公开(公告)号：WO1997036937A1

公开(公告)日：1997-10-09

申请号：PCT/US1997004247

申请日：1997-03-20

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  DEVORE, David, D. ,  TIMMERS, Francis, J. ,  NEITHAMER, David, R.

IPC: C08F04/603

CPC classification number: C08F10/00 ,  C08F4/61908 ,  C08F4/61916 ,  C08F4/6192 ,  C08F4/65908

Abstract: Boratabenzene cocatalysts, especially novel pentafluorophenyl boratabenzenes, are useful cocatalysts or activators with metallocenes. They are less expensive than prior art activators, are soluble and offer more irreversible reactions. Compositions comprise at least one metallocene catalyst and at least one dihydroboratabenzene or anion thereof. Processes include polymerizations with metallocenes in the presence of boratabenzene cocatalyst and activation process including bulk electrolysis techniques.

Abstract translation: 硼化物助催化剂，特别是新的五氟苯基硼苯偶氮，是具有金属茂的有用的助催化剂或活化剂。 它们比现有技术的活化剂便宜，是可溶的并且提供更多的不可逆反应。 组合物包含至少一种金属茂催化剂和至少一种二氢硼烷基或其阴离子。 方法包括在硼烷助催化剂存在下与茂金属的聚合，以及包括大量电解技术的活化方法。

公开(公告)号：WO1997025336A1

公开(公告)日：1997-07-17

申请号：PCT/US1996019281

申请日：1996-12-05

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  TIMMERS, Francis, J. ,  DEVORE, David, D. ,  NEITHAMER, David, R.

IPC: C07F17/00

CPC classification number: C07F17/00 ,  Y10S526/943

Abstract: Bicyclopentadienyl Group 4 transition metal complexes containing a conjugated diene ligand group wherein the diene is bound to the transition metal either in the form of a sigma -complex or a pi -complex are readily prepared by reacting in any order: a) a Group 4 metal salt corresponding to the formula M'X3 or M''X4, or a Lewis base adduct thereof, b) a conjugated diene, D', c) a reducing agent, and d) a compound of the formula: CpM* or (Cp-Cp)M*n, wherein M' is titanium, zirconium or hafnium in the +3 formal oxidation state; M'' is titanium, zirconium or hafnium in the +4 formal oxidation state; X is a halide, C1-6 hydrocarbyloxy or di(C1-6 hydrocarbyl)amido group; D' is an uncoordinated diene having the same number of carbons as D and the same substitution pattern as D; M* is a Group 1 or 2 metal cation, a Grignard reagent cation or a tri(C1-4 hydrocarbyl)silyl group; and n is 1 when M* is a Group 2 metal cation and n is 2 when M* is a Group 1 metal cation, a Grignard reagent cation, or a trihydrocarbylsisyl group with the proviso that reagents a) and d) are not contacted with one another in the absence of reagent c).

Abstract translation: 含有共轭二烯配体基团的双环戊二烯基4过渡金属配合物，其中二烯与σ-复合物或π-复合物形式的过渡金属结合，可容易地通过以下任何顺序进行反应：a）第4族金属 对应于式M'X3或M'X4的盐或其路易斯碱加合物，b）共轭二烯，D'，c）还原剂，和d）下式化合物：CpM *或（Cp -Cp）M * n，其中M'为钛，锆或铪为+3形式氧化态; M“是+4形式氧化态的钛，锆或铪; X是卤素，C 1-6烃氧基或二（C 1-6烃基）酰氨基; D'是具有与D相同数目的碳和与D相同的取代模式的不饱和二烯烃; M *是1或2族金属阳离子，格氏试剂阳离子或三（C 1-4烃基）甲硅烷基; 当M *为第2族金属阳离子时，n为1，当M *为第1族金属阳离子时，n为2，格利雅试剂阳离子或三烃基硅烷基，条件是试剂a）和d）不与 在没有试剂c）的情况下。

公开(公告)号：WO1996034001A1

公开(公告)日：1996-10-31

申请号：PCT/US1995012211

申请日：1995-09-22

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  ROSEN, Robert, K. ,  DEVORE, David, D.

IPC: C07F17/00

CPC classification number: C07F17/00

Abstract: A process for preparing titanium or zirconium diene complexes wherein the metal is in the + 2 formal oxidation state comprising contacting a conjugated or nonconjugated C4-40 diene compound with a hydrocarbyloxide containing precursor complex.

