公开(公告)号：US20050090631A1

公开(公告)日：2005-04-28

申请号：US10691809

申请日：2003-10-23

申请人： Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

发明人： Abbas Razavi ,  Vladimir Marin ,  Margarito Lopez

IPC分类号： C08F4/46 ,  C08F10/00 ,  C08F110/02 ,  C08F210/16

CPC分类号： C08F10/00 ,  C08F110/02 ,  C08F210/16 ,  C08F2410/04 ,  C08F2500/04 ,  C08F210/14 ,  C08F4/60089 ,  C08F4/7042

摘要： Ethylene polymerization processes employing bis-imino pyridinyl transition metal components which exhibit C2, C2v or Cs symmetry. Catalyst components of the same or different symmetries may be employed to control polymerization characteristics and characteristics of the resulting polymer products such as polymer yield and polymer molecular weight. The transition metal catalyst component is characterized by the formula: wherein M is a Group 4-11 transition metal, n is an integer within the range of 1-3, Q is a halogen or a C1-C2 alkyl group, and PY is a pyridinyl group which is coordinated with M through the nitrogen atom of the pyridinyl group. Further, with respect to formula (I), A is a methyl group, a phenyl group, or a substituted phenyl group and B, and B2 are the same or different aromatic groups depending on the symmetry of the catalyst component. The catalyst component and an activating co-catalyst component are contacted with ethylene in a polymerization reaction zone which is free of hydrogen or contains hydrogen in an amount which is less than 5 mole % of the ethylene under polymerization conditions to produce a polymer product which can be a ethylene homopolymer or a copolymer of ethylene and C3+ alpha olefin, specifically an ethylene-propylene copolymer.

摘要翻译： 使用显示C2，C2v或Cs对称性的双亚氨基吡啶基过渡金属组分的乙烯聚合方法。 可以使用相同或不同对称性的催化剂组分来控制所得聚合物产物的聚合特性和特性，例如聚合物产率和聚合物分子量。 过渡金属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，PY是通过吡啶基的氮原子与M配位的吡啶基。 此外，对于式（I），A是甲基，苯基或取代的苯基，B和B 2是相同或不同的芳族基团，取决于 催化剂组分。 催化剂组分和活化助催化剂组分在聚合反应区中与乙烯接触，所述聚合反应区在聚合条件下不含氢或含有小于乙烯5摩尔％的氢，以产生聚合物产物， 是乙烯均聚物或乙烯和C 3 +α烯烃的共聚物，特别是乙烯 - 丙烯共聚物。

公开(公告)号：US20050020438A1

公开(公告)日：2005-01-27

申请号：US10491207

申请日：2002-09-26

申请人： Abbas Razavi

发明人： Abbas Razavi

IPC分类号： C08F4/64 ,  C08F4/645 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/00 ,  B01J31/00 ,  C08F4/44

CPC分类号： C08F10/00 ,  C08F4/65912 ,  C08F4/65916 ,  Y10S526/941 ,  Y10S526/943 ,  C08F4/65927

摘要： Provided is a catalyst component for producing a polyolefin, which catalyst component comprises a metallocene catalyst having a structure according to formula (I): (THI)2R″MQp, wherein each THI is a tetrahydroindenyl derivative which may be substituted or unsubstituted, provided that at least one of the tetrahydroindenyl derivatives is substituted at the 2-position or the 4-position; R″ is a structural bridge to impart stereorigidity between the two THI groups; M is a metal from Group IIIB, IVB, VB or VIB; Q is a hydrocarbyl group having from 1-20 carbon atoms, or a halogen; and p is the valence of M minus 2.

摘要翻译： 提供了一种用于制备聚烯烃的催化剂组分，该催化剂组分包括具有式（I）结构的茂金属催化剂：（THI）2 R“MQp，其中每个THI是可被取代或未取代的四氢茚基衍生物， 至少一个四氢茚基衍生物在2-位或4-位被取代; R“是在两个THI组之间赋予立体刚度的结构桥; M是IIIB，IVB，VB或VIB族的金属; Q是具有1-20个碳原子的烃基或卤素; 而p是M的价数减去2。

公开(公告)号：US06559089B1

公开(公告)日：2003-05-06

申请号：US09424416

申请日：2000-02-15

申请人： Abbas Razavi ,  Vincenzo Bellia

发明人： Abbas Razavi ,  Vincenzo Bellia

IPC分类号： B01J3100

CPC分类号： C08F10/00 ,  C08F4/65904 ,  C08F4/65912 ,  C08F110/06 ,  Y10S526/943 ,  C08F4/65927 ,  C08F2500/12 ,  C08F2500/06 ,  C08F2500/15

摘要： Provided is a metallocene catalyst component for use if preparing isotactic polyolefins, which component has the general formula (I): R″ (CpR1R2R3)(Cp′R′n) MQ2 wherein Cp is a substituted cyclopentadienyl ring; Cp′ is substituted or unsubstituted fluorenyl ring; R″ is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vincinal to the distal substituent, and is of the formula YR#3, in which Y is chosen from Group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from Group IVA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, each R′ is the same or different and is hydrocarbyl having 1 to 20 carbon atoms in which 0≦n≦8; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.

