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1. 发明申请

US20130274429A1 ACTIVATING SUPPORTS 有权
标题翻译：活动支持
公开(公告)号：US20130274429A1
公开(公告)日：2013-10-17
申请号：US13994216
申请日：2012-01-12
申请人： Melanie Muron , Gaelle Pannier , Christopher John Whiteoak , Roger Spitz , Christophe Boisson
发明人： Melanie Muron , Gaelle Pannier , Christopher John Whiteoak , Roger Spitz , Christophe Boisson
IPC分类号： C08F4/76 , C08F4/52
CPC分类号： C08F4/76 , C08F4/52 , C08F4/6592 , C08F4/65927 , C08F10/00 , C08F210/16 , C08F2420/02 , Y10S526/943 , C08F4/65916 , C08F4/025 , C08F4/7006 , C08F210/14
摘要： 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.
摘要翻译：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。

2. 发明申请

US20130158215A1 MODIFIED ZIEGLER-NATTA CATALYST SYSTEMS 审中-公开
标题翻译：改性ZIEGLER-NATTA催化剂体系
公开(公告)号：US20130158215A1
公开(公告)日：2013-06-20
申请号：US13698025
申请日：2011-05-19
申请人： Elsa Martigny , Vincent Monteil , Roger Spitz , Aurélien Vantomme
发明人： Elsa Martigny , Vincent Monteil , Roger Spitz , Aurélien Vantomme
IPC分类号： C08F4/685 , C08F210/16 , C08F10/02 , C08F4/646 , C08F4/68
CPC分类号： C08F4/685 , C08F4/646 , C08F4/68 , C08F10/00 , C08F10/02 , C08F210/16 , C08F210/14 , C08F2500/23 , C08F4/02 , C08F4/657
摘要： This invention relates to modified Ziegler-Natta catalyst systems that have an excellent activity in homo- or co-polymerisation of ethylene and alpha-olefins and are able to produce polymers having reduced molecular weight distribution and improved incorporation of hexene with respect to conventional Ziegler-Natta catalyst systems.
摘要翻译：本发明涉及在乙烯和α-烯烃的均聚或共聚合中具有优异活性的改性齐格勒 - 纳塔催化剂体系，并且能够生产具有降低的分子量分布和改进己烯掺入的聚合物相对于常规的齐格勒 - 纳塔催化剂体系。

3. 发明授权

US08268949B2 Borohydride metallocene complex of a lanthanide, catalytic system including the said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method 有权
标题翻译：镧系元素的硼氢化物茂金属络合物，包括所述络合物的催化体系，使用其的聚合方法和使用所述方法获得的乙烯/丁二烯共聚物
公开(公告)号：US08268949B2
公开(公告)日：2012-09-18
申请号：US13290617
申请日：2011-11-07
申请人： Julien Thuilliez , Christophe Boisson , Roger Spitz
发明人： Julien Thuilliez , Christophe Boisson , Roger Spitz
IPC分类号： C08F236/06 , C08F4/52
CPC分类号： C08F210/02 , C07F17/00 , C08F10/00 , Y10S526/943 , C08F4/52 , C08F236/06
摘要： 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.
摘要翻译：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。

4. 发明申请

US20120149858A1 Controlled Distribution of Active Sites in Ziegler-Natta Catalyst Systems 审中-公开
标题翻译： Ziegler-Natta催化剂体系中活性位点的控制分布
公开(公告)号：US20120149858A1
公开(公告)日：2012-06-14
申请号：US13404757
申请日：2012-02-24
申请人： David Ribour , Roger Spitz , Jerome Gromada , Christophe Boisson
发明人： David Ribour , Roger Spitz , Jerome Gromada , Christophe Boisson
IPC分类号： C08F4/50
CPC分类号： C08F10/00 , C08F110/02 , C08F110/06 , C08F210/16 , C08F2410/01 , C08F4/657 , C08F4/6574 , C08F2500/04 , C08F2500/15 , C08F210/14
摘要： The present invention provides a method for improving and controlling the activity of Ziegler-Natta catalyst systems.
摘要翻译：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。