Abstract translation: 制备钛或锆二烯络合物的方法，其中金属处于+2形式氧化态，包括使共轭或非共轭的C 4-40二烯化合物与含有烃氧基的前体复合物接触。

公开(公告)号：WO1996004290A1

公开(公告)日：1996-02-15

申请号：PCT/US1995008813

申请日：1995-07-14

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  TIMMERS, Francis, J. ,  DEVORE, David, D. ,  STEVENS, James, C. ,  ROSEN, Robert, K. ,  PATTON, Jasson, T. ,  NEITHAMER, David, R.

IPC: C07F17/00

CPC classification number: C07F17/00 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/65916 ,  C08F4/65922 ,  C08F10/00 ,  Y10S526/901 ,  Y10S526/943

Abstract: Biscyclopentadienyl, Group 4 transition metal complexes are formed by contacting a biscyclopentadienyl Group 4 metal halide, hydrocarbyl, hydrocarbyloxy or amide complex with a conjugated diene. Uniquely, the ansa-rac diastereomer is selectively isolated and may be reconverted to the halide form if desired. When combined with standard activating cocatalysts or activated with an activating technique, the complexes form catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers.

Abstract translation: 通过使双环戊二烯基第4族金属卤化物，烃基，烃氧基或酰胺络合物与共轭二烯接触来形成双环戊二烯基，第4族过渡金属络合物。 独特的是，所述外消旋非对映异构体是选择性分离的，并且如果需要可以再转化为卤化物形式。 当与标准活化助催化剂结合或用活化技术活化时，络合物形成用于聚合烯烃，二烯烃和/或炔属不饱和单体的催化剂。

公开(公告)号：WO1995000683A1

公开(公告)日：1995-01-05

申请号：PCT/US1994004660

申请日：1994-04-28

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  DEVORE, David, D. ,  MUSSELL, Robert, D. ,  STEVENS, James, C. ,  TIMMERS, Francis, J.

IPC: C25B03/00

CPC classification number: C07F17/00 ,  B01J37/348 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/6592 ,  C08F10/00 ,  C08F2420/02 ,  Y10S526/943

Abstract: Group 4 metal complexes useful as addition polymerization catalysts are prepared by electrolysis of cyclopentadienyl metal complexes under inert electrolysis conditions.

Abstract translation: 可用作加成聚合催化剂的第4族金属络合物通过在惰性电解条件下电解环戊二烯基金属络合物来制备。

公开(公告)号：WO1996008519A2

公开(公告)日：1996-03-21

申请号：PCT/US1995008467

申请日：1995-07-06

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  DEVORE, David, D. ,  NEITHAMER, David, R. ,  LAPOINTE, Robert, E. ,  MUSSELL, Robert, D.

IPC: C08F10/00

CPC classification number: C25B3/02 ,  C07F5/027 ,  C07F7/0803 ,  C07F7/0805 ,  C07F17/00 ,  C08F4/65908 ,  C08F4/6592 ,  C08F10/00

Abstract: Catalyst systems useful in addition polymerisation reactions comprising a Group 4 metal complex and a silylium salt activating cocatalyst are prepared by contacting the metal complex with a silylium salt of a compatible, non-coordinating anion, optionally the silylium salt is prepared by electrochemical oxidation and splitting of the corresponding disilane compound.

Abstract translation: 通过使金属络合物与相容的非配位阴离子的甲硅烷鎓盐接触，制备可用于包含第4族金属络合物和甲硅烷鎓盐活化助催化剂的加成聚合反应的催化剂体系，任选地，通过电化学氧化和裂解制备甲硅烷基盐 的相应的乙硅烷化合物。

公开(公告)号：WO1996000742A1

公开(公告)日：1996-01-11

申请号：PCT/US1995007946

申请日：1995-06-23

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  PATTON, Jasson, T. ,  DEVORE, David, D. ,  TIMMERS, Francis, J. ,  SOTO, Jorge ,  SCHMIDT, Gregory, F. ,  WILSON, David, R.

IPC: C08F10/00

CPC classification number: C08F10/00 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/65916 ,  C08F4/6592

Abstract: Catalyst compositions comprising Group 4 metal complexes containing a diene moiety and activating cocatalysts are used as catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers. Vinylidene aromatic monomers, particularly styrene are polymerized to form highly syndiotactic polymers.

