Heterocyclic amino transition metal complex, its preparation and use

Abstract

Disclosed are heterocyclic amino transition metal complexes for olefin polymerization to prepare polyolefins, preferably multimodal polyolefins. The heterocyclic amino transition metal complexes are formed by chelating a tridentate dianionic heterocyclic amino ligand to a Group 3, 4 or 5 transition metal, wherein the tridentate ligand is coordinated to the metal to form a five-membered ring and an eight-membered ring.

Description

[0001] Inventors: John R.Hagadorn, Jo Ann M.Canich, Alexander Z.Voskoboynikov, Pavel S.Kulyabin, Georgy P.Goryunov and Dmitry V.Uborsky

[0002] Priority claim

[0003] This application claims priority to USSN 62 / 368,511 filed on July 29, 2016 and EP16188232.9 filed on September 12, 2016, and is hereby incorporated by reference in their entirety. Field of the Invention

[0004] The present invention relates to a heterocyclic amino transition metal complex and an intermediate and a method for preparing the heterocyclic amino complex. The transition metal complex can be used as a catalyst for an olefin polymerization process. Background of the Invention

[0006] Pyridylamines have been used to prepare Group 4 complexes which are useful as transition metal components in the polymerization of olefins, see for example US 2002 / 0142912, US 6,900,321 and US 6,103,657, wherein ligands are used in the complexes wherein the ligands coordinate to the transition metal atom in a bidentate or tridentate manner and wherein the pyridylamino ligands chelate to the transition metal to form a five-membered ring.

[0007] Davies and Solan in WO 2005 / 095469 describe catalyst compounds which employ tridentate ligands via two nitrogen atoms (one amino and one pyridyl) and one oxygen atom, wherein the tridentate ligands chelate to transition metals to form five- and six-membered rings.

[0008] US 2004 / 0220050 A1 and WO 2007 / 067965 disclose complexes in which the ligands are coordinated in a tridentate manner via two nitrogen (one amino and one pyridyl) and one carbon (aryl anion) donors, wherein the pyridylamino ligands chelate to the transition metal to form a five-membered ring.

[0009] The above pyridylamino complexes are known to undergo olefin insertion into the metal-aryl bond of the catalyst precursor during activation (Froese, RDJ et al., J. Am. Chem. Soc. 2007, 129, 7831-7840) to form activated catalysts with tridentate ligands chelated to the transition metal to form five- and seven-membered rings.

[0010] Kuhlman and Whiteker in US 2010 / 0227990 disclose pyridylamino complexes in which the ligands are chelated in a tridentate manner by two nitrogen (one amino and one pyridyl) and one carbon (alkyl anion) donors to form five- and seven-membered rings.

[0011] WO 2010 / 037059 discloses amine-containing pyridines for pharmaceutical applications.

[0012] US 7,973,116 and US 2011 / 0224391 describe pyridyldiamino complexes in which the ligands are chelated in a tridentate manner via three nitrogen donors (two amino groups and one pyridyl group) to form five- and seven-membered rings.

[0013] WO 2007 / 130307 describes hafnium complexes of heterocyclic ligands, in which the ligands are chelated in a tridentate manner by two nitrogen (an amino group and a heterocyclic Lewis base) and one carbon (aryl anion) donors to form five- and six-membered rings.

[0014] Other references of interest include: 1) Domski, GJ; Rose, JM; Coates, GW; Bolig, AD; Brookhart, M. "Living alkene polymerization: New methods for the precision synthesis of polyolefins" Prog. Polym. Sci. 2007, 32, 30-92; 2) Giambastiani, G.; Laconi, L.; Kuhlman, RL; Hustad, PD "Imino-and amido-pyridinate d-block metalcomplexes in polymerization / oligomerization catalysis" Chapter 5in OlefinUpgrading Catalysis by Nitrogen-based Metal Complexes I, Catalysis by MetalComplexes, Springer, 2011; 3) Vaughan, A; Davis, DS; Hagadorn, JRin Comprehensive Polymer Science, Vol. 3, Chapter 20, "Industrial catalysts for alkenepolymerization", 2012; 4) Gibson, VC; Spitzmesser, SK Chem. Rev. 2003, 103, 283; 5) Britovsek, GJP; Gibson, VC; Wass, DFA Angew. Chem. Int. Ed. 1999, 38, 428; 6) Inorganic Chemistry (2010) 49, (11), 5143-5156; 7) JACS, (1997) 119 (14), 3411-3412; 8) Organom etallics, (1997) 16(26), 5857-5868; 9) Organometallics, (1998), 17(3), 466-474; and 10)Inorganic Chimica Acta, (1997), 263(1-2), 287-299.

[0015] There remains a need for new catalyst complexes having improved performance in olefin polymerization.

[0016] Furthermore, there is a need in the art for new catalysts without symmetry (ie, C1 point group symmetry) that can polymerize alpha olefins to produce crystalline polymers. SUMMARY OF THE INVENTION

[0018] New catalyst compositions for olefin polymerization are described herein, characterized in that a Group 3, 4, or 5 metal is bonded to a tridentate dianionic ligand which chelates to the metal center to form five-membered and eight-membered rings. These new catalyst compositions are shown herein to be active for olefin polymerization, particularly for the preparation of polymers containing ethylene.

[0019] The present invention relates to novel dianionic tridentate transition metal complexes containing at least one amino donor group, wherein the tridentate ligand is chelated to the metal in a manner to form a five-membered and eight-membered ring. The present invention also relates to heterocyclic amino transition metal complexes represented by formula (A), (B), (C) or (D):

[0020]

[0021] in:

[0022] M is a Group 3, 4 or 5 metal;

[0023] Q 1 R is connected by three atomic bridges represented by the following formula 2 and R 3 Groups:

[0024] -G 1 -G 2 -G 3 -, where G 2 is a Group 15 or 16 atom that forms a coordination bond with M, G 1 and G 3 are each a Group 14 atom that are linked together through two or three additional Group 14, 15 or 16 atoms to form a heterocyclic ring or a substituted heterocyclic ring;

[0025] Q 2 is a group that forms an anionic bond with M, wherein Q 2 The group is selected from O, S, CH2, CHR 17 , C(R 17 )2, NR 17 or PR 17 , where each R 17 independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, silyl hydrocarbyl and polar groups;

[0026] Q 2' is a group that forms an anionic bond with M, wherein Q 2'The group is selected from N, P, CH or CR 17 , where R 17 As defined above;

[0027] Q 3 is -(TT)- or -(TTT)-, wherein each T is a substituted or unsubstituted Group 14, 15 or 16 element, so that it forms a five-membered or six-membered heterocyclic ring together with the "-CN=C-" moiety or a substituted heterocyclic ring;

[0028] R 1 is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl and silylhydrocarbyl;

[0029] R 2 -E(R 12 )(R 13 )-, where E is carbon, silicon or germanium, and each R 12 and R 13 independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, silyl hydrocarbyl and polar groups;

[0030] R 3 is C or N, and R 4 and R 5 is C, and R 3 and R 4 is part of a five-membered or six-membered carbocyclic or heterocyclic ring, which may be substituted or unsubstituted, and R 4 and R 5 is part of a five- or six-membered carbocyclic or heterocyclic ring, which may be substituted or unsubstituted;

[0031] Each J is independently selected from C, CH, CH2, CR 18 , CHR 18 , C(R 18 )2,Si(R 18 )2,SiH(R 18 ), NH, NR 18 , O or S, where R 18 is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, halogen, and silylhydrocarbyl;

[0032] Each x is independently 3 or 4, representing the number of J groups connected in series;

[0033] Y is selected from substituted and unsubstituted Group 14 elements, including, but not limited to CH2, CH(R 18 ), C(R 18 )2, C(O) and C(NR 18 ), where R 18As defined above, and wherein the heteroatom (such as O or N) is optionally bonded to M;

[0034] Y' is selected from substituted and unsubstituted Group 14 elements, including, but not limited to CH, C(R 18 ), where R 18 As defined above;

[0035] L is an anionic leaving group, wherein the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

[0036] L' is a neutral Lewis base;

[0037] n is 1, 2 or 3;

[0038] w is 0, 1, 2, or 3;

[0039] Where n+w is not greater than 4;

[0040] The tridentate dianionic ligand is chelated to the metal M in such a way that the complex forms an eight-membered ring and a five-membered ring, which are represented by the numbers 8 and 5 in formulae (A) to (D), respectively.