5. 发明授权

US08071800B2 Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerization method using same and ethylene/butadiene copolymer obtained using said method 有权
标题翻译：镧系元素的硼氢化物茂金属络合物，包括所述络合物的催化体系，使用其的聚合方法和使用所述方法获得的乙烯/丁二烯共聚物
公开(公告)号：US08071800B2
公开(公告)日：2011-12-06
申请号：US12084808
申请日：2006-10-31
申请人： Julien Thuilliez , Christophe Boisson , Roger Spitz
发明人： Julien Thuilliez , Christophe Boisson , Roger Spitz
IPC分类号： C07F17/00 , C07F5/00 , C08F4/52 , C08F36/00 , B01J31/22
CPC分类号： C08F210/02 , C07F17/00 , C08F10/00 , Y10S526/943 , C08F4/52 , C08F236/06
摘要： 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.
摘要翻译：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。

6. 发明授权

US08071700B2 Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerization method using same and ethylene/butadiene copolymer obtained using said method 有权
标题翻译：镧系元素的硼氢化物茂金属络合物，包括所述络合物的催化体系，使用其的聚合方法和使用所述方法获得的乙烯/丁二烯共聚物
公开(公告)号：US08071700B2
公开(公告)日：2011-12-06
申请号：US12084809
申请日：2006-10-31
申请人： Julien Thuilliez , Christophe Boisson , Roger Spitz
发明人： Julien Thuilliez , Christophe Boisson , Roger Spitz
IPC分类号： C07F17/00 , C07F5/00 , C08F36/00 , C08F4/52 , B01J31/22
CPC分类号： C08F210/02 , C07F17/00 , C08F10/00 , Y10S526/943 , C08F4/52 , C08F236/06
摘要： 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.
摘要翻译：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。

7. 发明授权

US07060767B2 Supported metallocene catalytic component and method for obtaining same 失效
标题翻译：负载金属茂催化剂组分及其制备方法
公开(公告)号：US07060767B2
公开(公告)日：2006-06-13
申请号：US10476152
申请日：2002-04-26
申请人： Frédéric Bortolussi , Christophe Boisson , Roger Spitz , Jean Malinge , Jean-Pierre Broyer
发明人： Frédéric Bortolussi , Christophe Boisson , Roger Spitz , Jean Malinge , Jean-Pierre Broyer
IPC分类号： C08F4/16 , C08F4/52 , C08F4/44 , C08F4/58
CPC分类号： C08F10/00 , C08F4/65908 , C08F4/65912 , C08F4/65925 , C08F4/65927 , C08F110/02 , Y10S526/943 , C08F4/65916 , C08F2500/12
摘要： The invention discloses a solid catalytic component comprising a metallocene, at least one first ligand of which comprises a cyclopentadienyl group chemically bonded via a methyl group to a support composed of a porous inorganic compound. It also discloses a process for the preparation of such a solid catalytic component.Application to the polymerization and copolymerization of olefins.
摘要翻译：本发明公开了一种包含茂金属的固体催化组分，其至少一种第一配体包括通过甲基与由多孔无机化合物组成的载体化学键合的环戊二烯基。它还公开了制备这种固体催化组分的方法。应用于烯烃的聚合和共聚。

8. 发明申请

US20050239639A1 Ethylene/butadiene copolymers, catalytic system and process for the synthesis thereof 有权
标题翻译：乙烯/丁二烯共聚物，催化体系及其合成方法
公开(公告)号：US20050239639A1
公开(公告)日：2005-10-27
申请号：US11106619
申请日：2005-04-15
申请人： Vincent Monteil , Roger Spitz , Christophe Boisson
发明人： Vincent Monteil , Roger Spitz , Christophe Boisson
IPC分类号： C08F210/12 , C08F10/00 , C08F210/02 , C08F236/06 , B01J31/00 , C08F4/44
CPC分类号： C08F10/00 , C08F210/02 , C08F236/06 , C08F4/52 , C08F232/00 , C08F2500/01
摘要： 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.
摘要翻译：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。

