公开(公告)号：US20120116033A1

公开(公告)日：2012-05-10

申请号：US13344368

申请日：2012-01-05

Applicant: Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

Inventor： Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

IPC: C08F4/80 ,  C08F210/16 ,  C08F36/04 ,  C08F10/02 ,  C08F10/00 ,  C08F4/70 ,  C08F110/02

CPC classification number: B01J31/1815 ,  B01J2231/122 ,  B01J2531/842 ,  C07F15/025 ,  C08F10/00 ,  C08F110/02 ,  C08F2500/12 ,  C08F2500/04 ,  C08F2500/20 ,  C08F2500/19 ,  C08F2500/17 ,  C08F4/60089 ,  C08F4/7042

Abstract: Catalyst compositions having Cs symmetry and processes utilizing Cs symmetric catalyst components for the polymerization of ethylenically unsaturated monomers to produce polymers, including copolymers or homopolymers. Monomers, which are polymerized or copolymerized include ethylene, C3+ alpha olefins and substituted vinyl compounds, such as styrene and vinyl chloride. The catalyst component is characterized by the formula: wherein M is a Group 4-11 transition metal, n is an integer of from 1-3, Q is halogen or a C1-C2 alkyl group, PY is a pyridinyl group, R′ and R″ are each C1-C20 hydrocarbyl group, A1 is a mononuclear aromatic group, and A2 is a polynuclear aromatic group, such as a terphenyl group. The catalyst component is used with an activating co-catalyst component such as an alumoxane. Also disclosed is a process for the preparation of a pyridinyl-linked bis-amino ligand suitable for use in forming the catalyst component.

Abstract translation: 具有Cs对称性的催化剂组合物和利用Cs对称催化剂组分用于烯键式不饱和单体聚合以产生聚合物（包括共聚物或均聚物）的方法。 聚合或共聚的单体包括乙烯，C 3+α-烯烃和取代的乙烯基化合物，例如苯乙烯和氯乙烯。 催化剂组分的特征在于下式：其中M是4-11族过渡金属，n是1-3的整数，Q是卤素或C 1 -C 2烷基，P Y是吡啶基，R'和 R“分别为C1-C20烃基，A1为单核芳香族基团，A2为三联苯基等多核芳香族基团。 催化剂组分与活化助催化剂组分如铝氧烷一起使用。 还公开了制备适于用于形成催化剂组分的吡啶基连接的双 - 氨基配体的方法。

公开(公告)号：US20120095174A1

公开(公告)日：2012-04-19

申请号：US13331459

申请日：2011-12-20

Applicant: Vladimir Marin ,  Margarito Lopez ,  Abbas Razavi ,  Tim Coffy ,  Michel Daumerie

Inventor： Vladimir Marin ,  Margarito Lopez ,  Abbas Razavi ,  Tim Coffy ,  Michel Daumerie

IPC: C08F4/52 ,  C08F10/00 ,  C08F2/00

CPC classification number: C08F10/00 ,  B01J21/12 ,  B01J37/26 ,  C08F4/65912 ,  C08F4/65927 ,  C08F10/06 ,  C08F110/06 ,  C08F210/06 ,  C08F2400/02 ,  Y10S526/943 ,  C08F4/65916 ,  C08F2/00 ,  C08F4/025 ,  C08F2500/20 ,  C08F2500/03 ,  C08F2500/12 ,  C08F210/14 ,  C08F2500/04 ,  C08F210/16

Abstract: Supported catalyst systems and methods of forming the same are described herein. In one specific embodiment, the methods generally include providing an inorganic support material and contacting the inorganic support material with an aluminum fluoride compound represented by the formula AlFpX3-pBq to form an aluminum fluoride impregnated support, wherein X is selected from Cl, Br and OH−, B is H2O, p is selected from 1 to 3 and q is selected from 0 to 6. The method further includes contacting the aluminum fluoride impregnated support with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n; wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

Abstract translation: 载体催化剂体系及其形成方法在此描述。 在一个具体实施方案中，方法通常包括提供无机载体材料并使无机载体材料与式AlFpX3-pBq表示的氟化铝化合物接触以形成氟化铝浸渍的载体，其中X选自Cl，Br和OH - ，B是H 2 O，p选自1至3，q选自0至6.该方法还包括使氟化铝浸渍的载体与过渡金属化合物接触以形成负载型催化剂体系，其中过渡金属化合物为 由式[L] mM [A] n表示; 其中L是大体积配体，A是离去基团，M是过渡金属，m和n使总配体的化合价对应于过渡金属的价态。

