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    Heterocyclic metallocenes and polymerization catalysts
    1.
    发明授权
    Heterocyclic metallocenes and polymerization catalysts 有权
    杂环金属茂和聚合催化剂

    公开(公告)号：US07851644B2

    公开(公告)日：2010-12-14

    申请号：US11823802

    申请日：2007-06-28

    申请人： John A. Ewen ,  Michael J. Elder ,  Robert L. Jones, Jr. ,  Yuri A. Dubitsky

    发明人： John A. Ewen ,  Michael J. Elder ,  Robert L. Jones, Jr. ,  Yuri A. Dubitsky

    IPC分类号： C08F7/00 ,  C07F17/00

    CPC分类号： C08F10/00 ,  C07D333/70 ,  C07D495/04 ,  C07F17/00 ,  C08F4/61912 ,  C08F4/65912 ,  C08F110/02 ,  C08F110/06 ,  C08F2420/05 ,  C08F4/65925 ,  C08F4/65927 ,  C08F4/619

    摘要： A new class of heterocyclic metallocenes, a catalytic system containing them and a process for polymerizing addition polymerizable monomers using the catalytic system are disclosed; the heterocyclic metallocenes correspond to the formula (I): YjR″iZjjMeQkPl wherein Y is a coordinating group containing a six π electron central radical directly coordinating Me, to which are associated one or more radicals containing at least one non-carbon atom selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te; R″ is a divalent bridge between the Y and Z groups; Z is a coordinating group, optionally being equal to Y; Me is a transition metal; Q is halogen or hydrocarbon substituents; P is a counterion; i is 0 or 1; j is 1-3; jj is 0-2; k is 1-3; and l is 0-2.

    摘要翻译： 公开了一类新的杂环金属茂，含有它们的催化体系和使用催化体系聚合加成聚合单体的方法; 杂环金属茂对应于式（I）：YjR“iZjjMeQkPl其中Y是含有6个pgr的配位基团; 电子中心自由基直接配位Me，其中一个或多个基团含有至少一个选自B，N，O，Al，Si，P，S，Ga，Ge，As，Se，In，Sn中的非碳原子 ，Sb和Te; R“是Y和Z基团之间的二价桥; Z是一个协调组，任选地等于Y; 我是过渡金属; Q是卤素或烃取代基; P是一个抗衡离子; 我是0或1; j为1-3; jj是0-2; k为1-3; 和l是0-2。

    Heterocyclic metallocenes and polymerization catalysts
    2.
    发明授权
    Heterocyclic metallocenes and polymerization catalysts 有权
    杂环金属茂和聚合催化剂

    公开(公告)号：US07238818B2

    公开(公告)日：2007-07-03

    申请号：US10395686

    申请日：2003-03-24

    申请人： John A. Ewen ,  Michael J. Elder ,  Robert L. Jones, Jr. ,  Yuri A. Dubitsky

    发明人： John A. Ewen ,  Michael J. Elder ,  Robert L. Jones, Jr. ,  Yuri A. Dubitsky

    IPC分类号： C07F17/00 ,  C08F7/00

    CPC分类号： C08F10/00 ,  C07D333/70 ,  C07D495/04 ,  C07F17/00 ,  C08F4/61912 ,  C08F4/65912 ,  C08F110/02 ,  C08F110/06 ,  C08F2420/05 ,  C08F4/65925 ,  C08F4/65927 ,  C08F4/619

    摘要： A new class of heterocyclic metallocenes, a catalytic system containing them and a process for polymerizing addition polymerizable monomers using said catalytic system are disclosed; the heterocyclic metallocenes correspond to the formula (I): YjR″iZjjMeQkPl wherein Y is a coordinating group containing a six π electron central radical directly coordinating Me, to which are associated one or more radicals containing at least one non-carbon atom selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te; R″ is a divalent bridge between the Y and Z groups; Z is a coordinating group, optionally being equal to Y; Me is a transition metal; Q is halogen or hydrocarbon substituents; P is a counterion; i is 0 or 1; j is 1–3; jj is 0–2; k is 1–3; and l is 0–2.

