catalyst component for the polymerisation of olefins.

Abstract translation: 本发明涉及一种在烯烃聚合中制备茂金属络合物的活化载体的方法，包括以下步骤：I）提供由至少一种多孔矿物氧化物形成的颗粒制备的载体; II）任选地将硅烷醇的速率固定在载体的表面上; III）使用含氟官能化剂的溶液功能化载体; IV）在惰性气体下，然后在氧气下加热步骤c）的官能化和氟化载体; V）检索活性氟化支持物。 该活化载体用于活化用于烯烃聚合的茂金属催化剂组分。

公开(公告)号：US07094854B2

公开(公告)日：2006-08-22

申请号：US11106619

申请日：2005-04-15

Applicant: Vincent Monteil ,  Roger Spitz ,  Christophe Boisson

Inventor： Vincent Monteil ,  Roger Spitz ,  Christophe Boisson

IPC: C08F236/06

CPC classification number: C08F10/00 ,  C08F210/02 ,  C08F236/06 ,  C08F4/52 ,  C08F232/00 ,  C08F2500/01

Abstract: Disclosed are ethylene and butadiene copolymers and a catalytic system usable for the synthesis of these copolymers. The copolymers have a molar content of units resulting from butadiene of ≧8%, said units comprising trans-1,2 cyclohexane linkages, and a number-average molecular mass Mn of ≧40,000 g/mol. The catalytic system includes: (i) an organometallic complex represented by one of the following formulae A or B: where Ln represents a lanthanide and X a halogen, where, in the formula A, two ligand molecules Cp1 and Cp2 each consisting of a fluorenyl group, are attached to Ln, where, in the formula B, a ligand molecule consisting of two fluorenyl groups Cp1 and Cp2, joined together by a bridge P of formula MR2, where M is an element of column IVa and R is an alkyl with 1 to 20 carbon atoms, is attached to Ln, and (ii) a co-catalyst selected from an alkylmagnesium, an alkyllithium, an alkylaluminium, a Grignard reagent, or a mixture of these constituents. The (co-catalyst/organometallic complex) molar ratio falls within a range of from 1 to 8.

Abstract translation: 公开了乙烯和丁二烯共聚物和可用于合成这些共聚物的催化体系。 共聚物具有由丁二烯> 8％产生的单元的摩尔含量，所述单元包含反式-1,2-环己烷键，且数均分子量Mn> 40,000g / mol。 催化体系包括：（i）由下式A或B之一表示的有机金属络合物：其中Ln表示镧系元素，X为卤素，其中在式A中，两个配体分子Cp 1 和由芴基组成的Cp 2 2连接到Ln，其中在式B中，由两个芴基Cp 1和Cp 2组成的配体分子， 其中M是式IVa的元素，其中M是第IVa列的元素，R是具有1至20个碳原子的烷基，连接到Ln的桥P上 ，和（ii）选自烷基镁，烷基锂，烷基铝，格氏试剂或这些组分的混合物的助催化剂。 （助催化剂/有机金属络合物）摩尔比在1〜8的范围内。

公开(公告)号：US20060160969A1

公开(公告)日：2006-07-20

申请号：US11350754

申请日：2006-02-10

Applicant: Christophe Boisson ,  Vincent Monteil ,  Roger Spitz

Inventor： Christophe Boisson ,  Vincent Monteil ,  Roger Spitz

IPC: C08F4/44 ,  B01J31/00

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

Abstract: A catalytic system usable for the copolymerization of at least one conjugated diene and at least one monoolefin, a process for preparing this catalytic system, a process for preparing a copolymer of a conjugated diene and at least one monoolefin using said catalytic system, and said copolymer are described. This catalytic system includes: (i) an organometallic complex represented by the following formula: {[P(Cp)(Fl)Ln(X)(Lx)}p   (1) where Ln represents a lanthanide atom to which is attached a ligand molecule comprising cyclopentadienyl Cp and fluorenyl Fl groups linked to one another by a bridge P of the formula MR1R2, M is an element from column IVa of Mendeleev's periodic table and R1 and R2 each represent alkyl groups of 1 to 20 carbon atoms or cycloalkyl or phenyl groups of 6 to 20 carbon atoms, X represents a halogen atom, L represents an optional complexing molecule, such as an ether, and optionally a substantially less complexing molecule, such as toluene, p is a natural integer greater than or equal to 1 and x is greater than or equal to 0, and (ii) a co-catalyst selected from alkylmagnesiums, alkyllithiums, alkylaluminums, Grignard reagents and mixtures of these constituents.