公开(公告)号：US08138285B2

公开(公告)日：2012-03-20

申请号：US12102226

申请日：2008-04-14

Applicant: Vladimir Marin

Inventor： Vladimir Marin

IPC: C08F4/02 ,  C08F4/60 ,  C08F4/6592 ,  B01J31/22

CPC classification number: C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F4/02

Abstract: Methods of forming supported catalyst systems, supported catalyst systems and polymerization processes utilizing the supported catalyst systems are described herein. The methods generally include providing an inorganic support material and contacting the inorganic support material with a support solvent to form a support solution. The methods further include contacting the support solution with a fluorine containing compound represented by the formula AlFpX3-pBq to impregnate the fluorine containing compound within the inorganic support material and form an intermediate, wherein X is selected from Cl, Br and OH−, B is H2O, p is selected from 1 to 3 and q is selected from 0 to 6. In addition, the methods include drying the intermediate to remove the solvent therefrom and heating the intermediate at a temperature of at least about 300° C. to form an impregnated support and contacting the impregnated support with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n; wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

Abstract translation: 在此描述形成负载型催化剂体系的方法，负载型催化剂体系和利用负载型催化剂体系的聚合方法。 所述方法通常包括提供无机载体材料并使无机载体材料与支持溶剂接触以形成支持溶液。 所述方法还包括将载体溶液​​与由式AlFpX3-pBq表示的含氟化合物接触以在无机载体材料中浸渍含氟化合物并形成中间体，其中X选自Cl，Br和OH-，B为 H 2 O，p选自1至3，q选自0至6.此外，所述方法包括干燥中间体以除去溶剂，并在至少约300℃的温度下加热中间体以形成 浸渍的载体并使浸渍的载体与过渡金属化合物接触以形成负载型催化剂体系，其中过渡金属化合物由式[L] mM [A] n表示; 其中L是大体积配体，A是离去基团，M是过渡金属，m和n使总配体的化合价对应于过渡金属的价态。

公开(公告)号：US20110313118A1

公开(公告)日：2011-12-22

申请号：US13220978

申请日：2011-08-30

Applicant: Vladimir Marin

Inventor： Vladimir Marin

IPC: C08F4/76 ,  C08F36/04 ,  C08F10/06 ,  C08F210/16

CPC classification number: C08F10/00 ,  Y10S526/943 ,  C08F4/52 ,  C08F4/02

Abstract: Methods of forming supported catalyst systems, supported catalyst systems and polymerization processes utilizing the supported catalyst systems are described herein. The methods generally include providing an inorganic support material and contacting the inorganic support material with a support solvent to form a support solution. The methods further include contacting the support solution with a fluorine containing compound represented by the formula AlFpX3−pBq to impregnate the fluorine containing compound within the inorganic support material and form an intermediate, wherein X is selected from Cl, Br and OH−, B is H2O, p is selected from 1 to 3 and q is selected from 0 to 6. In addition, the methods include drying the intermediate to remove the solvent therefrom and heating the intermediate at a temperature of at least about 300° C. to form an impregnated support and contacting the impregnated support with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n; wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

Abstract translation: 在此描述形成负载型催化剂体系的方法，负载型催化剂体系和利用负载型催化剂体系的聚合方法。 所述方法通常包括提供无机载体材料并使无机载体材料与支持溶剂接触以形成支持溶液。 所述方法还包括将载体溶液​​与由式AlFpX3-pBq表示的含氟化合物接触以在无机载体材料中浸渍含氟化合物并形成中间体，其中X选自Cl，Br和OH-，B为 H 2 O，p选自1至3，q选自0至6.此外，所述方法包括干燥中间体以除去溶剂，并在至少约300℃的温度下加热中间体以形成 浸渍的载体并使浸渍的载体与过渡金属化合物接触以形成负载型催化剂体系，其中过渡金属化合物由式[L] mM [A] n表示; 其中L是大体积配体，A是离去基团，M是过渡金属，m和n使总配体的化合价对应于过渡金属的价态。