    摘要翻译： 公开了一类新的杂环金属茂，含有它们的催化体系和使用所述催化体系聚合加成聚合单体的方法; 所述杂环金属茂对应于式（I）：Y Z i R Z Z 其中Y是包含直接配位Me的六个π电子中心基团的配位基团，其中与一个或多个选自B，N，O，Al的至少一个非碳原子相连; ，Si，P，S，Ga，Ge，As，Se，In，Sn，Sb和Te; R“是Y和Z基团之间的二价桥; Z是一个协调组，任选地等于Y; 我是过渡金属; Q是卤素或烃取代基; P是一个抗衡离子; 我是0或1; j为1-3; jj是0-2; k为1-3; 和l是0-2。

    Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom
    3.
    发明授权
    Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom 失效
    开戊二烯基金属茂，其前体和聚合催化剂

    公开(公告)号：US06403772B1

    公开(公告)日：2002-06-11

    申请号：US09029801

    申请日：1998-03-06

    申请人： John A. Ewen ,  Robert W. Strozier ,  Robert L. Jones, Jr. ,  Michael J. Elder

    发明人： John A. Ewen ,  Robert W. Strozier ,  Robert L. Jones, Jr. ,  Michael J. Elder

    IPC分类号： C07F708

    CPC分类号： C08F10/00 ,  C07F17/00 ,  C08F4/619 ,  C08F4/61912 ,  C08F4/6192

    摘要： New metallocene compounds are described where the ligand contains at least one open-pentadienyl containing radical characterized by a cyclic or acyclic, six &pgr; electron, delocalized, five atomic center structure. These metallocenes can advantageously be used in catalyst systems for the polymerization of olefins to generate a wide variety of different polymers including HDPE, LLDPE, ethylenelpropylene/(diene) elastomers, tactiospecific C3+&agr;-olefin polymers, intimate mixture thereof and the like.

    摘要翻译： 描述了新的茂金属化合物，其中配体含有至少一个含有开环戊二烯基的基团，其特征在于环状或非环状六个π电子，离域的五原子中心结构。 这些茂金属可以有利地用于烯烃聚合的催化剂体系中，以生成各种不同的聚合物，包括HDPE，LLDPE，乙烯 - 丙烯/（二烯）弹性体，触媒特异性C 3+α-烯烃聚合物及其紧密混合物等。

    Catalyst and process for polymerization of olefins
    5.
    发明授权
    Catalyst and process for polymerization of olefins 失效
    催化剂和烯烃聚合方法

    公开(公告)号：US5663249A

    公开(公告)日：1997-09-02

    申请号：US339842

    申请日：1994-11-15

    申请人： John A. Ewen ,  Michael J. Elder

    发明人： John A. Ewen ,  Michael J. Elder

    IPC分类号： C08F4/619 ,  C08F4/6192 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/643 ,  C08F10/00

    CPC分类号： C08F10/00 ,  C08F4/61908 ,  C08F4/61927 ,  C08F4/63908 ,  C08F4/63922 ,  Y10S526/943

    摘要： This invention uses a new method of producing ionic metallocene compounds. These compounds are useful as catalysts for polymerization of olefins, primarily propylene. This method uses an ionizing agent which ionizes the neutral metallocene compound. The ionizing ionic compound does not contain an active proton and contains a carbonium, oxonium or sulfonium cation. The anion of the ionizing ionic compound is not coordinated or is only loosely coordinated to the metallocene cation and is chemically unreactive with the metallocene cation. Examples of such compounds are triphenylcarbenium tetrakis(pentafluorophenyl)boronate, triphenylcarbenium tris(pentafluorophenyl)phenyl boronate and triphenylcarbenium tris(pentafluorophenyl)4-trimethylsilyl-2,3,5,6-tetrafluorophenylboronate.The process of making catalysts with this invention produces catalysts having high activity and does not produce by-products which can inhibit catalyst activity. This new synthesis is a clean reaction which does not produce a Lewis base. The process generates active catalysts by removing a methyl anion from a group IVB metallocene derivative.