[0041] The present invention further relates to a process for preparing the above complex, a process for preparing an intermediate for the above complex and a process for polymerizing olefins using the above complex.

[0042] The present invention further relates to a polymerization process for preparing polyolefins, comprising contacting one or more olefin monomers with a catalyst system comprising a catalyst compound as described herein and an activator and obtaining (e.g., by a recovery process utilizing liquid-solid, liquid-liquid, gas-liquid or gas-solid separation) an olefin polymer. DETAILED DESCRIPTION OF THE INVENTION

[0044] This specification describes transition metal complexes. The term complex is used to describe molecules in which ancillary ligands are coordinated to a central transition metal atom. The ligands may be coordinated to the transition metal by covalent bonds and / or electron donation or intermediate bonds. The transition metal complexes are usually activated using an activator to exert their polymerization or oligomerization functions, and it is believed that the activator produces a cation due to the removal of an anionic group, which is often referred to as a leaving group, from the transition metal.

[0045] As used herein, the numbering scheme for the Periodic Table of the Elements is that new as set forth in Chemical and Engineering News, 63(5), 27 (1985).

[0046] For purposes of this invention and the claims thereto, Me is methyl, Et is ethyl, Bu is butyl, t-Bu and tBu are tert-butyl, Pr is propyl, iPr and iPr are isopropyl, Cy is cyclohexyl, THF (also known as thf) is tetrahydrofuran, Bn is benzyl and Ph is phenyl.

[0047] Unless otherwise indicated, the term "substituted" means that a hydrogen group has been replaced by a hydrocarbyl group, a heteroatom or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group, and ethyl alcohol is an ethyl group substituted with an -OH group.

[0048] The terms "alkyl", "alkyl" and "alkyl group" are used interchangeably herein. Similarly, the terms "group", "radical" and "substituent" are used interchangeably herein. For the purposes of this disclosure, "alkyl" is defined as a C1-C 100 The group may be linear, branched or cyclic and, when cyclic, may be aromatic or non-aromatic.

[0049] Substituted hydrocarbyl groups are groups in which at least one hydrogen atom is replaced by at least one functional group, such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc., or in which at least one non-hydrocarbon atom or group is inserted into the hydrocarbyl group, such as -O-, -S-, -Se-, -Te-, -N(R*)-, =N-, - P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Si(R*)2-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, etc., wherein R* is independently a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0050] A haloalkyl group is a group in which one or more of the hydrogen atoms of the hydrocarbon group is replaced by at least one halogen (eg, F, Cl, Br, I) or a halogen-containing group (eg, CF3).

[0051] Substituted haloalkyl groups are groups in which at least one haloalkyl hydrogen or halogen atom is replaced by at least one functional group, such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc., or in which at least one non-carbon atom or group is inserted into the haloalkyl group, such as -O-, -S-, -Se- , -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Si(R*)2-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, etc., wherein R* is independently a hydrocarbon group or a halogenated hydrocarbon group, provided that at least one halogen atom remains on the original halogenated hydrocarbon group. In addition, two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0052] Silylcarbyl (also known as silylalkyl) is a group in which the silyl functionality is directly bonded to the indicated atom or atoms. Examples include SiH3, SiH2R*, SiHR*2, SiR*3, SiH2(OR*), SiH(OR*)2, Si(OR*)3, SiH2(NR*2), SiH(NR*2)2, Si(NR*2)3, etc., wherein R* is independently a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Preferred silylalkyl groups have the formula SiR*3.

[0053] Polar radical or polar group (also referred to as functional group) is such group, wherein heteroatom functionality is directly bonded to indicated one or more atoms.They comprise heteroatoms of the 13th-17th family of the periodic table of elements, either individually, or are connected to other elements by covalent bonds or other interactions such as ionic, van der Waals forces or hydrogen bonds.The example of functional group comprises carboxylic acid, acid halide, carboxylate, carboxylate, carboxylic anhydride, aldehyde and their sulfide (14th family) analogs, alcohol and phenol, ether, peroxide and hydroperoxide, carboxylic acid amide, hydrazide and imide, amidine and amide other nitrogen analogs, nitrile, amine and imine, azo, nitro, other nitrogen compounds, sulfuric acid, selenoic acid, mercaptan, sulfide, sulfoxide, sulfone, phosphine, phosphate or ester, other phosphorus-containing compounds, silane, borane, borate, alane, aluminate.Polar group can also widely comprise organic polymer carrier or inorganic carrier material, such as aluminum oxide and silicon dioxide. Examples of preferred polar groups include NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SnR*3, PbR*3, etc., wherein R* is independently a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, or a substituted halogenated hydrocarbon group as defined above, and two R* groups may be linked together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure. Examples of particularly preferred polar groups include NR*2 and PR*2.

[0054] The term "catalyst system" is defined to refer to a complex / activator pair. When "catalyst system" is used to describe such a pair before activation, it refers to the unactivated catalyst complex (procatalyst) and the activator and optional co-activator. When it is used to describe such a pair after activation, it refers to the activated complex and the activator or other charge balancing moiety. The transition metal compound can be neutral, as in a procatalyst, or a charged species with a counter ion, as in an activated catalyst system.

[0055] As used herein, complexes are also often referred to as catalyst precursors, procatalysts, catalysts, catalyst compounds, transition metal compounds or transition metal complexes. These terms are used interchangeably. Activators and cocatalysts are also used interchangeably.

[0056] Scavengers are compounds that are typically added to facilitate polymerization by scavenging impurities. Some scavengers may also function as activators and may be referred to as co-activators. Co-activators that are not scavengers may also be used in conjunction with activators to form activated catalysts. In some embodiments, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound.

[0057] "Olefins" alternatively referred to as "alkenes" are linear, branched or cyclic compounds of carbon and hydrogen having at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in the polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is described as having an "ethylene" content of 35 wt%-55 wt%, it is understood that the repeating units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present in 35 wt%-55 wt%, based on the weight of the copolymer. "Polymers" have two or more repeating units that are the same or different. "Homopolymers" are polymers having the same repeating units. "Copolymers" are polymers having two or more repeating units that are different from each other. "Terpolymers" are polymers having three repeating units that are different from each other. "Different" when used to describe repeating units means that the repeating units are different from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of copolymers includes terpolymers, etc. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole percent ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole percent propylene-derived units, and so forth.

[0058] For the purposes of this invention, ethylene shall be considered an alpha-olefin.

[0059] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight and Mz is the z-average molecular weight, wt% is the weight percent and mol% is the molar percent. Mole weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol.

[0060] Unless otherwise indicated, all melting points (Tm) are DSC second melts.

[0061] "Ring carbon atoms" are carbon atoms that are part of a cyclic ring structure. By this definition, a benzyl group has six ring carbon atoms, and p-methylstyrene also has six ring carbon atoms.

[0062] The term "aryl" or "aryl group" refers to a six-carbon aromatic ring and substituted variants thereof, including, but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced by a heteroatom, preferably N, O or S.