公开(公告)号：US07335711B2

公开(公告)日：2008-02-26

申请号：US11205934

申请日：2005-08-17

Applicant: Vladimir Marin ,  Abbas Razavi

Inventor： Vladimir Marin ,  Abbas Razavi

IPC: C08F4/63012 ,  C08F4/64

CPC classification number: C07F7/00 ,  B01J31/2282 ,  B01J2231/122 ,  B01J2531/0263 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C07F17/00 ,  C08F4/65912 ,  C08F4/65916 ,  C08F10/00 ,  C08F110/06 ,  Y10S526/943 ,  C08F4/65927 ,  C08F2500/20 ,  C08F2500/12 ,  C08F2500/04 ,  C08F2500/03

Abstract: Catalyst compositions and processes for the polymerization of ethylenically unsaturated monomers to produce polymers, including copolymers or homopolymers. Such monomers include ethylene, C3+ alpha olefins and substituted vinyl compounds, such as styrene and vinyl chloride. The polymerization catalyst characterized by the formula B(FluL)MQn in which Flu is a fluorenyl group substituted at at least the 2,7- and 3,6-positions by hydrocarbyl groups, preferably relatively bulky hydrocarbyl groups. L is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group or a heteroorgano group, XR, in which X is a heteroatom from Group 15 or 16 of the Periodic Table of Elements, such as nitrogen, R is an alkyl group, a cycloalkyl group or an aryl group and B is a structural bridge extending between the groups L and Flu, which imparts stereorigidity to the ligand structure, M is a Group 4 or Group 5 transition metal, such as titanium, zirconium or hafnium and Q is selected from the group consisting of chlorine, bromine, iodine, an alkyl group, an amino group, an aromatic group and mixtures thereof, with n being 1 or 2.

Abstract translation: 催化剂组合物和用于聚合烯属不饱和单体以生产聚合物的方法，包括共聚物或均聚物。 这些单体包括乙烯，C 3+α-烯烃和取代的乙烯基化合物，例如苯乙烯和氯乙烯。 其中Flu是在至少2,7-和3,6位被烃基取代的芴基的式B（FluL）MQ N n的特征的聚合催化剂，优选相对庞大的烃基 团体 L是取代或未取代的环戊二烯基，茚基或芴基或杂有机基团XR，其中X是元素周期表第15或16族的杂原子，例如氮，R是烷基，环烷基 或芳基，B是在基团L和Flu之间延伸的结构桥，其赋予配体结构立体刚性，M是第4族或第5族过渡金属，例如钛，锆或铪，Q选自 由氯，溴，碘，烷基，氨基，芳族基团及其混合物组成的组，n为1或2。

公开(公告)号：US20080027189A1

公开(公告)日：2008-01-31

申请号：US11459801

申请日：2006-07-25

Applicant: Vladimir Marin ,  Abbas Razavi

Inventor： Vladimir Marin ,  Abbas Razavi

IPC: C08F4/06

CPC classification number: C07F17/00 ,  C08F4/65912 ,  C08F4/65916 ,  C08F10/00 ,  C08F110/06 ,  C08F210/06 ,  Y10S526/941 ,  Y10S526/943 ,  C08F4/65927 ,  C08F2500/15 ,  C08F2500/20 ,  C08F210/16 ,  C08F2500/03 ,  C08F2500/12

Abstract: An olefin polymerization process comprising contacting one or more olefins and a catalyst component in a reaction zone under suitable reaction conditions to form a polyolefin, wherein the catalyst component is characterized by the formula: B(Cp)(Fl)MQ2 wherein M comprises a metal, Q comprises a halogen, an alkyl group or an aryl group or combinations thereof, Cp comprises a cyclopentadienyl group, Fl comprises a fluorenyl group, B is a bridging group that may be characterized by the general formula —YRH wherein Y comprises C or Si and R comprises an alkyl group, an aryl group, a poly-aryl group or combinations thereof.