摘要翻译： 提供制备全同立构聚烯烃所用金属茂催化剂组分，该组分具有通式（I）：R“（CpR1R2R3）（Cp'R'n）MQ2，其中Cp是取代的环戊二烯基环; Cp'是取代或未取代的芴基环; R“是赋予组分立体刚性的结构桥; R1是位于桥的远端的环戊二烯基环上的取代基，其远端取代基包含式XR * 3的大体积基团，其中X选自IVA族，每个R *相同或不同，并选自氢 或1至20个碳原子的烃基，R2是环戊二烯基环上的取代基，其在桥附近并且位于远离取代基的非正交位置，并且具有式YR＃3，其中Y选自IVA族 ，并且每个R＃相同或不同，并且选自氢或1至7个碳原子的烃基，R 3是在桥附近的环戊二烯基环上的取代基，并且是氢原子或具有式ZR $ 3， 其中Z选自IVA族，并且每个R $相同或不同，并且选自氢或1至7个碳原子的烃基，每个R'相同或不同，并且是具有1至20个碳原子的烃基，其中 0 <= n <= 8; M是IVB族过渡金属或钒; 并且每个Q是具有1至20个碳原子的烃基或是卤素。

公开(公告)号：US06245870B1

公开(公告)日：2001-06-12

申请号：US08474955

申请日：1995-06-07

申请人： Abbas Razavi

发明人： Abbas Razavi

IPC分类号： C08F464

CPC分类号： C08F297/06 ,  C08F4/65912 ,  C08F4/65927 ,  C08F10/00 ,  C08F110/06 ,  Y10S526/904 ,  C08F2500/03 ,  C08F2500/16 ,  C08F2500/15 ,  C08F2500/20

摘要： The invention provides a metallocene catalyst for use in preparing syndiotactic/isotactic block polyolefins. The catalyst comprises a bridged metallocene in which one of the cyclopentadienyl rings is substituted in a substantially different manner from the other ring and the cyclopentadienyl rings have lack of bilateral or pseudo-bilateral symmetry. The catalyst comprises a metallocene compound generally described by the formula R″(C5R4)(C4R′4C5C4R′4)MeQp wherein (C5R4) is a substituted cyclopentadienyl ring; (C4R′mC5C4R′n) is a fluorenyl ring or substituted fluorenyl ring; each R and R′ is hydrogen or hydrocarbyl radical having from 1-20 carbon atoms, a halogen, an alkoxy, and alkoxy alkyl or an alkylamino radical, each R and R′ may be the same or different; (C5R4) has a lack of bi-lateral symmetry; R″ is a structural bridge between the (C5R4) and (C4R′4C5C4R′4) rings to impart stereorigidity and, preferably, is a hydrocarbyl biradical having at least one carbon atom to form the bridge; Q is a hydrocarbyl radical, such as an alkyl, aryl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a Group IIIB, IVB, VB, or VIB metal as positioned in the Periodic Table of Elements; and p is the valence of Me minus 2. This catalyst is syndio-/iso-specific and produces a syndiotactic/isotactic block polymer.

摘要翻译： 本发明提供用于制备间规/全同立构嵌段聚烯烃的茂金属催化剂。 催化剂包含其中一个环戊二烯基环以与其它环基本上不同的方式被取代的桥连金属茂，并且环戊二烯基环缺乏双侧或伪双边对称性。 催化剂包括通式为R“（C 5 R 4）（C 4 R 4 C 5 C 4 R 4）MeQp所述的茂金属化合物，其中（C 5 R 4）为取代的环戊二烯基环; （C4R'mC5C4R'n）是芴基环或取代的芴基环; 每个R和R'是氢或具有1-20个碳原子的烃基，卤素，烷氧基和烷氧基烷基或烷基氨基，每个R和R'可以相同或不同; （C5R4）缺乏双侧对称性; R“是（C5R4）和（C4R'4C5C4R'4）环之间的结构桥，以赋予立体刚性，优选为具有至少一个碳原子的烃基双基以形成桥; Q是烃基，例如具有1-20个碳原子的烷基，芳基，烯基，烷基芳基或芳基烷基，或者是卤素; Me是位于元素周期表中的IIIB，IVB，VB或VIB族金属; 并且p是Me的化合价减2。该催化剂是聚合/异构体并产生间同立构/全同立构嵌段聚合物。