    摘要翻译： 本发明使用生产离子茂金属化合物的新方法。 这些化合物可用作烯烃聚合的催化剂，主要是丙烯。 该方法使用电离所述中性茂金属化合物的电离剂。 电离离子化合物不含有活性质子，并含有碳鎓，氧鎓或锍阳离子。 电离离子化合物的阴离子不配位或仅与金属茂阳离子松散配位，并且与金属茂阳离子化学反应。 这些化合物的实例是四（五氟苯基）硼酸三苯基碳鎓，三（五氟苯基）苯基硼酸三苯基碳鎓和三（五氟苯基）4-三甲基甲硅烷基-2,3,5,6-四氟苯基硼酸三苯基碳鎓。 用本发明制备催化剂的方法产生具有高活性且不产生可抑制催化剂活性的副产物的催化剂。 这种新的合成是不产生路易斯碱的干净的反应。 该方法通过从IVB族金属茂衍生物中除去甲基阴离子而产生活性催化剂。

    Process and catalyst for producing isotactic polyolefins
    6.
    发明授权
    Process and catalyst for producing isotactic polyolefins 失效
    用于生产全同立构聚烯烃的方法和催化剂

    公开(公告)号：US5416228A

    公开(公告)日：1995-05-16

    申请号：US772192

    申请日：1991-10-07

    申请人： John A. Ewen ,  Michael J. Elder

    发明人： John A. Ewen ,  Michael J. Elder

    IPC分类号： C08F4/642 ,  C08F4/60 ,  C08F4/602 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/00 ,  C07F17/00 ,  C07F9/00 ,  C07F11/00

    CPC分类号： C08F10/00 ,  C08F4/61912 ,  C08F4/61927

    摘要： This invention is for a metallocene catalyst component useful in preparing isotactic polyolefins, a catalyst system using this component and a process for polymerizing olefins using the catalyst component. The catalyst component consists of a bridged metallocene in which one of the cyclopentadienyl rings is substituted in a different manner from the other ring. One of the cyclopentadienyl ligands contains a bulky group in one and only one distal position and the other cyclopentadienyl ligand has bilateral or pseudobilateral symmetry. There is a steric difference between the two Cp rings.The catalyst component is a stereorigid metallocene described by the formula:R" (CpR.sub.n)(CpR'.sub.m)MeQ.sub.kwherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R.sub.n and R'.sub.m is a hydrocarbyl radical having 1-20 carbon atoms; R" is a structural bridge between the two Cp rings imparting stereorigidity to the Cp rings; Me is a transition metal; and each Q is a hydrocarbyl radical or is a halogen. R'.sub.m is selected so that (CpR'.sub.m) is a sterically different substituted cyclopentadienyl ring than (CpR'.sub.n). The use of a metallocene catalyst component with sterically different cyclopentadienyl rings in which one and only one of the distal positions of the cyclopentadienyl rings has a bulky group as a substituent produces isotactic polymer.

    摘要翻译： 本发明涉及可用于制备全同立构聚烯烃的茂金属催化剂组分，使用该组分的催化剂体系和使用该催化剂组分使烯烃聚合的方法。 催化剂组分由桥连金属茂组成，其中一个环戊二烯基环以与另一个环不同的方式被取代。 一个环戊二烯基配位体在一个且仅一个远端位置含有大体积基团，另一个环戊二烯基配体具有双边或假双边对称性。 两个Cp环之间有空间差异。 催化剂组分是由式：R“（CpRn）（CpR'm）MeQk描述的立体刚性金属茂，其中每个Cp是环戊二烯基或取代的环戊二烯基环; 每个Rn和R'm是具有1-20个碳原子的烃基; R“是两个Cp环之间的结构桥，赋予Cp环立体刚性; 我是过渡金属; 并且每个Q是烃基或是卤素。 选择R'm使得（CpR'm）是空间上不同于（CpR'n）的取代环戊二烯基环。 使用具有空间上不同的环戊二烯基环的茂金属催化剂组分，其中环戊二烯基环的一个且仅一个远端位置具有大体积基团作为取代基产生全同立构聚合物。