Abstract translation: 包含含有二烯部分和活化助催化剂的第4族金属络合物的催化剂组合物用作用于聚合烯烃，二烯烃和/或炔属不饱和单体的催化剂。 将亚乙烯基芳族单体，特别是苯乙烯聚合以形成高度间同立构聚合物。

公开(公告)号：WO1997035894A3

公开(公告)日：1997-10-02

申请号：PCT/US1997012821

申请日：1997-03-11

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  NICKIAS, Peter, N. ,  DEVORE, David, D. ,  TIMMERS, Francis, J.

IPC: C08F04/64

公开(公告)号：WO1996000734A1

公开(公告)日：1996-01-11

申请号：PCT/US1995007776

申请日：1995-06-19

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  DEVORE, David, D. ,  TIMMERS, Francis, J. ,  STEVENS, James, C. ,  ROSEN, Robert, K.

IPC: C07F17/00

CPC classification number: C07F17/00 ,  C08F4/65908 ,  C08F4/65916 ,  C08F4/6592 ,  C08F10/00 ,  C08F10/02 ,  Y10S526/943

Abstract: Novel Group 4 metal complexes containing one and only one cyclic delocalized, anionic, pi -bonded group wherein the metal is in the + 4 formal oxidation state and having a bridged ligand structure, also referred to as constrained geometry complexes and a conjugated diene divalent anionic ligand group; catalytic derivatives of such complexes including novel zwiterionic complexes; and the use thereof as catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers.

Abstract translation: 含有一个且仅一个环离域，阴离子，π键合基团的新型4族金属络合物，其中金属处于+ 4正式氧化态并具有桥连配体结构，也称为约束几何配合物和共轭二烯二价阴离子 配体基团 这种络合物的催化衍生物，包括新型的三嗪配合物; 以及其作为用于聚合烯烃，二烯烃和/或炔属不饱和单体的催化剂的用途。

公开(公告)号：WO1995000526A1

公开(公告)日：1995-01-05

申请号：PCT/US1994006834

申请日：1994-06-16

Applicant: THE DOW CHEMICAL COMPANY

Inventor： THE DOW CHEMICAL COMPANY ,  DEVORE, David, D. ,  CRAWFORD, Lenore, H. ,  STEVENS, James, C. ,  TIMMERS, Francis, J. ,  MUSSELL, Robert, D. ,  WILSON, David, R. ,  ROSEN, Robert, K.

IPC: C07F17/00

CPC classification number: C07F17/00 ,  C08F4/65904 ,  C08F4/65908 ,  C08F4/65912 ,  C08F4/65916 ,  C08F4/6592 ,  C08F10/00 ,  C08F210/02 ,  C08F210/16 ,  C08F210/18 ,  Y10S526/901 ,  Y10S526/905 ,  Y10S526/943 ,  C08F212/08 ,  C08F2500/12 ,  C08F210/14 ,  C08F210/06 ,  C08F2500/17 ,  C08F236/20 ,  C08F2500/25

Abstract: Novel titanium or zirconium complexes containing one and only one cyclic delocalized, anionic, pi -bonded, group, said complexes corresponding to formula (I), wherein: M is titanium or zirconium in the +2 formal oxidation state; L is a group containing a cyclic, delocalized, anionic, pi -system through which the group is bound to M, and which group is also bound to Z; Z is a moiety bound to M via a sigma -bond, comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 60 non-hydrogen atoms; and X is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said X having up to 40 carbon atoms and forming a pi -complex with M; are catalytically activated for use as addition polymerization catalysts. Preferably, L is an optionally substituted cyclopentadienyl or fused ring cyclopentadienyl group.

Abstract translation: 所述新型钛或锆络合物含有一个且仅一个环状离域阴离子，π键合的基团，所述络合物对应于式（I），其中：M是+2形式氧化态的钛或锆; L是含有环，离域，阴离子，π-系统的基团，其中该基团与M结合，并且该基团也与Z结合; Z是通过σ键与M结合的部分，包括硼，或元素周期表第14族的成员，并且还包含氮，磷，硫或氧，所述部分具有至多60个非氢 原子; 并且X是任选被一个或多个烃基取代的中性，共轭或非共轭二烯，所述X具有至多40个碳原子并与M形成π-复合物; 被催化活化用作加成聚合催化剂。 优选地，L是任选取代的环戊二烯基或稠环环戊二烯基。