[0063] The term "ring atom" refers to an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms, while tetrahydrofuran has five ring atoms.

[0064] The terms heteroaryl, heterocycle, heterocyclic ring, and heterocyclic ligand are used interchangeably herein.

[0065] A heterocyclic ring is a ring having heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which a hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocyclic ring, while 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. A heterocyclic ring may be saturated, aromatic, pseudoaromatic, partially unsaturated, or fully unsaturated. A substituted heterocycle is a heterocyclic ring in which a hydrogen group on a ring atom is replaced by a hydrocarbyl, heteroatom, polar group, or substituted hydrocarbyl.

[0066] As used herein, the term "aromatic" also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents having similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but are not aromatic by definition; similarly, the term aromatic also refers to substituted aromatics.

[0067] The terms carbocycle, carbocyclic ring, and carbocyclic ligand are used interchangeably herein. A carbocycle is a ring of carbon atoms which may be saturated, unsaturated, or aromatic. Carbocycles may be fused together to form a carbocycle containing multiple rings, such as indan, naphthalene, or anthracene. A substituted carbocycle is a ring of carbon atoms in which the hydrogen groups on the ring atoms are replaced by a hydrocarbyl, heteroatom, polar group, or substituted hydrocarbyl.

[0068] The term "continuous" refers to a system that operates without interruption or suspension. For example, a continuous process to make a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0069] Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or a monomer or a blend thereof. Solution polymerization is typically homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is soluble in the polymerization medium. Such a system is preferably not chaotic, as described in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627.

[0070] Bulk polymerization refers to a polymerization process in which the monomers and / or comonomers being polymerized are used as solvents or diluents, with little or no inert solvents being used as solvents or diluents. A small proportion of inert solvents may be used as carriers for catalysts and scavengers. Bulk polymerization systems contain less than 25 wt% inert solvents or diluents, preferably less than 10 wt%, preferably less than 1 wt%, preferably 0 wt%.

[0071] Unless otherwise stated, "catalyst activity" is a measure of how many grams of polymer (P) are produced over a period of time T hours using a polymerization catalyst comprising W mmol of a transition metal; and can be expressed as: P / (T x W).

[0072] Room temperature is 23°C unless otherwise stated.

[0073] Catalyst complex

[0074] In the first aspect of the present invention, there is provided a heterocyclic amino transition metal complex represented by formula (A), (B), (C) or (D) (optionally for olefin polymerization):

[0075]

[0076] in:

[0077] M is a Group 3, 4 or 5 metal;

[0078] Q 1 The connection R is represented by the following formula 2 and R 3 The three-atom bridging group:

[0079] -G 1 -G 2 -G 3 -, where G 2 is a Group 15 or 16 atom that forms a coordination bond with M, G 1 and G 3 are each a Group 14 atom that are linked together through two or three additional Group 14, 15 or 16 atoms to form a heterocyclic ring or a substituted heterocyclic ring;

[0080] Q 2 is a group that forms an anionic bond with M, wherein Q 2 The group is selected from O, S, CH2, CHR 17 , C(R 17 )2. NR 17 or PR 17 , where each R 17 independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, silyl hydrocarbyl and polar groups;

[0081] Q 2' is a group that forms an anionic bond with M, wherein Q 2' The group is selected from N, P, CH or CR 17 , where R 17 As defined above;

[0082] Q 3is -(TT)- or -(TTT)-, wherein each T is a substituted or unsubstituted Group 14, 15 or 16 element, so that it forms a five-membered or six-membered heterocyclic ring together with the "-CN=C-" moiety or a substituted heterocyclic ring;

[0083] R 1 is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl and silylhydrocarbyl;

[0084] R 2 -E(R 12 )(R 13 )-, where E is carbon, silicon or germanium, and each R 12 and R 13 independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, silyl hydrocarbyl and polar groups;

[0085] R 3 C or N and R 4 and R 5 is C, and R 3 and R 4 is part of a five-membered or six-membered carbocyclic or heterocyclic ring, which may be substituted or unsubstituted, and R 4 and R 5 is part of a five- or six-membered carbocyclic or heterocyclic ring, which may be substituted or unsubstituted;

[0086] Each J is independently selected from C, CH, CH2, CR 18 , CHR 18 , C(R 18 )2,Si(R 18 )2,SiH(R 18 ), NH, NR 18 , O or S, where R 18 is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, halogen, and silylhydrocarbyl;

[0087] Each x is independently 3 or 4, representing the number of J groups connected in series;

[0088] Y is selected from substituted and unsubstituted Group 14 elements, including, but not limited to CH2, CH(R 18 ), C(R 18 )2, C(O) and C(NR 18 ), where R 18 As defined above and wherein the heteroatom (such as O or N) may be coordinately bonded to M;

[0089] Y' is selected from substituted and unsubstituted Group 14 elements, including, but not limited to CH, C(R18 ), where R 18 As defined above;

[0090] L is an anionic leaving group, wherein the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

[0091] L' is a neutral Lewis base;

[0092] n is 1, 2 or 3;

[0093] w is 0, 1, 2, or 3;

[0094] where n+w is not greater than 4; and

[0095] The tridentate dianionic ligand is chelated to the metal M in such a way that the complex forms an eight-membered ring and a five-membered ring, which are represented by the numbers 8 and 5 in formulae (A) to (D), respectively.

[0096] In another aspect of the present invention, there is provided a heterocyclic amino transition metal complex represented by formula (E), (F), (G), (H), (I) or (J) (optionally for olefin polymerization).

[0097]

[0098] in:

[0099] M, R 1 , R 2 ,L,L',n,w,Y,Y',Q 2 and Q 2' As defined above; E 2 and E 3 is independently selected from O, S, NH or NR 9 , where R 9 is a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, a halogen, a silyl hydrocarbon group or a polar group;

[0100] Each R 7 Independently selected from hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, halogenated hydrocarbon group, substituted halogenated hydrocarbon group, silyl hydrocarbon group and polar group, preferably hydrocarbon group;

[0101] Each R 8 Independently selected from hydrogen, halogen, hydrocarbon, substituted hydrocarbon, halogenated hydrocarbon, substituted halogenated hydrocarbon, silyl hydrocarbon and polar groups, preferably hydrogen.

[0102] In any embodiment of the invention described herein, M may be Ti, Hf or Zr, preferably Hf or Zr.

[0103] In any of the embodiments of the invention described herein, Q 1 It may be a substituted or unsubstituted imidazole, oxazole or thiazole group, which is attached to R via the carbons at the 2 and 4 positions of the heterocyclic ring. 3 and R 2 , where G 2 The radical is the atom at position 3, using the numbering scheme for imidazole, oxazole, and thiazole shown below.

[0104]

[0105] In any of the embodiments of the invention described herein, G 1 and G 3 Each is a Group 14 atom that is linked together through two or three additional Group 14, 15 or 16 atoms to form a heterocyclic ring or a substituted heterocyclic ring.

[0106] In a preferred embodiment, Q 2 For CHR 17 , CH2 or C(R 17 )2, where R 17 is selected from hydrocarbon groups (such as alkyl and aryl), substituted hydrocarbon groups (such as heteroaryl) and silyl hydrocarbon groups, preferably R 17 is a phenyl group or a substituted phenyl group, which is optionally substituted with one to five substituents, including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl and alkyl groups having 1-10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and their isomers.

[0107] In a preferred embodiment, Q 2 NR 17 , where R 17 is selected from hydrocarbon groups (such as alkyl and aryl), substituted hydrocarbon groups (such as heteroaryl) and silyl hydrocarbon groups, preferably R 17 is a phenyl group or a substituted phenyl group, which is optionally substituted with one to five substituents, including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl and alkyl groups having 1-10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and their isomers.

