公开(公告)号：US06403732B2

公开(公告)日：2002-06-11

申请号：US09863721

申请日：2001-05-23

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： C07F1700

CPC分类号： B01J31/2295 ,  B01J31/146 ,  B01J31/1608 ,  B01J2531/39 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C07F17/00 ,  C08F4/61908 ,  C08F4/6592 ,  C08F10/00 ,  C08G65/12 ,  C08G65/20 ,  Y10S526/943 ,  C08F4/52

摘要： The organo-Lewis acids are novel triarylboranes which are are highly fluorinated. Triarylboranes of one such type contain at least one ring substituent other than fluorine. These organoboranes have a Lewis acid strength essentially equal to or greater than that of the corresponding organoborane in which the substituent is replaced by fluorine, or have greater solubility in organic solvents. Another type of new organoboranes have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these triorganoboranes, because of their ligand abstracting properties, produce corresponding anions which are capable of only weakly, if at all, coordinating to the metal center, and thus do not interfere in various polymerization processes such as are described.

摘要翻译： 有机路易斯酸是高度氟化的新型三芳基硼烷。 一种这样的三芳基硼烷含有除氟以外的至少一个环取代基。 这些有机硼烷具有基本上等于或大于其中取代基被氟代替的有机硼烷的路易斯酸强度，或者在有机溶剂中具有更大的溶解度。 另一种新型有机硼烷具有1-3个全氟化稠环基团和2-0个全氟苯基。 当作为助催化剂用于与具有至少一个离去基团如甲基的d-或f-嵌段金属化合物形成新的催化络合物时，由于它们的配体抽出性质，这些三有机硼烷产生相应的阴离子，其能够 只有在与金属中心配位的情况下才是弱的，因此不会干扰如所述的各种聚合方法。

公开(公告)号：US06291695B1

公开(公告)日：2001-09-18

申请号：US09329765

申请日：1999-06-10

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： C07F1700

CPC分类号： B01J31/2295 ,  B01J31/146 ,  B01J31/1608 ,  B01J2531/39 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C07F17/00 ,  C08F4/61908 ,  C08F4/6592 ,  C08F10/00 ,  C08G65/12 ,  C08G65/20 ,  Y10S526/943 ,  C08F4/52

摘要： The organo-Lewis acids are novel triarylboranes which are highly fluorinated. Triarylboranes of one such type contain at least one ring substituent other than fluorine. These organoboranes have a Lewis acid strength essentially equal to or greater than that of the corresponding organoborane in which the substituent is replaced by fluorine, or have greater solubility in organic solvents. Another type of new organoboranes have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these triorganoboranes, because of their ligand abstracting properties, produce corresponding anions which are capable of only weakly, if at all, coordinating to the metal center, and thus do not interfere in various polymerization processes such as are described.

摘要翻译： 有机路易斯酸是高度氟化的新型三芳基硼烷。 一种这样的三芳基硼烷含有除氟以外的至少一个环取代基。 这些有机硼烷具有基本上等于或大于其中取代基被氟代替的有机硼烷的路易斯酸强度，或者在有机溶剂中具有更大的溶解度。 另一种新型有机硼烷具有1-3个全氟化稠环基团和2-0个全氟苯基。 当作为助催化剂用于与具有至少一个离去基团如甲基的d-或f-嵌段金属化合物形成新的催化络合物时，由于它们的配体抽出性质，这些三有机硼烷产生相应的阴离子，其能够 只有在与金属中心配位的情况下才是弱的，因此不会干扰如所述的各种聚合方法。

公开(公告)号：US06262200B1

公开(公告)日：2001-07-17

申请号：US09329764

申请日：1999-06-10

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： C08F499

CPC分类号： B01J31/143 ,  B01J31/1608 ,  B01J31/2295 ,  B01J2531/46 ,  B01J2531/48 ,  C07F5/062 ,  C07F17/00 ,  C08F4/6592 ,  C08F4/65922 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  Y10S526/943 ,  C08F4/65908 ,  C08F2500/20 ,  C08F2500/15

摘要： The (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium are novel weakly coordinating anions which are are highly fluorinated. (Polyfluoroaryl)fluoroanions of one such type contain at least one ring substituent other than fluorine. These (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium have greater solubility in organic solvents, or have a coordinative ability essentially equal to or less than that of the corresponding (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium in which the substituent is replaced by fluorine. Another type of new (polyfluoroaryl)fluoroanion of aluminum, gallium, and indium have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these anions, because of their weak coordination to the metal center, do not interefere in the ethylene polymerization process, while affecting the the propylene process favorably, if highly isotactic polypropylene is desired. Thus, the (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of this invention are useful in various polymerization processes such as are described.