Abstract translation: 一种可用于共聚二烯和至少一种单烯烃的催化体系，该催化体系的制备方法，使用所述催化体系制备共轭二烯和至少一种单烯烃的共聚物的方法，所述共聚物 被描述。 该催化体系包括：（i）由下式表示的有机金属络合物：<？in-line-formula description =“In-line formula”end =“lead”？> {[P（Cp）（Fl）Ln （1）<？in-line-formula description =“In-line Formulas”end =“tail”？>其中Ln表示（x）（L x x） 连接有配体分子的镧系元素原子，该配体分子包含通过式MR 1的桥P彼此连接的环戊二烯基Cp和芴基F 1基团，M是 Mendeleev的元素周期表IVa的元素和R 1和R 2各自表示1-20个碳原子的烷基或6-20个碳原子的环烷基或苯基， X表示卤素原子，L表示任选的络合分子，例如醚，以及任选的基本上较少络合的分子如甲苯，p是大于或等于1的自然整数，x大于或等于0 ，和（ii）助催化剂，选自烷基镁， 烷基锂，烷基铝，格氏试剂和这些组分的混合物。

公开(公告)号：US08946368B2

公开(公告)日：2015-02-03

申请号：US13318022

申请日：2010-04-27

Applicant: Christophe Boisson ,  Olivier Rolland ,  Julien Thuilliez

Inventor： Christophe Boisson ,  Olivier Rolland ,  Julien Thuilliez

IPC: C08F36/06 ,  C08F36/08 ,  C08F4/52 ,  C08F4/602

CPC classification number: C08F4/545 ,  C08F36/04

Abstract: The present invention relates to a multi-component catalytic system that can be used for the cis-1,4 stereospecific polymerization of conjugated dienes. The system is based on: (i) a rare-earth complex of Formula (II) Ln(A)3(B)n, Ln being a rare-earth metal, A a ligand, B a Lewis base or a solvent molecule and n a number from 0 to 3; (ii) an alkylating agent; (iii) a compound based on an aromatic ring and having at least two heteroatoms chosen from the elements O, N, S, P, and corresponding to the Formula (III): in which the R groups each denote hydrogen, an alkyl radical optionally comprising one or more heteroatoms (N, O, P, S, Si) or one or more halogen atoms, a halogen atom, a group based on one or more heteroatoms (N, O, P, S, Si); x and y are integers from 0 to 6; D is a group having a chemical function, one of the atoms of which has a non-bonding pair; L being an atom from column 1 of the Periodic Table.

Abstract translation: 本发明涉及可用于共轭二烯的顺式-1,4-立体有择聚合的多组分催化体系。 该系统基于：（i）式（II）Ln（A）3（B）n的稀土络合物，Ln是稀土金属，A a配体，B路易斯碱或溶剂分子，以及 na数从0到3; （ii）烷基化剂; （iii）基于芳环并且具有至少两个选自元素O，N，S，P的杂原子并且对应于式（III）的化合物：其中R基团各自表示氢，任选的烷基 包括一个或多个杂原子（N，O，P，S，Si）或一个或多个卤素原子，卤素原子，基于一个或多个杂原子（N，O，P，S，Si）的基团。 x和y是0〜6的整数; D是具有化学功能的基团，其原子之一具有非键合对; L是周期表第1列的原子。

公开(公告)号：US20130274429A1

公开(公告)日：2013-10-17

申请号：US13994216

申请日：2012-01-12

Applicant: Melanie Muron ,  Gaelle Pannier ,  Christopher John Whiteoak ,  Roger Spitz ,  Christophe Boisson

Inventor： Melanie Muron ,  Gaelle Pannier ,  Christopher John Whiteoak ,  Roger Spitz ,  Christophe Boisson