[0108] In a preferred embodiment, Q 2 is O.

[0109] In a preferred embodiment, Q 2' is N.

[0110] In a preferred embodiment, M is Zr or Hf, n is 2 and w is zero.

[0111] In a preferred embodiment, Q 2' CH or CR 17 , where R 17 is selected from hydrocarbon groups (such as alkyl and aryl), substituted hydrocarbon groups (such as heteroaryl) and silyl hydrocarbon groups, preferably R 17 is a phenyl group or a substituted phenyl group, which is optionally substituted with one to five substituents, including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl and alkyl groups having 1-10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and their isomers.

[0112] In any embodiment of the present invention described herein, each T may be independently selected from CH, C(alkyl), O, S, NH, N(alkyl), NMe and NEt, wherein alkyl is preferably C1-C 40 Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or isomers thereof.

[0113] In any of the embodiments of the invention described herein, E may be C, Si or Ge.

[0114] In any of the embodiments of the invention described herein, Y may be CH2, CH(Ph), CH(Me), CH(t-Bu), CH(i-Pr), C(O), C(N-iPr), C(NMe), C(NEt), C(Nt-Bu) or C(NPh).

[0115] In any of the embodiments of the invention described herein, Y' may be CH, C(Ph), C(Me), C(t-Bu), C(Et), C(Pr), C(Bu), C(hexyl), or C(i-Pr).

[0116] In any of the embodiments of the invention described herein, Q 2 It can be O, N(Ph), N(mesityl), N(2,6-dimethylphenyl), N(2,6-diethylphenyl), N(2-methylphenyl), N(2-ethylphenyl), N(butyl), N(propyl), N(isopropyl), N(cyclohexyl), N(t-butyl) or N(2,6-diisopropylphenyl).

[0117] In any of the embodiments of the invention described herein, Q 2It can be CH2, CHMe, CHEt, CHBu, CH(pentyl), CH(hexyl), CH(hexyl), CH(octyl), CH(nonyl), CH(decyl) or CHPh, O, N(Ph), N(mesityl), N(2,6-dimethylphenyl), N(2,6-diethylphenyl), N(2-methylphenyl), N(2-ethylphenyl), N(butyl), N(propyl), N(isopropyl), N(cyclohexyl), N(t-butyl) or N(2,6-diisopropylphenyl).

[0118] In any of the embodiments of the invention described herein, Q 2' It can be N, P, CH, C(Ph), C(Me), C(t-Bu) or C(i-Pr).

[0119] In any embodiment of the invention described herein, preferably L is selected from halide, alkyl, aryl, alkoxy, amino, hydrido, phenoxy, hydroxyl, silyl, allyl, alkenyl, alkylsulfonate, alkylcarboxylate, arylcarboxylate and alkynyl, preferably benzyl, methyl, trimethylsilylmethyl, dimethylamino, diethylamino, fluoride and chloride. The choice of leaving group depends on the synthetic route used to obtain the complex and can be modified by additional reactions to suit the activation method in the subsequent polymerization. For example, when a non-coordinating anion activator is used, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)borane, preferably L is an alkyl group. In another embodiment, two L groups can be connected to form a dianionic leaving group, such as oxalate.

[0120] In any embodiment of the invention described herein, preferably L' is selected from ethers, thioethers, amines, nitriles, imines, pyridines and phosphines, preferably ethers, preferably diethyl ether, dimethyl sulfide, tetrahydrofuran and tetrahydrothiophene.

[0121] In any embodiment of the invention described herein, n is 1, 2 or 3 and w is 0, 1, 2 or 3, wherein n+w is no greater than 4, preferably n is 1 or 2 and w is 0 or 1 and n+w is 2. Alternatively, n is 2, w is 0 and n+w is 2.

[0122] In any of the embodiments of the invention described herein, R 1 It can be selected from alkyl, aryl, heteroaryl and silyl groups, preferably R 1is selected from phenyl groups, which are substituted in various ways with zero to five substituents, including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl and alkyl groups with 1-10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and their isomers. Some specific examples include R selected from the group including 1 : 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 2,6-dimethylphenyl, mesityl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-methyl-6-isopropylphenyl and 2-ethyl-6-methylphenyl.

[0123] In any of the embodiments of the invention described herein, R 2 may be selected from the group consisting of moieties wherein E is carbon, in particular -C(R 12 )(R 13 )-part, where R 12 for hydrogen and R 13 is an aryl group or a benzyl group (preferably the phenyl ring is attached to the C atom via an alkylene moiety such as a methylene group). The phenyl group may then be treated as above for R 1 The one in question is replaced. Useful R 2 The groups include CH2, CMe2, SiMe2, SiEt2, SiPr2, SiBu2, SiPh2, Si(aryl)2, Si(alkyl)2, CH(aryl), CH(Ph), CH(alkyl), CH(mesityl) and CH(2-isopropylphenyl). Particularly useful R 2 The groups include CH2, CMe2, SiMe2, SiEt2, SiPr2, SiBu2, SiPh2, Si(aryl)2 and Si(alkyl)2, CH(aryl), CH(Ph), CH(alkyl), CH(mesityl) and CH(2-isopropylphenyl), where the alkyl group is C1-C 40 Alkyl group, aryl is C5-C 40 Aryl group.

[0124] In some embodiments of the present invention, R 2 Preferred is CH (mesityl).

[0125] In any of the embodiments of the invention described herein, R 2 It is expressed by the following formula:

[0126]

[0127] Where R 12 is hydrogen, alkyl, aryl or halogen; and R 13is hydrogen, alkyl, aryl or halogen.

[0128] In any of the embodiments of the invention described herein, R 12 and R 13 may be independently hydrogen, C1-C 20 alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or isomers thereof) or C5-C 40 Aryl group (preferably C6-C 20 Aryl groups, preferably phenyl or substituted phenyl or their isomers, preferably phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0129] In any of the embodiments of the invention described herein, R 3 Can be C or N.

[0130] In any of the embodiments of the invention described herein, R 4 and R 5 For C.

[0131] In any of the embodiments of the invention described herein, each J may be independently selected from C, CH, CH2, Si(R 18 )2、SiH(R 18 ), NR 18 , O or S, where R 18 Selected from hydrocarbyl, substituted hydrocarbyl and silyl hydrocarbyl.

[0132] In any of the embodiments of the invention described herein, each x may be 3 or 4.

[0133] In any of the embodiments of the invention described herein, R 1 and R 17 Each contains 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms.

[0134] In any embodiment of the invention described herein, M may be Ti, Zr or Hf and E is carbon, with complexes based on Zr or Hf being particularly preferred.

[0135] In alternative embodiments of the invention described herein, E is carbon and R 1 is selected from a phenyl group substituted with 0, 1, 2, 3, 4 or 5 substituents selected from F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, hydrocarbyl and substituted hydrocarbyl groups having one to ten carbons.

[0136] In a preferred embodiment, Q 2'is nitrogen and Y' is CH or C(hydrocarbyl), wherein the hydrocarbyl group contains 1-20 carbon atoms.

[0137] In a preferred embodiment, Q 2' and Y' are each independently CH or C(hydrocarbyl), wherein each hydrocarbyl group contains 1-20 carbon atoms.

[0138] In a preferred embodiment, Q 2 is N(hydrocarbyl) and Y is CH2 or CH(hydrocarbyl), wherein the hydrocarbyl group is independently selected from a group containing 1 to 20 carbon atoms.

[0139] In a preferred embodiment, Q 2 and Y are each independently CH2 or CH(hydrocarbyl), wherein each hydrocarbyl group contains 1-20 carbon atoms.

