公开(公告)号：US06218332B1

公开(公告)日：2001-04-17

申请号：US09634144

申请日：2000-08-08

Applicant: Tobin J. Marks ,  You-Xian Chen

Inventor： Tobin J. Marks ,  You-Xian Chen

IPC: B01J3100

CPC classification number: 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

Abstract: 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.

Abstract translation: 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：US6075103A

公开(公告)日：2000-06-13

申请号：US874188

申请日：1997-06-13

Applicant: Tobin J. Marks ,  Kwangmo Koo

Inventor： Tobin J. Marks ,  Kwangmo Koo

IPC: C08F2/38 ,  C08F4/606 ,  C08F4/646 ,  C08F4/659 ,  C08F10/00 ,  C08F110/06 ,  C08F110/14 ,  C08F210/16 ,  C08F4/64

CPC classification number: C08F10/00 ,  C08F110/06 ,  C08F110/14 ,  C08F210/16 ,  C08F4/65908

Abstract: There is disclosed a method for synthesizing polyolefins having a silyl group at one terminus, the method comprising reacting a monomer of an .alpha.-olefin (C.ltoreq.3.ltoreq.10) and a tetrasubstituted silyl radical in the presence of a metallocene catalyst.

Abstract translation: 公开了一种在一端合成具有甲硅烷基的聚烯烃的方法，该方法包括在茂金属催化剂存在下使α-烯烃（C 3 = 10）和四取代甲硅烷基的单体反应 。

公开(公告)号：US5939346A

公开(公告)日：1999-08-17

申请号：US132736

申请日：1993-10-06

Applicant: Tobin J. Marks ,  Xinmin Yang ,  Stanley B. Mirviss

Inventor： Tobin J. Marks ,  Xinmin Yang ,  Stanley B. Mirviss

IPC: B01J31/02 ,  B01J31/14 ,  B01J31/22 ,  C07F5/06 ,  C08F4/64 ,  C08F10/00

CPC classification number: B01J31/143 ,  B01J31/0214 ,  C07F5/068 ,  C08F10/00 ,  B01J2531/48 ,  B01J31/2295

Abstract: Aryloxyaluminoxanes containing the unit ##STR1## where R is unsubstituted or substituted aryl, such as phenyl or naphthyl, are useful as a cocatalysts in Ziegler-Natta and Kaminsky-type olefin polymerization catalysts. They can be formed by reaction of a source of water with an organoaluminum compound containing the desired aryloxy moiety or by reaction of preformed aluminoxane with an organic compound, such as a phenol, containing such a moiety.

Abstract translation: 含有R为未取代或取代的芳基（如苯基或萘基）的单元的芳氧基亚氨基烷氧基可用作齐格勒 - 纳塔和卡明斯基型烯烃聚合催化剂中的助催化剂。 它们可以通过水源与含有所需芳氧基部分的有机铝化合物的反应或通过预形成的铝氧烷与含有这种部分的有机化合物如苯酚的反应形成。

公开(公告)号：US5856258A

公开(公告)日：1999-01-05

申请号：US950912

申请日：1997-10-15

Applicant: Tobin J. Marks ,  You-Xian Chen

Inventor： Tobin J. Marks ,  You-Xian Chen

IPC: 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 classification number: 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

Abstract: 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.

Abstract translation: 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：US5500398A

公开(公告)日：1996-03-19

申请号：US336864

申请日：1994-11-09

Applicant: Tobin J. Marks ,  Xinmin Yang

Inventor： Tobin J. Marks ,  Xinmin Yang

IPC: B01J31/14 ,  B01J31/22 ,  C07C2/34 ,  B01J31/38

CPC classification number: C07C2/34 ,  B01J31/146 ,  B01J31/2295 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  C07C2531/22

Abstract: A new class of olefin dimerization catalysts and an efficient method for their preparation is disclosed. B(C.sub.6 F.sub.5).sub.3 reacts quantitatively with Group 4 metallocene type catalysts to yield highly reactive cationic complexes as follows:(L.sub.2 MR.sup.2).sup.+ X.sup.- whereL=R.sub.2 (C.sub.5 H.sub.3); R=a C.sub.3 -C.sub.20 tert-alkyl group; R.sup.2 =a C.sub.1 -C.sub.20 alkyl group, HM=Ti, Zr, Hf;X.sup.- =RB(C.sub.5 F.sub.3).sup.-.sub.3, or methylalumoxane, where R"=a C.sub.1 -C.sub.20 alkyl group, H.These complexes are potent catalysts and may be used in the dimerization of .alpha.-olefins.