IPC: C08F4/76 ,  C08F4/52

CPC classification number: C08F4/76 ,  C08F4/52 ,  C08F4/6592 ,  C08F4/65927 ,  C08F10/00 ,  C08F210/16 ,  C08F2420/02 ,  Y10S526/943 ,  C08F4/65916 ,  C08F4/025 ,  C08F4/7006 ,  C08F210/14

Abstract: Activating supports may be suitably prepared by the following procedure (a) providing a porous mineral oxide support material, (b) treating the support with a phosphorus-containing compound, (c) treating the support from step (b) with an organometallic compound, (d) heating the functionalized support from step (c) under an inert gas and then under an atmosphere comprising oxygen, (e) fluorinating the support with a fluorinating agent, and (f) recovering an activating support. The activating supports are suitable used in combination with single site catalysts for the polymerization of olefins. The supports are most preferably used in combination with metallocene complexes. The preparative route for the activating supports provides for supported polymerization catalyst systems having excellent activities.

Abstract translation: 活化载体可以通过以下步骤（a）适当地制备：（a）提供多孔无机氧化物载体材料，（b）用含磷化合物处理载体，（c）用有机金属化合物处理步骤（b）的载体， （d）在惰性气体下，然后在包含氧的气​​氛下加热步骤（c）的官能化载体，（e）用氟化剂氟化载体，和（f）回收活化载体。 活化载体适合与用于烯烃聚合的单中心催化剂组合使用。 载体最优选与茂金属络合物组合使用。 用于活化载体的制备路线提供了具有优异活性的负载型聚合催化剂体系。

公开(公告)号：US08268949B2

公开(公告)日：2012-09-18

申请号：US13290617

申请日：2011-11-07

Applicant: Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

Inventor： Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

IPC: C08F236/06 ,  C08F4/52

CPC classification number: C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

Abstract: Borohydride metallocene complex of lanthanide, preparation process, catalytic system incorporating it, copolymerization of olefins employing catalytic system and ethylene/butadiene copolymer, the butadiene units comprise 1,2-cyclohexane or 1,2- and 1,4-cyclohexane links. The complex corresponds to of formulae A and/or B: where, in A two ligands Cp1 and Cp2, each of a fluorenyl group, are connected to the lanthanide Ln, where, in B, a ligand molecule, composed of two fluorenyl groups Cp1 and Cp2 are connected via bridge P of formula MR1R2, is an element from group IVa, R1 and R2, which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, connected to lanthanide Ln, L is alkali metal, N is molecule of a complexing solvent, x is integral or non-integral number ≧0 and p is integer ≧1.

Abstract translation: 镧系元素的硼氢化物茂金属络合物，制备方法，结合其的催化体系，使用催化体系的烯烃共聚和乙烯/丁二烯共聚物，丁二烯单元包括1,2-环己烷或1,2-和1,4-环己烷连接。 络合物对应于式A和/或B：其中在A两配体Cp1和Cp2中，每个芴基连接到镧系元素Ln，其中在B中，由两个芴基Cp1组成的配体分子 Cp2通过式MR1R2的桥P连接，是相同或不同的来自IVa，R1和R2的元素，代表与镧系元素Ln连接的含有1至20个碳原子的烷基，L是碱金属， N是络合溶剂的分子，x是整数或非整数，≧0，p是整数≧1。

公开(公告)号：US20120149858A1

公开(公告)日：2012-06-14

申请号：US13404757

申请日：2012-02-24

Applicant: David Ribour ,  Roger Spitz ,  Jerome Gromada ,  Christophe Boisson

Inventor： David Ribour ,  Roger Spitz ,  Jerome Gromada ,  Christophe Boisson

IPC: C08F4/50

CPC classification number: C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  C08F210/16 ,  C08F2410/01 ,  C08F4/657 ,  C08F4/6574 ,  C08F2500/04 ,  C08F2500/15 ,  C08F210/14

Abstract: The present invention provides a method for improving and controlling the activity of Ziegler-Natta catalyst systems.