[0140] In a preferred embodiment, Y is selected from CH2 or CH(alkyl) and Q 2 Not CH2, CH(alkyl) or C(alkyl)2, wherein the alkyl group is independently selected from a group containing 1 to 20 carbon atoms.

[0141] In a preferred embodiment, Q 2 Not CH2, CH(alkyl) or C(alkyl)2, wherein the alkyl group is independently selected from a group containing 1 to 20 carbon atoms.

[0142] In a preferred embodiment, M is zirconium, n is 2, w is 0 and R 1 It is a 2,6-dialkylphenyl group containing 8 to 20 carbon atoms.

[0143] In a preferred embodiment, M is hafnium, n is 2, w is 0 and R 1 It is a 2,6-dialkylphenyl group containing 8 to 20 carbon atoms.

[0144] In a preferred embodiment, M is zirconium, L is a hydrocarbon group containing 1 to 6 carbon atoms, n is 2, w is 0 and R 1 It is a 2,6-dialkylphenyl group containing 8 to 20 carbon atoms.

[0145] In a preferred embodiment, M is hafnium, L is a hydrocarbon group containing 1 to 6 carbon atoms, n is 2, w is 0 and R 1 It is a 2,6-dialkylphenyl group containing 8 to 20 carbon atoms.

[0146] In a preferred embodiment, M is zirconium, L is a hydrocarbon group containing 1 to 6 carbon atoms, n is 2, w is 0 and Q 2' For nitrogen.

[0147] In a preferred embodiment, M is hafnium, L is a hydrocarbon group containing 1 to 6 carbon atoms, n is 2, w is 0 and Q 2' For nitrogen.

[0148] Preferred pair R 2 and Y group (expressed as R 2 & Y) include: (CH2 & CH(Ph)), (CMe2 & CH(Ph)), (CH2 & CH(aryl)), (CH2 & CH(alkyl)), (CH(aryl) & CH(aryl)), (CH(aryl) & CH(alkyl)), (CH(mesityl) & CH(aryl)) and (CH(mesityl) & CH(alkyl)), wherein the alkyl group is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 Aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0149] Preferred pair R 1 and R 2 Group (expressed as R 1 &R 2 ) include: (2,6-diisopropylphenyl & CH2), (2,6-diisopropylphenyl & CH(mesityl)), (2,6-diisopropylphenyl & CHPh), (2,6-diisopropylphenyl & CH(aryl)), (2,6-disubstituted phenyl & CH(aryl)), wherein the alkyl group is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 Aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0150] Preferred pair R 1 and Q 2 Group (expressed as R 1 &Q 2 ) include: (2,6-di(alkyl)phenyl & N(alkyl)), wherein the alkyl is C1-C 40 Alkyl groups (preferably C1-C 20The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 Aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0151] Preferred pair R 1 and Q 2 Group (expressed as R 1 &Q 2 ) include: (2,6-diisopropylphenyl & CH2), (2,6-diisopropylphenyl & CH(alkyl)), (2,6-diisopropylphenyl & CHPh), (2,6-di(alkyl)phenyl & N(alkyl)), wherein the alkyl group is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 Aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0152] In another embodiment, R 2 is CH2 or CMe2 and Y is selected from CH(Ph), CH(aryl), CH(mesityl) and CH(alkyl), wherein alkyl is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 Aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0153] In any of the embodiments described herein, E is preferably carbon.

[0154] In a preferred embodiment, the heterocyclic amino transition metal complex is of formula (A), (B), (C) or (D) represented above and M is a Group 4 metal, preferably Zr or Hf, preferably Hf.

[0155] In a preferred embodiment, the heterocyclic amino transition metal complex is of formula (A), (B), (C) or (D) represented above, and in R 2 In the group, R 12 For H and R 13 is a group containing 1-100 (preferably 6-40, preferably 6-30) carbon atoms, M is a Group 4 metal (preferably Zr or Hf, preferably Hf), E is carbon, and R 2 In the group, R 12 With R 13 The same and are preferably hydrogen or methyl.

[0156] In a preferred embodiment, the heterocyclic amino transition metal complex is of formula (A), (B), (C) or (D) represented above, and R 2 R in the group 12 and R 13 All are C1-C 100 Alkyl group (preferably C6-C 40 Alkyl group, preferably C6-C 30 Alkyl group, alternatively C1-C 12 alkyl group, alternatively a C1-C6 alkyl group, alternatively a methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl or isomers thereof).

[0157] In another aspect of the present invention, various methods are provided for synthesizing the complexes described herein.

[0158] Synthesis method

[0159] The complexes described herein can be prepared by reacting a molecule containing a reactive double or triple bond (shown as XY in the figure below) with a suitable transition metal complex (shown as intermediate A in the figure below). The transition metal complex that can be used in the method can be neutral or cationic and have a metal-carbon bond that reacts with the double or triple bond of the unsaturated reactant to formally insert the aforementioned metal-carbon bond via the XY bond to form the complex of the present invention. The product of such an insertion reaction will be characterized by a new covalent bond between the transition metal center and at least one atom of the XY group. Such a reaction can be used to prepare the complex of the present invention for the purpose of separation. Alternatively, these reactions can be used to generate the complex of the present invention in situ, and it is expected that the complex will be applied to olefin polymerization methods. General examples of insertion reactions are shown in the following two equations.

[0160] Insertion reactions involving XY molecules containing a reactive triple bond:

[0161]

[0162] Insertion reactions involving XY molecules with reactive double bonds:

[0163]

[0164] In useful embodiments, the reactive XY molecule has a reactive CO double bond. Such molecules that may be suitable for such applications include, but are not limited to, ketones, aldehydes, isocyanates, amides, formamides, esters and carbon dioxide. When X is oxygen, the insertion product formed will typically have a new transition metal-oxygen bond. The Y group is usefully selected from a list including, but not limited to, CH2, CH(alkyl), CH(aryl), C(alkyl)2, C(aryl)2, C(alkyl)(aryl), C=N(alkyl), C=N(aryl), C(NH)(alkyl), C(NH)(aryl), C(alkyl)(alkoxy), C(alkyl)(aryloxy), C(aryl)(alkoxy), C(aryl)(aryloxy) and CO.

[0165] In another embodiment, the reactive XY molecule has a reactive CN double bond. Such molecules that may be suitable for such applications include, but are not limited to, imines, azomethines, and carbodiimides. The resulting insertion product will typically have a new transition metal-nitrogen bond, whereby the X group is NH, N(alkyl), N(aryl), or another type of substituted nitrogen. The Y group is selected from a list including, but not limited to, CH(alkyl), CH(aryl), CH2, CN(alkyl), and CN(aryl).

[0166] In another embodiment, the reactive XY molecule has a reactive CN triple bond. Such molecules that may be suitable for such applications include, but are not limited to, nitriles. The insertion product formed will typically have a new transition metal-nitrogen bond, so that the X group is nitrogen. The Y group is selected from a list including, but not limited to, CH, C (alkyl) and C (aryl).

[0167] In another embodiment, the reactive XY molecule has a reactive C-C double bond. Such molecules that may be suitable for such applications include, but are not limited to, ethylene, propylene, alpha olefins, internal olefins, propadiene, dienes, and styrene. The insertion product formed will typically have a new transition metal-carbon bond, whereby the X group is CH2, CH(alkyl), CH(aryl), C(alkyl)2, C(aryl)2, C(alkyl)(aryl) or other disubstituted carbon, wherein the alkyl is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20The Y group is selected from a list including but not limited to: CH2, CH(alkyl), CH(aryl), C(alkyl)2, C(aryl)2, C(alkyl)(aryl) and other disubstituted carbons, wherein the alkyl group is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 aryl group, preferably phenyl or substituted phenyl).