公开(公告)号：US06218330B1

公开(公告)日：2001-04-17

申请号：US09296034

申请日：1999-04-21

申请人： Abbas Razavi ,  Guy Debras

发明人： Abbas Razavi ,  Guy Debras

IPC分类号： B01J3100

CPC分类号： B01J31/143 ,  B01J31/2295 ,  B01J2531/48 ,  B01J2531/49 ,  C08F4/65912 ,  C08F4/65927 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  C08F210/16 ,  Y10S526/943 ,  C08F4/65916 ,  C08F2500/12 ,  C08F2500/18 ,  C08F210/14

摘要： A process for the preparation of supported metallocene-alumoxane catalysts comprising the steps of: a) reacting a metallocene with an alumoxane at a temperature comprised between 15 and 50° C., b) recovering a mixture comprising an alkylmetallocenium cation and an anionic alumoxane oligomer, c) reacting said mixture with a support, and d) recovering a supported metallocene-alumoxane catalyst as a dry solid, the reaction with the support being carried out at a temperature comprised between 85° C. and 110° C., preferably between 90 and 130° C., and their use for the polymerization or copolymerization of olefins.

摘要翻译： 一种制备负载型茂金属 - 铝氧烷催化剂的方法，包括以下步骤：a）在15-50℃的温度下使茂金属与铝氧烷反应，b）回收包含烷基金属茂阳离子和阴离子铝氧烷低聚物 c）使所述混合物与载体反应，和d）回收作为干固体的负载型茂金属 - 铝氧烷催化剂，与载体的反应在85℃至110℃之间，优选在90℃ 和130℃，以及它们用于烯烃聚合或共聚的用途。

公开(公告)号：US5914289A

公开(公告)日：1999-06-22

申请号：US797800

申请日：1997-02-07

申请人： Abbas Razavi

发明人： Abbas Razavi

IPC分类号： C08F4/60 ,  C08F4/642 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/00 ,  C08F210/16 ,  B01J31/00 ,  B01J37/00 ,  C08F4/02

CPC分类号： C08F210/16 ,  C08F10/00 ,  C08F4/65912 ,  C08F4/65916 ,  C08F4/65927 ,  Y02P20/52 ,  Y10S526/934 ,  Y10S526/943

摘要： The present invention relates to the production of high density polyethylene homopolymers or copolymers having a broad and monomodal molecular weight distribution wherein the polymerization process is conducted in the presence of supported metallocene-alumoxane catalysts wherein the metallocene is bridged, comprises at least a hydrogenated indenyl or fluorenyl and a metal M which may be Ti, Zr or Hf, wherein a plurality of conformers of the metallocene are formed and isolated on the support by reaction of the metallocene with the alumoxane and depositing the product formed on the support at a temperature in the range 85.degree. C. to 110.degree. C.

摘要翻译： 本发明涉及具有广泛和单峰分子量分布的高密度聚乙烯均聚物或共聚物的生产，其中聚合方法在其中茂金属桥接的负载金属茂 - 铝氧烷催化剂存在下进行，包括至少氢化茚基或 芴基和可以是Ti，Zr或Hf的金属M，其中通过茂金属与铝氧烷的反应在载体上形成并分离多个茂金属构象，并将形成在载体上的产物在 范围85℃至110℃

公开(公告)号：US5719241A

公开(公告)日：1998-02-17

申请号：US224604

申请日：1994-04-07

申请人： Abbas Razavi ,  Guy L.G. Debras

发明人： Abbas Razavi ,  Guy L.G. Debras

IPC分类号： C08F4/642 ,  C08F4/60 ,  C08F4/602 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/6592 ,  C08F10/00 ,  C08F110/02 ,  C08F210/16

CPC分类号： C08F210/16 ,  C08F10/00 ,  C08F110/02 ,  C08F4/63904 ,  C08F4/63912 ,  C08F4/63916 ,  C08F4/63922 ,  Y10S526/905 ,  Y10S526/943

摘要： The present invention provides a process for preparing polyolefins having a multimodal or at least bimodal molecular weight distribution by contacting in a reaction mixture under polymerization conditions at least one olefin and a catalyst system comprising a supported catalyst-component comprising an alumoxane and at least two metallocenes containing the same transition metal and selected from mono, di, and tri-cyclopentadienyls and substituted cyclopentadienyls of a transition metal and wherein at least one of the metallocenes is bridged and at least one of the metallocenes is unbridged.