Abstract translation: 烯烃聚合方法包括在合适的反应条件下使反应区中的一种或多种烯烃和催化剂组分接触以形成聚烯烃，其中催化剂组分的特征在于下式： 公式“end =”lead“？> B（Cp）（F1）MQ <？in-line-formula description =”In-line Formulas“end =”tail“？> 金属，Q包括卤素，烷基或芳基或其组合，Cp包含环戊二烯基，Fl包含芴基，B是可以由通式-YRH表征的桥连基团，其中Y包含C 或Si和R包括烷基，芳基，聚芳基或其组合。

公开(公告)号：US20070255022A1

公开(公告)日：2007-11-01

申请号：US11413791

申请日：2006-04-28

Applicant: Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

Inventor： Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

IPC: C08F4/44 ,  B01J31/00

CPC classification number: B01J21/12 ,  B01J37/26 ,  C08F10/00 ,  C08F10/06 ,  C08F110/06 ,  C08F210/06 ,  C08F2400/02 ,  C08F2/00 ,  C08F4/025 ,  C08F2500/20 ,  C08F2500/03 ,  C08F2500/12 ,  C08F210/14 ,  C08F2500/04 ,  C08F210/16

Abstract: Supported catalyst systems and methods of forming the same are generally described herein. The methods generally include providing an inorganic support composition, wherein the inorganic support composition includes a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof and contacting the inorganic support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n; wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

Abstract translation: 载体催化剂体系及其形成方法一般在此描述。 所述方法通常包括提供无机载体组合物，其中所述无机载体组合物包括选自Si-O-Al-F，F-Si-O-Al，F-Si-O-Al-F及其组合的键合序列， 使无机载体组合物与过渡金属化合物接触以形成负载型催化剂体系，其中过渡金属化合物由式[L] M [A] ; 其中L是大体积配体，A是离去基团，M是过渡金属，m和n使总配体的化合价对应于过渡金属的价态。

公开(公告)号：US20070117943A1

公开(公告)日：2007-05-24

申请号：US11285479

申请日：2005-11-21

Applicant: Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

Inventor： Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

IPC: C08F4/06

CPC classification number: C07F7/00 ,  B01J31/122 ,  B01J31/143 ,  B01J31/1815 ,  B01J31/2243 ,  B01J2531/0244 ,  B01J2531/40 ,  B01J2531/48 ,  B01J2531/49 ,  B01J2531/50 ,  C08F110/02 ,  C08F110/06 ,  C08F210/16 ,  C08F4/64093 ,  C08F4/64151 ,  C08F4/64113 ,  C08F2500/20 ,  C08F2500/12 ,  C08F2500/04 ,  C08F2500/24 ,  C08F210/14 ,  C08F2500/15

Abstract: In accordance with the present invention, there is provided a transition metal olefin polymerization catalyst component characterized by the formula: where, M is a Group IV or a Group IV transition metal, B is a bridge group containing at least two carbon atoms, A′ and A″ are organogroups, each containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus, X is selected from the group consisting of chlorine, bromine, iodine, a C1-C20 alkyl group, a C6-C30 aromatic group and mixtures thereof, and n is 1, 2 or 3. The invention also encompasses a method for the polymerization of an ethylenically unsaturated monomer which comprises contacting a transition metal catalyst component as characterized by formula (1) above and an activating co-catalyst component in a polymerization reaction zone with an ethylenically unsaturated monomer under polymerization conditions to produce a polymer product.

Abstract translation: 根据本发明，提供一种过渡金属烯烃聚合催化剂组分，其特征在于下式：其中M是IV族或IV族过渡金属，B是含有至少两个碳原子的桥基，A' 和A“是有机基团，各自含有选自氧，硫，氮和磷的杂原子，X选自氯，溴，碘，C 1 - C 20烷基，C 6 -C 30芳族基团及其混合物，n为1,2或3.本发明还涉及 包括烯属不饱和单体的聚合方法，该方法包括在聚合反应条件下，将聚合反应区中的式（1）表示的过渡金属催化剂组分与活化助催化剂组分与烯属不饱和单体接触，以产生 聚合物产品。

公开(公告)号：US20070117713A1

公开(公告)日：2007-05-24

申请号：US11452692

申请日：2006-06-14

Applicant: Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

Inventor： Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

IPC: B01J27/24

CPC classification number: C08F10/00 ,  B01J31/122 ,  B01J31/143 ,  B01J31/1815 ,  B01J31/2243 ,  B01J2531/0244 ,  B01J2531/40 ,  B01J2531/48 ,  B01J2531/49 ,  B01J2531/50 ,  C07F7/00 ,  C08F110/02 ,  C08F110/06 ,  C08F210/16 ,  C08F2500/04 ,  C08F2500/20 ,  C08F2500/18 ,  C08F2500/12 ,  C08F210/14 ,  C08F210/08 ,  C08F2500/15 ,  C08F4/64113 ,  C08F4/64151 ,  C08F4/64093 ,  C08F2500/24