[0168] In another embodiment, the reactive XY molecule has a reactive C-C triple bond. Such molecules that may be suitable for such applications include, but are not limited to, acetylene, terminal alkynes, and internal alkynes. The insertion product formed will typically have a new transition metal-carbon bond, whereby the X group is CH, C(alkyl) or C(aryl), where alkyl is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 The Y group is selected from the group including but not limited to the following list, CH, C (alkyl) and C (aryl), wherein alkyl is C1-C 40 Alkyl groups (preferably C1-C 20 The alkyl group is preferably one or more of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, and the aryl group is C5-C 40 Aryl group (preferably C6-C 20 aryl group, preferably phenyl or substituted phenyl).

[0169] In another embodiment, the transition metal complexes of the present invention are directed to coordinated tridentate dianionic ligands having a central neutral coordination donor (N 配位 ) and a pair of anion donor groups (N 阴离子 and X). By [N 阴离子 -N 配位 -X] tridentate ligand chelated to the transition metal center (ignoring any additional bonding to the Y group) to form two rings with sizes of 5 and 8 atoms. These are shown in the figure below. The 8-membered chelate ring contains the transition metal M, X, Y, N配位 and four additional atoms forming N excluding M 配位 The shortest connection between and Y. The 5-membered chelate ring contains transition metals M, N 配位 、N 阴离子 and two additional atoms, which form N excluding M 配位 and N 阴离子 The shortest connection between .

[0170]

[0171] In another embodiment, the transition metal complex of the present invention relates to a coordinated tridentate dianionic ligand, as drawn below. Ring A represents a 5- or 6-membered heterocyclic ring having a nitrogen atom capable of forming a coordination bond with the metal M. Examples of ring A include, but are not limited to, derivatives of imidazole, N-alkylimidazole, thiazole, and oxazole. Ring B and ring C are each a 5- or 6-membered ring containing hydrogen and a Group 14, 15, and / or 16 element. Ignoring any additional bonding to the Y group, the ring is bound by [N 阴离子 -N 配位 The two chelate rings formed by the coordination of the tridentate ligand to the transition metal center have sizes of 5 and 8 atoms. The 8-membered chelate ring contains transition metals M, X, Y, N 配位 and four additional atoms forming N excluding M 配位 The shortest connection between and Y. The 5-membered chelate ring contains transition metals M, N 配位 、N 阴离子 and two additional atoms, which form N excluding M 配位 and N 阴离子 The shortest connection between .

[0172]

[0173] In another embodiment, the complex of the present invention is prepared by a route that does not involve the reaction of an intermediate transition metal complex (e.g., intermediate A) with a small molecule XY. Alternatively, a neutral multidentate ligand is preformed in a multistep organic synthesis. Then, the preformed ligand can be coordinated to a transition metal using a known method. For example, the "free alkali" form of a multidentate ligand can be deprotonated to form a lithium salt (i.e., Li2[ligand]) of a ligand with two equivalents of a strong base (e.g., butyllithium). Then the lithium salt can be reacted with a transition metal halide, such as HfCl4, ZrCl4, TiCl4, or TiCl3 to form a desired complex (e.g., [ligand] HfCl2, [ligand] ZrCl2, [ligand] TiCl2, or [ligand] TiCl), and the lithium chloride byproduct is removed. Alternatively, the free base ligand can be reacted with a basic transition metal reagent such as Hf(CH2Ph)4, Hf(CH2Ph)2Cl2(OEt2), Zr(CH2Ph)4, Zr(CH2Ph)2Cl2(OEt2), Zr(NMe2)4, Hf(NEt2)4 or Hf(NMe2)2Cl2(1,2-dimethoxyethane) to form the desired complex (e.g., [ligand]Hf(CH2Ph)2, [ligand]HfCl2, [ligand]Zr(NMe2)2, [ligand]ZrCl2) and remove the byproduct conjugate acid from the acid-base reaction.

[0174] Activator

[0175] After the complex is synthesized, the catalyst system can be formed by combining the complex with an activator in any manner known from the literature, including loading them for slurry or gas phase polymerization. The catalyst system can also be added to solution polymerization or bulk polymerization (in monomer) or produced in solution polymerization or bulk polymerization (in monomer). The catalyst system typically comprises a complex as described above and an activator such as aluminoxane or a non-coordinating anion. Activation can be carried out using an aluminoxane solution, including methylaluminoxane, referred to as MAO, and modified MAO, referred to as MMAO herein, containing some higher alkyl groups to improve solubility. Particularly useful MAO can be purchased from Albemarle, which is typically a 10wt% solution in toluene. The catalyst system used in the present invention preferably uses an activator selected from aluminoxanes, such as methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, etc.

[0176] When an alumoxane or modified alumoxane is used, the molar ratio of complex to activator is about 1:3000-10:1; alternatively 1:2000-10:1; alternatively 1:1000-10:1; alternatively 1:500-1:1; alternatively 1:300-1:1; alternatively 1:200-1:1; alternatively 1:100-1:1; alternatively 1:50-1:1; alternatively 1:10-1:1. When the activator is an alumoxane (modified or unmodified), some embodiments select a maximum amount of activator, i.e., a 5000-fold molar excess relative to the catalyst precursor (per metal catalytic site). The preferred minimum activator to complex ratio is a 1:1 molar ratio.

[0177] Activation can also be carried out using the non-coordinating anion (being referred to as NCA) of the type described in EP 277 003 A1 and EP 277 004 A1.NCA can be added in the form of ion pair using, for example, [DMAH]+[NCA]-, wherein N,N-dimethylanilinium (DMAH) cation reacts with the alkaline leaving group on the transition metal complex to form transition metal complex cation and [NCA]-.Cation in the precursor can alternatively be trityl.Alternatively, the transition metal complex can react with neutral NCA precursors such as B(C6F5), and anionic groups are grabbed from the complex to form activated substances.Useful activators include N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate (i.e. [PhNMe2H]B(C6F5)4) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl) borate, wherein Ph is phenyl and Me is methyl.

[0178] Additionally, preferred activators useful herein include those described in US Pat. No. 7,247,687 at column 169, line 50 to column 174, line 43, especially column 172, line 24 to column 173, line 53.

[0179] Non-coordinating anions (NCA) are defined as anions that do not coordinate with the catalyst metal cation or coordinate with the metal cation but only weakly. The term NCA is also defined as including multi-component activators containing NCA, such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, which contains acidic cationic groups and non-coordinating anions. The term NCA is also defined as including neutral Lewis acids, such as tris (pentafluorophenyl) boron, which can react with the catalyst to form an activated species by extracting anionic groups. The NCA coordination is weak enough so that a neutral Lewis base such as an olefinic or acetylenic unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible weakly coordinated complex can be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus and silicon. Stoichiometric activators can be neutral or ionic. The terms ionic activator and stoichiometric ionic activator can be used interchangeably. Similarly, the terms neutral stoichiometric activator and Lewis acid activator may be used interchangeably.The term non-coordinating anion includes neutral stoichiometric activators, ionic stoichiometric activators, ionic activators, and Lewis acid activators.

[0180] In embodiments of the invention described herein, the non-coordinating anion activator is represented by the following formula (1):

[0181] (Z) d + (A d- ) (1)

[0182] Wherein Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH)+ is a Bronsted acid; A d- is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.

[0183] When Z is (LH), the cationic component is (LH) d + The cationic component may include a Bronsted acid, such as a protonated Lewis base, which is capable of protonating a moiety, such as an alkyl or aryl group, from the catalyst precursor to produce a cationic transition metal species, or an activating cation (LH) d +The Brønsted acid is a Bronsted acid that can donate a proton to a transition metal catalyst precursor to generate a transition metal cation, including ammonium, oxonium, phosphonium, silyl onium and mixtures thereof, preferably the following ammonium: methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, the following phosphonium: triethylphosphine, triphenylphosphine and diphenylphosphine, the following oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, the following sulfonium from sulfide such as diethyl sulfide and tetrahydrothiophenol, and mixtures thereof.