摘要翻译： 铝，镓和铟的（多氟芳基）氟代阴离子是高度氟化的新型弱配位阴离子。 这种类型的（多氟芳基）氟代阴离子含有除氟以外的至少一个环取代基。 铝，镓和铟的这些（多氟芳基）氟代阴离子在有机溶剂中具有更大的溶解度，或具有基本上等于或小于铝，镓或铟的相应（多氟芳基）氟阴离子的配位能力，其中取代基是 被氟取代。 铝，镓和铟的另一种新型（多氟芳基）氟阴离子具有1-3个全氟化稠环基团和2-0个全氟苯基。 当作为助催化剂用于与具有至少一个离去基团如甲基的d-或f-嵌段金属化合物形成新型催化络合物时，由于这些阴离子与金属中心的配位弱，因此不会干扰 乙烯聚合方法，同时有利地影响丙烯方法，如果需要高度全同立构聚丙烯。 因此，本发明的铝，镓和铟的（多氟芳基）氟代阴离子可用于各种聚合方法如所述。

公开(公告)号：US6087460A

公开(公告)日：2000-07-11

申请号：US220741

申请日：1998-12-23

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： B01J31/14 ,  B01J31/16 ,  B01J31/22 ,  C07F5/00 ,  C07F5/02 ,  C07F7/00 ,  C07F17/00 ,  C08F4/603 ,  C08F4/619 ,  C08F4/643 ,  C08F4/6592 ,  C08F10/00 ,  C08G65/12 ,  C08G65/20 ,  C08F4/44

CPC分类号： C08G65/20 ,  B01J31/146 ,  B01J31/1608 ,  B01J31/2295 ,  C07F17/00 ,  C08F10/00 ,  C08G65/12 ,  B01J2531/39 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C08F4/61908 ,  C08F4/6592 ,  Y10S526/943

摘要： The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

摘要翻译： 描述了有机 - 路易斯酸全氟联苯硼烷（PBB）的合成和用于形成各种高活性均相齐格勒 - 纳塔茂金属烯烃聚合，共聚和开环聚合催化剂的金属茂的活化。

公开(公告)号：US5854166A

公开(公告)日：1998-12-29

申请号：US912617

申请日：1997-08-18

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： B01J31/14 ,  B01J31/16 ,  B01J31/22 ,  C07F5/06 ,  C07F17/00 ,  C08F4/02 ,  C08F4/44 ,  C08F4/60 ,  C08F4/6592 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  B01J31/00 ,  C07F5/00

CPC分类号： B01J31/143 ,  B01J31/1608 ,  B01J31/2295 ,  C07F17/00 ,  C07F5/062 ,  C08F10/00 ,  B01J2531/46 ,  B01J2531/48 ,  C08F110/02 ,  C08F110/06 ,  C08F4/6592 ,  C08F4/65922 ,  Y10S526/943

摘要： A trityl perfluorophenyl alumninate such as tris(2,2',2"-nonafluorobiphenyl) fluoroaluminate (PBA.sup.-) and its role as a cocatalyst in metallocene-mediated olefin polymerization is disclosed.

摘要翻译： 公开了三茂乙基全氟苯基胺（如三（2,2'，2“ - 九氟联苯）氟铝酸盐（PBA-））及其在金属茂介导的烯烃聚合中作为助催化剂的作用。

公开(公告)号：US06635597B1

公开(公告)日：2003-10-21

申请号：US09463713

申请日：2000-05-12

申请人： Tobin J. Marks ,  Liting Li ,  You-Xian Chen ,  Mark H. McAdon ,  Peter N. Nickias

发明人： Tobin J. Marks ,  Liting Li ,  You-Xian Chen ,  Mark H. McAdon ,  Peter N. Nickias

IPC分类号： B01J2102

CPC分类号： C07C17/093 ,  C07F5/027 ,  C07F17/00 ,  C07F17/02 ,  C08F4/6592 ,  C08F4/65925 ,  C08F10/00 ,  C08F110/02 ,  C07C25/22 ,  C08F4/65908 ,  C08F4/643

摘要： A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising a neutral (Lewis acid) or charge separated (cation/anion pair) comprising a boron ligand containing a fluorinated organic group containing from 10 to 1000 non-hydrogen atoms.