摘要翻译： 本发明提供了一种制备具有多峰或至少双峰分子量分布的聚烯烃的方法，所述聚烯烃在聚合条件下在反应混合物中接触至少一种烯烃和催化剂体系，所述催化剂体系包含负载型催化剂组分，其包含铝氧烷和至少两种金属茂 含有相同的过渡金属并选自过渡金属的单，二和三环戊二烯基和取代的环戊二烯基，并且其中至少一个金属茂被桥接并且至少一个金属茂是未桥接的。

公开(公告)号：US5334677A

公开(公告)日：1994-08-02

申请号：US792974

申请日：1991-11-15

申请人： Abbas Razavi ,  John A. Ewen

发明人： Abbas Razavi ,  John A. Ewen

IPC分类号： B01J37/00 ,  B01J31/22 ,  C07F17/00 ,  C08F4/60 ,  C08F4/62 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/6592 ,  C08F4/74 ,  C08F4/82 ,  C08F10/00 ,  C08F10/06 ,  C08F110/04 ,  C08F110/06 ,  C08F110/14 ,  C08F4/622 ,  C08F4/626

CPC分类号： C08F110/06 ,  C07F17/00 ,  C08F10/00 ,  C08F4/63912 ,  C08F4/63927 ,  Y10S526/943

摘要： The invention provides a metallocene catalyst for use in preparing syndiotactic polyolefins. The catalyst comprises a bridged metallocene in which one of the cyclopentadienyl rings is substituted in a substantially different manner from the other ring. It was discovered that this type of catalyst is highly syndiospecific, and it also produces a polymer with a novel microstructure. The invention further includes the use of one or more of the catalysts in a polymerization process. The catalyst is generally described by the formulaR"(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 the same or different and is a hydrocarbyl radicals having 1-20 carbon atoms; R" is a structural bridge between the two Cp rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; 0.ltoreq.k.ltoreq.3; 0.ltoreq.n.ltoreq.4; 1.ltoreq.m.ltoreq.4; and wherein R'.sub.m is selected such that (CpR'.sub.m) is a sterically different ring than (CpR.sub.n).

摘要翻译： 本发明提供用于制备间同立构聚烯烃的茂金属催化剂。 该催化剂包括其中一个环戊二烯基环以与另一个环基本不同的方式被取代的桥连茂金属。 发现这种催化剂具有高度的同分子特异性，并且还产生具有新颖微观结构的聚合物。 本发明还包括在聚合过程中使用一种或多种催化剂。 催化剂通常由式R“（CpRn）（CpR'm）MeQk描述，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相同或不同，是具有1-20个碳原子的烃基; R“是赋予催化剂立体刚性的两个Cp环之间的结构桥; Me是元素周期表中的4b，5b或6b族金属; 每个Q是具有1-20个碳原子的烃基或是卤素; 0

公开(公告)号：US5225500A

公开(公告)日：1993-07-06

申请号：US874304

申请日：1992-04-24

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 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/64 ,  C08F10/00 ,  C08F110/06

CPC分类号： C08F110/06 ,  C07F17/00 ,  C08F10/00 ,  C08F4/63912 ,  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 polymerization 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。

公开(公告)号：US5162278A

公开(公告)日：1992-11-10

申请号：US419157

申请日：1989-10-10

申请人： Abbas Razavi

发明人： Abbas Razavi

IPC分类号： C07F17/00 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/659 ,  C08F4/6592 ,  C08F4/74 ,  C08F10/00 ,  C08F110/06

CPC分类号： C08F110/06 ,  C07F17/00 ,  C08F10/00 ,  C08F4/63912 ,  C08F4/63927 ,  C08F4/65912 ,  C08F4/65925 ,  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 substituted vinyl compound. The catalysts comprise unbalanced stereorigid metallocenes in which a structural bridge is not required for stereorigidity. The ring structures of the metallocene catalyst are substituted cyclopentadienyl rings, which are sterically different from one another. The substituent groups on the cyclopentadienyl rings impart stereorigidity to the catalyst by virtue of a sterically hindered relationship between the rings sufficient to prevent rotation of the rings, or by virtue of the cyclopentadienyl groups being at a low kinetic energy state induced by the substituents to prevent rotation of the rings about their coordination axes at the temperature of the catalyst. The catalyst is contacted with a C3+ alpha olefin or other ethylenically unsaturated compound in a polymerization reaction zone and maintained in contact with the catalyst in the reaction zone under polymerization 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属不饱和单体的聚合物链的间同扩链的间同立构催化剂和方法，或者是取代的乙烯基化合物。 催化剂包括不平衡立体刚性金属茂，其中立体刚性不需要结构桥。 茂金属催化剂的环结构是取代的环戊二烯基环，它们在空间上彼此不同。 环戊二烯基环上的取代基由于环之间的空间位阻关系给予催化剂立体刚性，足以防止环的旋转，或者由于取代基诱导的低动能状态下的环戊二烯基阻止 在催化剂的温度下环绕其配位轴的旋转。 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。