Abstract translation: 公开了一类新的烯烃二聚催化剂及其制备方法。 B（C6F5）3与第4族金属茂型催化剂定量反应，得到高反应性阳离子络合物如下：（L2MR2）+ X-，其中L = R2（C5H3）; R = C 3 -C 20叔烷基; R2 = C1-C20烷基，H M = Ti，Zr，Hf; X = RB（C5F3）-3或甲基铝氧烷，其中R“= C1-C20烷基，H.这些络合物是有效的催化剂，可用于α-烯烃的二聚。

公开(公告)号：US5447895A

公开(公告)日：1995-09-05

申请号：US209668

申请日：1994-03-10

Applicant: Tobin J. Marks ,  Li Ja ,  Xinmin Yang

Inventor： Tobin J. Marks ,  Li Ja ,  Xinmin Yang

IPC: B01J31/02 ,  B01J31/14 ,  B01J31/22 ,  C08F4/619 ,  C08F10/00 ,  B01J31/16

CPC classification number: B01J31/146 ,  B01J31/2295 ,  C08F10/00 ,  B01J2531/48 ,  C08F4/619 ,  C08F4/61908

Abstract: A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula ##STR1## where R is branched lower alkyl, such as t-butyl.

Abstract translation: 如果与环戊二烯基取代的茂金属阳离子组分如二茂锆茂金属组合，则非配位阴离子优选含有空间屏蔽的二硼氢化物，是有用的烯烃聚合催化剂组分。 阴离子优选具有式“IMAGE”，其中R是支链低级烷基，例如叔丁基。

公开(公告)号：US5300598A

公开(公告)日：1994-04-05

申请号：US962390

申请日：1992-10-16

Applicant: Tobin J. Marks ,  Xinmin Yang ,  Li Jia

Inventor： Tobin J. Marks ,  Xinmin Yang ,  Li Jia

IPC: C08F4/642 ,  B01J31/22 ,  C07F17/00 ,  C08F4/64 ,  C08F4/643 ,  C08F4/6592 ,  C08F210/02 ,  C08G61/06 ,  C03G61/06

CPC classification number: B01J31/146 ,  B01J31/2295 ,  C07F17/00 ,  C08F210/02 ,  C08G61/06 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  Y10S526/943

Abstract: The regiospecific (1,2-Me.sub.2 C.sub.5 H.sub.3).sub.2 ZrMe.sup.+ MeB(C.sub.6 F.sub.5).sub.3.sup.- mediated ring-opening polymerization of methylenecyclobutane and its copolymerization with ethylene to polyolefins of microstructure--{CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.2)]--.sub.n and {--[CH.sub.2 CHR]--.sub.x [CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.2)]--.sub.y }.sub.n' respectively, is disclosed.

Abstract translation: 区域特异性（1,2-Me2C5H3）2ZrMe + MeB（C6F5）3-介导的亚甲基环丁烷的开环聚合及其与乙烯与微观结构的聚烯烃（CH 2 CH 2 CH 2 C（CH 2）） - n和（ - （CH 2 CHR） （CH 2 CH 2 CH 2 C（CH 2）） - y）n'。

公开(公告)号：US5156918A

公开(公告)日：1992-10-20

申请号：US676992

申请日：1991-03-28

Applicant: Tobin J. Marks ,  DeQuan Li

Inventor： Tobin J. Marks ,  DeQuan Li

IPC: B05D1/18 ,  G02F1/361

CPC classification number: B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  G02F1/3617 ,  Y10T428/31612 ,  Y10T428/31663

Abstract: Polymer-based second harmonic generation materials are disclosed, including electric field poled, chromophore-functionalized polyphenylene ethers with second harmonic coefficients (d.sub.33) as high as 65.times.10.sup.-9 esu, Tg.apprxeq.173.degree. C., and with superior temporal stability of the poling-induced chromophore orientation. Procedures for simultaneously poling and diepoxide cross-linking chromophore-functionalized poly(.rho.-hydroxystyrene) are set forth, resulting in a significant improvement in the temporal stability of chromophore orientation. Chromophore immobilization is disclosed involving highly cross-linkable epoxy matrices. In a first procedure chromophore molecules are embedded in a matrix which can be simultaneously poled and thermally cured. In a second procedure, a functionalized high-.beta. chromophore is synthesized for use as an epoxy matrix component.