Abstract translation: 本发明提供了改善和控制齐格勒 - 纳塔催化剂体系的活性的方法。

公开(公告)号：US08071800B2

公开(公告)日：2011-12-06

申请号：US12084808

申请日：2006-10-31

Applicant: Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

Inventor： Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

IPC: C07F17/00 ,  C07F5/00 ,  C08F4/52 ,  C08F36/00 ,  B01J31/22

CPC classification number: C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

Abstract: A borohydride metallocene complex of a lanthanide, its process of preparation, a catalytic system incorporating it, a process for the copolymerization of olefins employing this catalytic system and an ethylene/butadiene copolymer obtained by this process, the butadiene units of which comprise 1,2-cyclohexane or 1,2- and 1,4-cyclohexane links. This complex corresponds to one or other of the following formulae A and B: where, in the formula A, two ligand molecules Cp1 and Cp2, each composed of a fluorenyl group, are connected to the lanthanide Ln, such as Nd, and where, in the formula B, a ligand molecule, composed of two fluorenyl groups Cp1 and Cp2 which are connected to one another via a bridge P of formula MR1R2, where M is an element from group IVa, such as Si, and where R1 and R2, which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to the lanthanide Ln, where L represents an alkali metal, such as Li, where N represents a molecule of a complexing solvent, such as THF, where x is an integral or non-integral number greater than 0 and where p is an integer equal to or greater than 1.

Abstract translation: 镧系元素的硼氢化物茂金属络合物，其制备方法，其结合的催化体系，使用该催化体系的烯烃共聚方法和通过该方法获得的乙烯/丁二烯共聚物，其丁二烯单元包含1,2 环己烷或1,2-和1,4-环己烷连接。 该络合物对应于下式A和B中的一种或其中之一：其中，在式A中，由芴基组成的两个配体分子Cp1和Cp2连接到镧系元素Ln如Nd， 在式B中，配体分子由两个芴基Cp1和Cp2组成，它们通过式MR1R2的桥P相互连接，其中M是Ⅳa族元素，如Si，其中R1和R2， 其相同或不同，表示含有1至20个碳原子的烷基，连接到镧系元素Ln，其中L表示碱金属，例如Li，其中N表示络合溶剂如THF的分子， 其中x是大于0的整数或非整数，其中p是等于或大于1的整数。

公开(公告)号：US08071700B2

公开(公告)日：2011-12-06

申请号：US12084809

申请日：2006-10-31

Applicant: Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

Inventor： Julien Thuilliez ,  Christophe Boisson ,  Roger Spitz

IPC: C07F17/00 ,  C07F5/00 ,  C08F36/00 ,  C08F4/52 ,  B01J31/22

CPC classification number: C08F210/02 ,  C07F17/00 ,  C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F236/06

Abstract: A borohydride metallocene complex of a lanthanide, its process of preparation, a catalytic system incorporating a borohydride metallocene complex and a process for the copolymerization of olefins employing this catalytic system. Such a complex corresponds to one or other of the following formulae A and B: where, in the formula A, two ligands Cp1 and Cp2, each composed of a cyclopentadienyl group, are connected to the lanthanide Ln, such as Nd, and where, in the formula B, a ligand molecule, composed of two cyclopentadienyl groups Cp1 and Cp2 which are connected to one another via a bridge P of formula MR1R2, where M is an element from group IVa, such as Si, and where R1 and R2, which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to the lanthanide Ln, where L represents an alkali metal, such as Li, where N represents a molecule of a complexing solvent, such as THF, where x is an integral or non-integral number greater than 0, where p is an integer equal to or greater than 1 and where y is an integer which is equal to or greater than 0.

Abstract translation: 镧系元素的硼氢化物茂金属络合物，其制备方法，掺入硼氢化物茂金属络合物的催化体系和使用该催化体系的烯烃共聚方法。 这样的复合物对应于下式A和B中的一种或其中之一：其中，在式A中，每个由环戊二烯基组成的两个配体Cp1和Cp2连接到镧系元素Ln如Nd， 在式B中，配体分子由两个环戊二烯基Cp1和Cp2组成，它们通过式MR1R2的桥P相互连接，其中M是Ⅳa族元素，如Si，其中R1和R2， 其相同或不同，表示含有1至20个碳原子的烷基，连接到镧系元素Ln，其中L表示碱金属，例如Li，其中N表示络合溶剂如THF的分子， 其中x是大于0的整数或非整数，其中p是等于或大于1的整数，其中y是等于或大于0的整数。