摘要翻译： 一种催化剂活化剂，特别适用于活化金属3-10金属络合物，用于聚合烯属不饱和可聚合单体，特别是烯烃，包括中性（路易斯酸）或电荷分离（阳离子/阴离子对），其包含硼 配体含有含有10至1000个非氢原子的氟化有机基团。

公开(公告)号：US06403733B2

公开(公告)日：2002-06-11

申请号：US09899698

申请日：2001-07-05

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： C07F1700

CPC分类号： C08G65/20 ,  B01J31/146 ,  B01J31/1608 ,  B01J31/2295 ,  B01J2531/39 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C07F17/00 ,  C08F4/61908 ,  C08F4/6592 ,  C08F10/00 ,  C08G65/12 ,  Y10S526/943 ,  C08F4/52

摘要： Organo-Lewis acids of the formula BR′R″2 wherein B is boron, R′ is fluorinated biphenyl, and R″ is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

摘要翻译： 式BR'R''2的有机路易斯酸，其中B是硼，R'是氟化联苯，R“是氟化苯基，氟化联苯或氟化多环稠环基团，和由此形成的阳离子茂金属络合物。 这种络合物可用作聚合催化剂。

公开(公告)号：US06218332B1

公开(公告)日：2001-04-17

申请号：US09634144

申请日：2000-08-08

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： B01J3100

CPC分类号： B01J31/143 ,  B01J31/1608 ,  B01J31/2295 ,  B01J2531/46 ,  B01J2531/48 ,  C07F5/062 ,  C07F17/00 ,  C08F4/6592 ,  C08F4/65922 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  Y10S526/943 ,  C08F4/65908 ,  C08F2500/20 ,  C08F2500/15

摘要： The (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium are novel weakly coordinating anions which are highly fluorinated. (Polyfluoroaryl)fluoroanions of one such type contain at least one ring substituent other than fluorine. These (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium have greater solubility in organic solvents, or have a coordinative ability essentially equal to or less than that of the corresponding (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium in which the substituent is replaced by fluorine. Another type of new (polyfluoroaryl)fluoroanion of aluminum, gallium, and indium have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these anions, because of their weak coordination to the metal center, do not interfere in the ethylene polymerization process, while affecting the propylene process favorably, if highly isotactic polypropylene is desired. Thus, the (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of this invention are useful in various polymerization processes such as are described.

摘要翻译： 铝，镓和铟的（多氟芳基）氟代阴离子是高度氟化的新型弱配位阴离子。 这种类型的（多氟芳基）氟代阴离子含有除氟以外的至少一个环取代基。 铝，镓和铟的这些（多氟芳基）氟代阴离子在有机溶剂中具有更大的溶解度，或具有基本上等于或小于铝，镓或铟的相应（多氟芳基）氟阴离子的配位能力，其中取代基是 被氟取代。 铝，镓和铟的另一种新型（多氟芳基）氟阴离子具有1-3个全氟化稠环基团和2-0个全氟苯基。 当用作助催化剂形成具有至少一个离去基团如甲基的d-或f-嵌段金属化合物的新型催化复合物时，由于这些阴离子与金属中心的配位弱，因此不会干扰 乙烯聚合方法，同时有利地影响丙烯方法，如果需要高度全同立构聚丙烯。 因此，本发明的铝，镓和铟的（多氟芳基）氟代阴离子可用于各种聚合方法如所述。

公开(公告)号：US5856258A

公开(公告)日：1999-01-05

申请号：US950912

申请日：1997-10-15

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： B01J31/22 ,  C07F17/00 ,  C08F4/02 ,  C08F4/44 ,  C08F4/60 ,  C08F4/64 ,  C08F4/659 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  B01J31/00 ,  C07F7/00 ,  C07F7/28