Abstract translation: 公开了基于聚合物的二次谐波发生材料，其包括具有高达65×10 -9 esu的二次谐波系数（d33）的电场极化，发色团官能化聚苯醚，Tg约为173℃，并且具有优异的极化时间稳定性 诱导发色团取向。 阐述了同时极化和双环氧化物交联发色团官能化的聚（对羟基苯乙烯）的方法，导致发色团取向的时间稳定性的显着改善。 公开涉及高度可交联的环氧基质的发色团固定化。 在第一步骤中，发色团分子嵌入基质中，其可以同时极化并热固化。 在第二程序中，合成功能化的高β发色团用作环氧基质组分。

公开(公告)号：US5110948A

公开(公告)日：1992-05-05

申请号：US492823

申请日：1990-03-13

Applicant: Tobin J. Marks ,  Steven P. Nolan ,  Michel R. Gagne

Inventor： Tobin J. Marks ,  Steven P. Nolan ,  Michel R. Gagne

IPC: C07D209/08 ,  C07D295/023

CPC classification number: C07D295/023 ,  C07D209/08

Abstract: The reaction of a samarium catalyst [.eta..sup.5 --(CH.sub.3).sub.5 C.sub.5 ].sub.2 Sm(THF).sub.2 with amino-olefins provides a straightforward route to a heterocyclic compound. Alternatively, the reaction of olefins with the samarium catalyst in the presence of an amine results in an aminoalkane.

Abstract translation: 钐催化剂[η5（CH3）5C5] 2Sm（THF）2与氨基烯烃的反应为杂环化合物提供了直接的途径。 或者，烯烃与钐催化剂在胺存在下的反应产生氨基烷烃。

公开(公告)号：US4716257A

公开(公告)日：1987-12-29

申请号：US29186

申请日：1987-05-14

Applicant: Tobin J. Marks ,  Heiko Mauermann

Inventor： Tobin J. Marks ,  Heiko Mauermann

IPC: B01J31/16 ,  B01J31/22 ,  C07C5/03 ,  C07F5/00 ,  C07F7/02 ,  C07F17/00 ,  C08F10/00

CPC classification number: C07F17/00 ,  B01J31/2295 ,  C07C5/03 ,  C07F5/00 ,  C07F7/025 ,  C08F10/00 ,  B01J2231/12 ,  B01J2231/645 ,  B01J2531/37 ,  B01J2531/38 ,  C07C2531/22

Abstract: The reaction of the organolanthanide complexes [.eta..sup.5 --(CH.sub.3).sub.5 C.sub.5 ].sub.2 MCl.sub.2.sup.- Li((C.sub.2 H.sub.5).sub.2 O).sub.2.sup.+, M=La, Nd, Sm, Lu, with LiCH[Si(CH.sub.3).sub.3 ].sub.2 provides a straight-forward route to ether-free and halide-free bis(pentamethylcyclopentadienyl) lanthanide alkyls, (.eta..sup.5 (CH.sub.3).sub.5 C.sub.5).sub.2 MCH-[Si(CH.sub.3).sub.3 ].sub.2. The (.eta..sup.5 (CH.sub.3).sub.5 C.sub.5).sub.2 NdCH[Si(CH.sub.3).sub.3 ].sub.2 complexes react with H.sub.2 under mild conditions to yield the corresponding hydrides [(.eta..sup.5 (CH.sub.3).sub.5 C.sub.5).sub.2 MH].sub.2. These complexes have been found to be extremely active homogeneous olefin polymerization catalysts, as well as catalysts for olefin and acetylene hydrogenation.