[0184] When Z is a reducible Lewis acid, it can be represented by the following formula: (Ar3C+), wherein Ar is an aromatic group or is substituted by a heteroatom or a C1-C 40 The aryl group substituted with a hydrocarbon group, a reducible Lewis acid can be represented by the following formula: (Ph3C + ), wherein Ph is phenyl or is replaced by heteroatoms and / or C1-C 40 Hydrocarbyl-substituted phenyl. In one embodiment, the reducible Lewis acid is triphenylcarbonium.

[0185] Anionic component A d- Embodiments include those having the formula [M k + Q n ] d - Those wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6, or 3, 4, 5 or 6; nk = d; M is an element selected from Group 13 of the Periodic Table of Elements or boron or aluminum, and Q is independently a hydride, a bridged unbridged dialkylamino, a halide, an alkoxy, an aryloxy, a hydrocarbon group, wherein Q has up to 20 carbon atoms, provided that Q is a halide at no more than one occurrence and two Q groups can form a ring structure. Each Q may be a fluorinated hydrocarbon group having 1-20 carbon atoms, or each Q is a fluorinated aryl group, or each Q is a pentafluoroaryl group. Suitable A d- Examples of components also include diboron compounds disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.

[0186] In any embodiment of NCA represented by Formula 1 above, the anionic component A d- From the formula [M*k*+Q*n*]d* -represents, wherein k* is 1, 2 or 3; n* is 1, 2, 3, 4, 5 or 6 (or 1, 2, 3 or 4); n*-k*=d*; M* is boron; and Q* is independently selected from hydride, bridged unbridged dialkylamino, halogen, alkoxy, aryloxy, hydrocarbon, said Q* having up to 20 carbon atoms, provided that Q* is halogen in no more than 1 occurrence.

[0187] The present invention also relates to a method for polymerizing olefins, comprising contacting an olefin (such as propylene) with the above catalyst complex and an NCA activator represented by formula (2):

[0188] R n M**(ArNHal) 4-n (2)

[0189] wherein R is a monoanionic ligand; M** is a Group 13 metal or metalloid; ArNHal is a halogenated nitrogen-containing aromatic ring, a polycyclic aromatic ring, or an aromatic ring assembly in which two or more rings (or fused ring systems) are directly linked to each other or linked together; and n is 0, 1, 2 or 3. Typically, the NCA comprising an anion of Formula 2 also comprises a suitable cation that does not substantially interfere with the ionic catalyst complex formed with the transition metal compound, or the cation is Z as described above. d + .

[0190] In any embodiment of NCA including an anion represented by Formula 2 above, R is selected from C1-C 30 In one embodiment, C1-C 30 The alkyl group may be substituted by one or more C1-C 20 Hydrocarbyl, halide, hydrocarbon-substituted organometallic, dialkylamino, alkoxy, aryloxy, alkylsulfido, arylsulfido, alkylphospho, arylphosphide or other anionic substituents; fluoride; bulky alkoxide substituted, wherein bulky refers to C4-C 20 Alkyl; -SR a , -NR a 2and-PR a 2, where each R a independently a monovalent C4-C 20 A hydrocarbon group, or a C4-C6 group having a molecular volume greater than or equal to that of an isopropyl group 20 Hydrocarbyl-substituted organometallics.

[0191] In any embodiment of the NCA represented by Formula 2 above that includes an anion, the NCA further comprises a cation that includes a reducible Lewis acid represented by the formula: (AR 3 C+), wherein Ar is an aromatic group or is substituted by heteroatoms and / or C1-C 40 A hydrocarbon-substituted aromatic group, or a reducible Lewis acid represented by the following formula: (Ph3C+), wherein Ph is a phenyl group or is replaced by one or more heteroatoms and / or C1-C 40 Hydrocarbyl-substituted phenyl.

[0192] In any embodiment of the NCA represented by Formula 2 above that includes an anion, the NCA may further include a cation represented by the following formula: (LH)d+, wherein L is a neutral Lewis base; H is hydrogen; (LH) is a Bronsted acid; and d is 1, 2 or 3, or (LH)d+ is a Bronsted acid selected from ammonium, oxonium, phosphonium, silyl onium and mixtures thereof.

[0193] Further examples of useful activators include those disclosed in US 7,297,653 and US 7,799,879, which are incorporated herein by reference.

[0194] In one embodiment, the activators useful herein comprise a salt of a cationic oxidant and a non-coordinating compatible anion, as shown in formula (3):

[0195] (OX e+ ) d (A d- ) e (3)

[0196] Among them, OX e+ is a cationic oxidant having a charge of e+; e is 1, 2 or 3; d is 1, 2 or 3; and A d- is a non-coordinating anion having a charge d- (as further described above). Examples of cationic oxidants include: ferrocene, hydrocarbyl-substituted ferrocene, Ag + or Pb +2 . A d- Suitable embodiments include tetrakis(pentafluorophenyl)borate.

[0197] Activators useful for the catalyst systems of the present invention include trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, and those disclosed in U.S. Pat. No. 7,297,653, which is incorporated herein by reference.

[0198] Suitable activators also include: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonium tetrakis(perfluorophenyl)borate, [Ph3C + ][B(C6F5)4 - ],[Me3NH + ][B(C6F5)4 - ]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyridinium; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0199] In one embodiment, the activator includes a triarylcarbonium (such as triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

[0200] In one embodiment, two NCA activators can be used for polymerization, and the molar ratio of the first NCA activator to the second NCA activator can be any ratio. In one embodiment, the molar ratio of the first NCA activator to the second NCA activator is 0.01:1-10,000:1 or 0.1:1-1000:1 or 1:1-100:1.

[0201] In an embodiment of the present invention, the ratio of NCA activator to catalyst is 1:1 molar ratio or 0.1:1-100:1 or 0.5:1-200:1 or 1:1-500:1 or 1:1-1000: 1. In one embodiment, the ratio of NCA activator to catalyst is 0.5:1-10:1 or 1:1-5:1.

[0202] In one embodiment, the catalyst compound may be combined with a combination of aluminoxane and NCA (see, for example, US 5,153,157; ​​US 5,453,410; EP 0 573 120 Bl; WO 94 / 07928; and WO 95 / 14044, which discuss the use of aluminoxanes in combination with ionizing activators, all of which are incorporated herein by reference).

[0203] In a preferred embodiment of the invention, when an NCA (e.g., an ionic or neutral stoichiometric activator) is used, the molar ratio of complex to activator is typically 1:10-1:1; 1:10-10:1; 1:10-2:1; 1:10-3:1; 1:10-5:1; 1:2-1.2:1; 1:2-10:1; 1:2-2:1; 1:2-3:1; 1:2-5:1; 1:3-1.2:1; 1:3-10:1; 1:3-2:1; 1:3-3:1; 1:3-5:1; 1:5-1:1; 1:5-10:1; 1:5-2:1; 1:5-3:1; 1:5-5:1; 1:1-1:1.2.

[0204] Alternatively, a co-activator or chain transfer agent, such as a Group 1, 2 or 13 organometallic substance (e.g., an alkyl aluminum compound such as tri-n-octylaluminum) may also be used in the catalyst system of the present invention. The molar ratio of complex to co-activator is 1:100-100:1; 1:75-75:1; 1:50-50:1; 1:25-25:1; 1:15-15:1; 1:10-10:1; 1:5-5:1; 1:2-2:1; 1:100-1:1; 1:75-1:1; 1:50-1:1; 1:25-1:1; 1:15-1:1; 1:10-1:1; 1:5-1:1; 1:2-1:1; 1:10-2:1.