    Metallocene compounds, process for their preparation and their use in catalytic systems for the polymerization of olefins
    7.
    发明授权
    Metallocene compounds, process for their preparation and their use in catalytic systems for the polymerization of olefins 有权
    茂金属化合物，其制备方法及其在烯烃聚合催化体系中的应用

    公开(公告)号：US06635779B1

    公开(公告)日：2003-10-21

    申请号：US09913742

    申请日：2001-11-20

    申请人： John A. Ewen ,  Michael J. Elder ,  Robert L. Jones

    发明人： John A. Ewen ,  Michael J. Elder ,  Robert L. Jones

    IPC分类号： C07F1700

    CPC分类号： C07F17/00 ,  C07D333/78 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/65916 ,  C08F10/00 ,  C08F110/06 ,  C08F110/08 ,  C08F210/06 ,  C08F2420/06 ,  Y10S526/943 ,  C08F4/65927 ,  C08F2500/17 ,  C08F210/08 ,  C08F2500/20 ,  C08F210/16

    摘要： A class of metallocene compounds is disclosed having general formula (I) wherein Y is a moiety of formula (II) wherein A, B, and D, same or different from each other, are selected from an element of the groups 14 to 16 of the Periodic Table of the Elements (new IUPAC version), with the exclusion of nitrogen and oxygen; R1, R2, R3, R4 and R5 are hydrogen or hydrocarbon groups, Z is selected from a moiety of formula (II) as described above and from a moiety of formula (III) wherein R6, R7, R8 and R9, are hydrogen or hydrocarbon groups; L is a divalent bridging group; M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements (new IUPAC version), X, same or different, is hydrogen, a halogen, a R10, OR10, OSO2CF3, OCOR10, SR10, NR102 or PR102 group, wherein the substituents R10 are hydrogen or alkyl groups; p is an integer of from 1 to 3, being equal to the oxidation state of the metal M minus 2. The above metallocenes are particularly useful in the polymerization of propylene.

    摘要翻译： 公开了一类茂金属化合物，其具有通式（I），其中Y是式（II）的部分，其中A，B和D彼此相同或不同，选自第14〜16族的元素 元素周期表（新的IUPAC版本），排除氮和氧; R 1，R 2，R 3，R 4和R 5是氢或烃基，Z选自如上所述的式（II）部分和式 （III）其中R 6，R 7，R 8和R 9是氢或烃基; L是二价桥基; M是选自属于第3,4,5,6族的过渡金属的原子或元素周期表中的镧系元素或锕系元素（新的IUPAC版本），X相同或不同，为氢， 卤素，R 10，OR 10，OSO 2 CF 3，OCOR 10，SR 10，NR 10或PR 10，其中取代基R 10是氢或烷基 团体 p是1至3的整数，等于金属M的氧化态减去2.上述金属茂特别可用于丙烯的聚合。

    Addition of aluminum alkyl for improved metallocene catalyst
    9.
    发明授权
    Addition of aluminum alkyl for improved metallocene catalyst 失效
    为改善金属茂催化剂添加烷基铝

    公开(公告)号：US5519100A

    公开(公告)日：1996-05-21

    申请号：US830812

    申请日：1992-02-04

    申请人： John A. Ewen ,  Michael J. Elder

    发明人： John A. Ewen ,  Michael J. Elder

    IPC分类号： C07F17/00 ,  C08F4/60 ,  C08F4/602 ,  C08F4/649 ,  C08F4/657 ,  C08F4/659 ,  C08F4/6592 ,  C08F4/76 ,  C08F10/00 ,  C08F4/643 ,  C08F4/642