Abstract: A process for the preparation of a tridentate transition metal catalyst components incorporating pyridinyl bis-amino or monoamino ligand structures which do not require π bonding of the transition metal through the use of cyclopentadienyl rings. The ligand structure incorporates a heteroatom group that involves nitrogen in one organogroup and either oxygen or nitrogen in another organogroup. The process of preparing the catalyst component involves the reaction of a bis-amino or oxyamino pyridenyl ligand compound with an organo transition metal compound involving a tetrabenzyl ligand or other functional group ligands linked to a transition metal such as titanium zirconium or hafnium.

Abstract translation: 制备结合吡啶基双氨基或单氨基配体结构的三齿过渡金属催化剂组分的方法，其不需要通过使用环戊二烯基环的过渡金属的键合。 配体结构包含在一个有机组中涉及氮的杂原子基团和另一有机基团中的氧或氮。 制备催化剂组分的方法包括双 - 氨基或氧氨基吡啶基配体化合物与涉及四苄基配体或与过渡金属例如钛锆或铪连接的其它官能团配体的有机过渡金属化合物的反应。

公开(公告)号：US20070015946A1

公开(公告)日：2007-01-18

申请号：US11440276

申请日：2006-06-29

Applicant: Vladimir Marin ,  Abbas Razavi

Inventor： Vladimir Marin ,  Abbas Razavi

IPC: C07C2/70

CPC classification number: C07C17/2632 ,  C07C1/26 ,  C07C1/28 ,  C07C1/321 ,  C07C1/325 ,  C07C17/12 ,  C07C17/32 ,  C07C2531/24 ,  C07C2603/18 ,  C08F110/02 ,  C08F110/06 ,  C07C13/567 ,  C07C25/18 ,  C07C25/22 ,  C07C22/04 ,  C08F2500/15 ,  C08F2500/16

Abstract: Methods for the preparation of fluorenyl-type ligand structures and substituted fluorenyl groups which may be employed in metallocene-type olefin polymerization catalysts. There is provided a 2,2′-dihalogen-diphenylmethylene having a methylene bridge connecting a pair of phenyl groups. Each phenyl group has a halogen on a proximal carbon atom relative to the methylene bridge. The halogenated diphenylmethylene is reacted with a coupling agent comprising a Group 2 or 12 transition metal in the presence of a nickel or palladium-based catalyst to remove the halogen atoms from the phenyl groups and couple the phenyl groups at the proximal carbon atoms to produce a fluorene ligand structure. The coupling agent may be zinc, cadmium or magnesium and the catalyst may be a monophosphene nickel complex. The halogenated diphenylmethylene may be an unsubstituted ligand structure or a monosubstituted or disubstituted ligand structure. The halogenated diphenylmethylene may be monosubstituted with a tertiary butyl group or may be a dialkyl diphenylmethylene having alkyl substituents at the directly distal positions of the phenyl groups relative to the methylene bridge.

Abstract translation: 可用于茂金属型烯烃聚合催化剂中的芴基型配体结构和取代的芴基的制备方法。 提供了具有连接一对苯基的亚甲基桥的2,2'-二卤代 - 二苯基亚甲基。 每个苯基相对于亚甲基桥在近端碳原子上具有卤素。 卤化二苯基亚甲基与含有2或12族过渡金属的偶联剂在镍或钯基催化剂存在下反应，以从苯基除去卤素原子，并将近邻碳原子上的苯基偶联，生成 芴配体结构。 偶联剂可以是锌，镉或镁，催化剂可以是单磷酸镍络合物。 卤代二苯基亚甲基可以是未取代的配体结构或单取代或二取代的配体结构。 卤化二苯基亚甲基可以用叔丁基单取代，或者可以是在苯基相对于亚甲基桥的直接远端位置具有烷基取代基的二烷基二苯基亚甲基。