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    Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
    11.
    发明授权
    Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems 失效
    使用茂金属催化剂体系控制间同立构聚烯烃的熔点和分子量的方法

    公开(公告)号：US5710222A

    公开(公告)日：1998-01-20

    申请号：US903058

    申请日：1992-06-22

    申请人： John A. Ewen ,  B. R. Reddy ,  Michael J. Elder

    发明人： John A. Ewen ,  B. R. Reddy ,  Michael J. Elder

    IPC分类号： C08F4/642 ,  C07F17/00 ,  C08F4/60 ,  C08F4/612 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/622 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/659 ,  C08F4/6592 ,  C08F8/00 ,  C08F10/00 ,  C08F110/06

    CPC分类号： C08F10/00 ,  C07F17/00 ,  C08F110/06 ,  C08F4/61908 ,  C08F4/61912 ,  C08F4/61927 ,  C08F4/63927 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/65927 ,  Y10S526/943

    摘要： This invention is for a method for varying the melting points and molecular weights of syndiotactic polyolefins by using metallocene catalysts with substituents on the aryl rings of a fluorene ligand in certain positions. Electron donating substituents, for example, dialkylamino, halogen, and alkoxy groups, when present on fluorene at C1, C2, C3 or C2 and C7 render the catalyst less active and decrease the polymer molecular weight. Electron donating substituents, such as alkyl, dialkylamino, halogen or alkoxy, at C4 not only increased the catalyst efficiency but also dramatically increased the polymer molecular weight. Bulky hydrocarbyl substituents, such as alkyl, cyaloalkyl and aryl groups, at C2 and C7 increase the melting point. Bulky substituents such as hydrocarbyl groups like alkyl, cycloalkyl, aryl, alkoxy and dialkylamino groups etc., at C4/C5 decrease the melting point. When multiple substituents are present on fluorene, their effects are additive.

    摘要翻译： 本发明是通过在某些位置使用在芴配体的芳环上具有取代基的金属茂催化剂来改变间规聚烯烃的熔点和分子量的方法。 当C 1，C 2，C 3或C 2和C 7存在于芴上时，给电子取代基例如二烷基氨基，卤素和烷氧基使得催化剂活性降低并降低聚合物分子量。 C4中的电子给体取代基如烷基，二烷基氨基，卤素或烷氧基不仅提高了催化剂效率，而且显着提高了聚合物分子量。 C 2和C 7上的大量烃基取代基如烷基，芳烷基和芳基增加了熔点。 在C4 / C5时，大量取代基如烃基如烷基，环烷基，芳基，烷氧基和二烷基氨基等降低了熔点。 当芴上存在多个取代基时，它们的作用是添加剂。

    Preparation of metallocene catalysts for polymerization of olefins
    12.
    发明授权
    Preparation of metallocene catalysts for polymerization of olefins 失效
    烯烃聚合茂金属催化剂的制备

    公开(公告)号：US5387568A

    公开(公告)日：1995-02-07

    申请号：US867572

    申请日：1992-04-13

    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 ,  B01J31/00

    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 triphenylcarbeniumtris(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苯基碳鎓三（五氟苯基）4-三甲基甲硅烷基-2,3,5,6-四氟苯基硼酸盐。 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。

    Catalyst and process for polymerization of olefins
    14.
    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
    15.
    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。

    Heterocyclic metallocenes and polymerization catalysts
    16.
    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。

    Polymerization catalysts, organic transition metal compounds, process for preparing polyolefins and polyolefins
    17.
    发明授权
    Polymerization catalysts, organic transition metal compounds, process for preparing polyolefins and polyolefins 失效
    聚合催化剂，有机过渡金属化合物，制备聚烯烃和聚烯烃的方法

    公开(公告)号：US07544749B2

    公开(公告)日：2009-06-09

    申请号：US10543961

    申请日：2004-02-05

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

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

    IPC分类号： C08F4/72 ,  C08F4/64

    CPC分类号： C08F10/06 ,  C07F7/003 ,  C08F4/65912 ,  C08F4/65916 ,  C08F10/00 ,  C08F110/06 ,  C08F210/06 ,  C08F210/16 ,  C08F2410/03 ,  C08F4/65927 ,  C08F2500/17 ,  C08F2500/15 ,  C08F2500/03 ,  C08F2500/26 ,  C08F4/025 ,  C08F4/64189 ,  C08F4/69474

    摘要： A catalyst system obtained by reacting at least one chiral transition metal compound and at least one cocatalyst, where the chiral transition metal compound is a transition metal compound of formula (Ia) or one of its enantiomers of the formula (Ia*), where M is an element of Group 4, Z are each halogen, hydrogen, C1-C10-alkyl, C6-C14-aryl, alkylaryl or arylalkyl having from 1 to 4 carbon atoms in the alkyl part and from 6 to 10 carbon atoms in the aryl part, n1 and n2 are each 0 or 1, R1 and R2 are each a C1-C40 radical, or R1 and R2 together with the atoms connecting them form a cyclic or polycyclic ring system, R5 and R6 are each hydrogen or a C1-C40 radical, R10, R11 are each hydrogen, t-butyl or phenyl, R12 are each t-butyl or phenyl, and R13 are each hydrogen or a C1-C40 radical.

    摘要翻译： 一种通过使至少一种手性过渡金属化合物和至少一种助催化剂反应而获得的催化剂体系，其中所述手性过渡金属化合物是式（Ia）的过渡金属化合物或其式（Ia *）的一种对映异构体，其中M 是4族的元素，Z是卤素，氢，C 1 -C 10 - 烷基，C 6 -C 14 - 芳基，烷基芳基或在烷基部分具有1至4个碳原子且在芳基中具有6至10个碳原子的芳烷基 部分，n1和n2各自为0或1，R1和R2各自为C1-C40基团，或R1和R2与连接它们的原子一起形成环状或多环系统，R5和R6各自为氢或C1- C 40基团，R 10，R 11各自为氢，叔丁基或苯基，R 12各自为叔丁基或苯基，R 13各自为氢或C 1 -C 40基。

    Heterocyclic metallocenes and polymerization catalysts
    19.
    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。

    Catalyst system using aluminum alkyl with ion-pair metallocene catalysts
    20.
    发明授权
    Catalyst system using aluminum alkyl with ion-pair metallocene catalysts 失效
    使用烷基铝与离子对金属茂催化剂的催化剂体系

    公开(公告)号：US5614457A

    公开(公告)日：1997-03-25

    申请号：US449197

    申请日：1995-05-24

    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

    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 catalysts. 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. Polymerization 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。