    CPC分类号： C08F10/00 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/65922

    摘要： This invention is for a catalyst system for polymerization of olefins using an ionic metallocene catalyst with aluminum alkyl. The metallocene catalyst is an ion pair formed from a neutral metallocene compound and an ionizing compound. The invention can be used in any method of producing ionic metallocene catalyst. Use of aluminum alkyl with an ionic metallocene catalyst eliminates the need for using methylaluminoxane (MAO). Catalysts produced by the method of this invention have high activity. The invention reduces catalyst poisons which cause low activity, no activity or uncontrolled polymerizations. Polymerizations using this catalyst system are reproducible and controllable.

    摘要翻译： 本发明涉及使用具有烷基铝的离子金属茂催化剂烯烃聚合的催化剂体系。 金属茂催化剂是由中性茂金属化合物和电离化合物形成的离子对。 本发明可用于制备离子金属茂催化剂的任何方法。 使用烷基铝与离子金属茂催化剂不需要使用甲基铝氧烷（MAO）。 通过本发明的方法生产的催化剂具有高活性。 本发明减少了引起低活性，无活性或不受控聚合的催化剂毒物。 使用该催化剂体系的聚合是可重现和可控的。

    Process and catalyst for producing syndiotactic polyolefins
    10.
    发明授权
    Process and catalyst for producing syndiotactic polyolefins 失效
    制备间同立构聚烯烃的方法和催化剂

    公开(公告)号：US5155080A

    公开(公告)日：1992-10-13

    申请号：US419055

    申请日：1989-10-10

    申请人： Michael J. Elder ,  Abbas Razavi ,  John A. Ewen

    发明人： Michael J. Elder ,  Abbas Razavi ,  John A. Ewen

    IPC分类号： C07F17/00 ,  C08F4/60 ,  C08F4/602 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/642 ,  C08F4/6592 ,  C08F4/76 ,  C08F8/00 ,  C08F10/00 ,  C08F10/06 ,  C08F110/06

    CPC分类号： C08F10/00 ,  C07F17/00 ,  C08F110/06 ,  C08F4/61908 ,  C08F4/61912 ,  C08F4/61927 ,  C08F4/65908 ,  C08F4/65912 ,  Y10S526/943

    摘要： Syndiospecific catalysts and processes for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer which contains 3 or more carbon atoms or is a substituted vinyl compound. The catalysts comprise an unbalanced metallocene cation, characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, and a stable noncoordinating counter anion for the metallocene cation. One of said ring structures is a substituted or unsubstituted cyclopentadienyl ring and the other of the ring structures is a substituted cyclopentadienyl group which is sterically different from the first cyclopentadienyl group. A structural bridge between cyclopentadienyl groups imparts stereorigidity to the catalyst. The catalyst is contacted with a C.sub.3 + alpha olefin or other ethylenically unsaturated compound in a polymerization reaction zone and maintained in contact with the catalyst in the reaction zone under polymerizatio conditions to produce a syndiotactic polymer.

    摘要翻译： 来自含有3个或更多个碳原子的烯键式不饱和单体的聚合物链的间同扩散的间同立构催化剂和方法，或者是取代的乙烯基化合物。 催化剂包含不平衡的茂金属阳离子，其特征在于阳离子茂金属配体具有与正电荷的配位过渡金属原子连接的空间异相环结构，以及用于金属茂阳离子的稳定的非配位抗衡阴离子。 所述环结构之一是取代或未取代的环戊二烯基环，另一个环结构是与第一环戊二烯基空间上不同的取代的环戊二烯基。 环戊二烯基之间的结构桥将催化剂赋予立体刚性。 催化剂在聚合反应区中与C3 +α烯烃或其它烯属不饱和化合物接触，并在聚合条件下与反应区中的催化剂保持接触，以产生间同立构聚合物。