CPC分类号： B01J31/2226 ,  B01J31/146 ,  B01J31/2295 ,  C07F17/00 ,  C08F10/00 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C08F110/02 ,  C08F110/06 ,  C08F4/65908 ,  C08F4/65912 ,  Y10S526/943

摘要： The subject invention involves a method of preparing and the constrained geometry catalyst thereby prepared of the general formula Ar'R4(O)Ar"R'.sub.4 M(CH.sub.2 Ph).sub.2 where Ar' is a phenyl or naphthyl group; Ar" is a cyclopentadienyl or indenyl group, R and R' are H or alkyl substituents (C.ltoreq.10) and M is Ti, Zr or Hf. The synthetic method involves a simple alkane elimination approach which permits a "one-pot" procedure. The catalyst, when combined with a cocatalyst such as Pb.sub.3 C.sup.+ B(Ar.sub.3.sup.F).sub.4 BAr.sub.3.sup.F or methyl alumoxane where Ar.sup.F is a fluoroaryl group, is an effective catalyst for the polymerization of .alpha.-olefins such as ethylene, propylene and styrene.

摘要翻译： 本发明涉及一种制备和约束的几何催化剂的方法，由此制备通式Ar'R 4（O）Ar'R'4M（CH 2 Ph）2，其中Ar'是苯基或萘基; Ar“是环戊二烯基或茚基，R和R'是H或烷基取代基（C 10），M是Ti，Zr或Hf。 合成方法涉及简单的烷烃消除方法，其允许“一锅”方法。 当与助催化剂如Pb3C + B（Ar3F）4BAr3F或甲基铝氧烷（其中ArF是氟代芳基）组合时，该催化剂是α-烯烃如乙烯，丙烯和苯乙烯的聚合的有效催化剂。

公开(公告)号：US06388114B1

公开(公告)日：2002-05-14

申请号：US09810967

申请日：2001-03-16

申请人： Tobin J. Marks ,  You-Xian Chen

发明人： Tobin J. Marks ,  You-Xian Chen

IPC分类号： C07F506

CPC分类号： B01J31/143 ,  B01J31/1608 ,  B01J31/2295 ,  B01J2531/46 ,  B01J2531/48 ,  C07F5/062 ,  C07F17/00 ,  C08F4/6592 ,  C08F4/65922 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  Y10S526/943 ,  C08F4/65908 ,  C08F2500/20 ,  C08F2500/15

摘要： The (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium are novel weakly coordinating anions which are highly fluorinated. (Polyfluoroaryl)fluoroanions of one such type contain at least one ring substituent other than fluorine. These (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium have greater solubility in organic solvents, or have a coordinative ability essentially equal to or less than that of the corresponding (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium in which the substituent is replaced by fluorine. Another type of new (polyfluoroaryl)fluoroanion of aluminum, gallium, and indium have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these anions, because of their weak coordination to the metal center, do not interfere in the ethylene polymerization process, while affecting the propylene process favorably, if highly isotactic polypropylene is desired. Thus, the (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of this invention are useful in various polymerization processes such as are described.

摘要翻译： 铝，镓和铟的（多氟芳基）氟代阴离子是高度氟化的新型弱配位阴离子。 这种类型的（多氟芳基）氟代阴离子含有除氟以外的至少一个环取代基。 铝，镓和铟的这些（多氟芳基）氟代阴离子在有机溶剂中具有更大的溶解度，或具有基本上等于或小于铝，镓或铟的相应（多氟芳基）氟阴离子的配位能力，其中取代基是 被氟取代。 铝，镓和铟的另一种新型（多氟芳基）氟阴离子具有1-3个全氟化稠环基团和2-0个全氟苯基。 当用作助催化剂形成具有至少一个离去基团如甲基的d-或f-嵌段金属化合物的新型催化复合物时，由于这些阴离子与金属中心的配位弱，因此不会干扰 乙烯聚合方法，同时有利地影响丙烯方法，如果需要高度全同立构聚丙烯。 因此，本发明的铝，镓和铟的（多氟芳基）氟代阴离子可用于各种聚合方法如所述。