9. 发明授权

US06949489B1 Solid supported catalyst usable for the polymerization of conjugated dienes, process for the preparation thereof and a process for the polymerization of conjugated dienes using this catalyst 有权
标题翻译：可用于共轭二烯聚合的固体负载催化剂，其制备方法和使用该催化剂共轭二烯聚合的方法
公开(公告)号：US06949489B1
公开(公告)日：2005-09-27
申请号：US09688376
申请日：2000-10-11
申请人： Fanny Barbotin , Christophe Boisson , Roger Spitz
发明人： Fanny Barbotin , Christophe Boisson , Roger Spitz
IPC分类号： C08F4/06 , C08F4/54 , C08F4/618 , C08F4/6192 , C08F36/04 , B01J31/00 , B01J37/00 , C08F4/02 , C08F4/60
CPC分类号： C08F36/04 , C08F4/545 , C08F4/52
摘要： The present invention relates to a solid supported catalyst usable for the polymerization of conjugated dienes, to a process for the preparation of said catalyst and to a process for the polymerization of conjugated dienes using said catalyst. The solid supported catalyst according to the invention comprises the reaction product of a) a complex represented by formula M(Ar)(AlX4)3, where M is a rare earth metal selected from among the metals having an atomic number of from 57 to 71, inclusive in Mendeleyev's periodic table of elements, Ar is an aromatic hydrocarbon solvent, Al is aluminum and X is selected from the group consisting of fluorine, chlorine, bromine and iodine, and b) a solid support comprising at least one inorganic metal oxide compound. The invention also provides a polymerization process for conjugated dienes in an inert hydrocarbon solvent in which the said catalyst is used to polymerize the conjugated dienes in the presence of an activator compound comprising a trialkylaluminum or dialkylaluminum hydride.
摘要翻译：本发明涉及可用于共轭二烯的聚合的固体负载催化剂，制备所述催化剂的方法和使用所述催化剂聚合共轭二烯的方法。根据本发明的固体负载型催化剂包括a）由式M（Ar）（Al x S 3）3 N 3表示的络合物的反应产物，其中M是稀土选自Mendeleyev元素周期表中的原子序数为57〜71的金属中的金属，Ar为芳烃溶剂，Al为铝，X为氟，氯，溴，碘等和b）包含至少一种无机金属氧化物化合物的固体载体。本发明还提供了在惰性烃溶剂中的共轭二烯的聚合方法，其中所述催化剂用于在包含三烷基铝或二烷基铝氢化物的活化剂化合物的存在下聚合共轭二烯。

10. 发明授权

US06818714B1 Method for polymerizing olefins in the presence of nickel complexes and corresponding catalytic system 失效
标题翻译：在镍络合物和相应的催化体系存在下使烯烃聚合的方法
公开(公告)号：US06818714B1
公开(公告)日：2004-11-16
申请号：US09936902
申请日：2002-02-04
申请人： Atanas Tomov , Roger Spitz , Thierry Saudemont
发明人： Atanas Tomov , Roger Spitz , Thierry Saudemont
IPC分类号： C08F444
CPC分类号： C08F10/00 , B01J31/1845 , B01J31/1895 , B01J31/2291 , B01J2531/847 , C07F15/04 , C08F10/02 , C08F110/02 , C08F210/16 , C08F4/80 , C08F4/26 , C08F2/24 , C08F2500/04 , C08F2500/20 , C08F210/06 , C08F2500/03
摘要： This system consists of (A) at least one ligand (I) and (B) at least one nickel compound chosen from nickel complexes of zero oxidation state; &pgr;-allylnickels; and compounds of the bis(allyl)nickel type where E, E′=O, S; X, X′=P, As, Sb; R1, R′1=H, alkyl, aryl, arylalkyl, alkylaryl, halogen, OH, alkoxide where R′=a hydrocarbon radical of the C1-C15 type; —SO3Y where Y=Li, Na, NH4+, NR″4+ (R″=C1-C15 hydrocarbon radical); R2, R′2, R3, R′3, R4 and R′4=alkyl, arylalkyl; and R=divalent radical.
摘要翻译：该系统由（A）至少一种配体（I）和（B）至少一种选自零氧化态的镍络合物的镍化合物组成; 二烯丙基镍和双（烯丙基）镍类化合物E，E'= O，S; X，X'= P，As，Sb; R 1，R'1 = H，烷基，芳基，芳基烷基，烷基芳基，卤素，OH，烷氧基，其中R'= C1-C15型的烃基; -SO3Y，其中Y = Li，Na， +，NR'4 +（R“= C1-C15烃基）; R 2，R'2，R 3，R'3，R 4和R'4 =烷基，芳基烷基; 和R =二价基团。

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