[0205] Chain transfer agent

[0206] A "chain transfer agent" is any agent capable of exchanging hydrocarbon and / or polymer-based groups between the coordinated polymerization catalyst and the metal center of the chain transfer agent during the polymerization process. The chain transfer agent may be any desired chemical compound, such as those disclosed in WO 2007 / 130306. Preferably, the chain transfer agent is selected from a Group 2, 12 or 13 alkyl or aryl compound; preferably a zinc, magnesium or aluminum alkyl or aryl; preferably wherein the alkyl is C1-C 30 Alkyl, alternatively C2-C 20 Alkyl, alternatively C3-C 12 The alkyl group is typically independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl and dodecyl; and among these diethylzinc is particularly preferred.

[0207] In a particularly useful embodiment, the present invention is directed to a catalyst system comprising an activator, a catalyst complex as described herein, and a chain transfer agent, wherein the chain transfer agent is selected from Group 2, 12 or 13 alkyl or aryl compounds.

[0208] In particularly useful embodiments, the chain transfer agent is selected from dialkyl zinc compounds wherein the alkyl groups are independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl and phenyl.

[0209] In particularly useful embodiments, the chain transfer agent is selected from trialkylaluminum compounds wherein the alkyl groups are independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl and phenyl.

[0210] Useful chain transfer agents are typically present in 10 or 20 or 50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalents relative to the catalyst component. Alternatively, the chain transfer agent ("CTA") is present in the following molar ratio of catalyst complex to CTA: about 1:3000-10:1; alternatively 1:2000-10:1; alternatively 1:1000-10:1; alternatively, 1:500-1:1; alternatively 1:300-1:1; alternatively 1:200-1:1; alternatively 1:100-1:1; alternatively 1:50-1:1; alternatively 1:10-1:1.

[0211] Useful chain transfer agents include diethylzinc, tri-n-octylaluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, dibutylzinc, di-n-propylzinc, di-n-hexylzinc, di-n-pentylzinc, di-n-decylzinc, di-n-dodecylzinc, di-n-tetradecylzinc, di-n-hexadecylzinc, di-n-octadecylzinc, diphenylzinc, diisobutylaluminum hydride, diethylaluminum hydride, di-n-octylaluminum hydride, dibutylmagnesium, diethylmagnesium, dihexylmagnesium and triethylboron.

[0212] Carrier

[0213] In some embodiments, the complexes described herein may be loaded (with or without an activator) by any method that effectively loads other coordination catalyst systems, effectively meaning that the catalysts prepared in this way can be used for oligomerization or polymerization of olefins in a heterogeneous process. Catalyst precursors, activators, co-activators as required, suitable solvents and supports can be added in any order or simultaneously. Typically, the complex and activator can be combined in a solvent to form a solution. The support is then added and the mixture is stirred for 1 minute to 10 hours. The total solution volume may be greater than the pore volume of the support, but some embodiments limit the total solution volume to less than required, thereby forming a gel or slurry (about 90%-400%, preferably about 100-200% of the pore volume). After stirring, the residual solvent is removed under vacuum, typically at ambient temperature and over 10-16 hours. Longer or shorter times and higher or lower temperatures are also possible.

[0214] The complex can also be supported without an activator; in such a case, the activator (and, if necessary, a co-activator) is added to the liquid phase of the polymerization process. In addition, two or more different complexes can be placed on the same support. Similarly, two or more activators or an activator and a co-activator can be placed on the same support.

[0215] Suitable solid particulate carriers are typically polymers or refractory oxide materials, each preferably porous. Preferably, any carrier material with an average particle size greater than 10 μm is suitable for the present invention. Various embodiments select porous carrier materials, such as, for example, talc, inorganic oxides, inorganic chlorides, such as magnesium chloride, and resinous carrier materials, such as polystyrene, polyolefins or polymer compounds, or any other organic carrier materials, etc. Some embodiments select inorganic oxide materials as carrier materials, including metals or metalloid oxides of Groups 2, 3, 4, 5, 13 or 14. The catalyst carrier materials selected in some embodiments include silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides can be used alone or in combination with silica, alumina or silica-alumina. These are magnesium oxide, titanium dioxide, zirconium oxide, etc. Lewis acid materials such as montmorillonite and similar clays can also be used as carriers. In this case, the carrier can optionally also be used as an activator component, however, another activator can also be used.

[0216] The support material can be pretreated by any number of methods. For example, the inorganic oxide can be calcined, chemically treated with a dehydroxylating agent such as an aluminum alkyl, or both.

[0217] As mentioned above, polymer supports are also suitable according to the present invention, see for example WO 95 / 15815 and US 5,427,991 for description. The disclosed methods can be applied to the catalyst complexes, activators or catalyst systems of the present invention to adsorb or absorb them on polymer supports, especially in the case of porous particles, or can be chemically bound to polymer chains or polymer chains via functional groups.

[0218] Useful supports typically have a surface area of ​​10-700 m 2 / g, a pore volume of 0.1-4.0 cc / g and an average particle size of 10-500 μm. Some embodiments select a surface area of ​​50-500 m 2 / g, a pore volume of 0.5-3.5cc / g or an average particle size of 20-200μm. Other embodiments select a surface area of ​​100-400m 2 / g, a pore volume of 0.8-3.0 cc / g and an average particle size of 30-100 μm. Useful supports typically have a pore size of 10-1000 angstroms, alternatively 50-500 angstroms or 75-350 angstroms.

[0219] The catalyst complex described herein is typically deposited on the support at the following loadings: 10-100 micromoles of complex per gram of solid support; alternatively 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support. However, larger or smaller values ​​may also be used, provided that the total amount of solid complex does not exceed the pore volume of the support.

[0220] polymerization

[0221] The catalyst complexes of the present invention can be used to polymerize unsaturated monomers that are generally known to undergo metallocene-catalyzed polymerizations, such as solution, slurry, gas phase, and high pressure polymerizations. Typically, one or more complexes described herein, one or more activators, and one or more monomers are contacted to prepare the polymer. In certain embodiments, the complexes can be supported and are therefore particularly useful in known fixed bed, moving bed, fluidized bed, slurry, solution, or bulk operating modes performed in single, series, or parallel reactors.

[0222] One or more reactors in series or in parallel can be used for the present invention. The complex, activator and co-activator when needed can be transported to the reactor as a solution or slurry, activated online just before the reactor, or pre-activated and pumped to the reactor as an activated solution or slurry. Polymerization is carried out in a single reactor operation, wherein monomer, comonomer, catalyst / activator / co-activator, optional scavenger and optional modifier are continuously added to a single reactor, or operated in a series reactor, wherein the above components are added to each of two or more reactors connected in series. Catalyst components can be added to the first reactor in series. Catalyst components can also be added to two reactors, wherein one component adds the first reaction, and another component adds another reactor. In a preferred embodiment, the complex is activated in the presence of olefins in the reactor.

[0223] In a particularly preferred embodiment, the polymerization process is a continuous process.

[0224] The polymerization process used herein typically comprises contacting one or more olefin monomers with a complex (and optional activator) as described herein. For the purposes of the present invention, olefins are defined as including polyenes (such as dienes) and olefins having only one double bond. The polymerization may be homogeneous (solution or bulk polymerization) or heterogeneous (slurry in a liquid diluent or gas phase in a gaseous diluent). In the case of heterogeneous slurry or gas phase polymerization, the complex and activator may be supported. Silica may be used as a carrier here. Chain transfer agents (such as hydrogen or diethyl zinc) may be used in the practice of the present invention.

[0225] The present polymerization process can be carried out under conditions preferably including a temperature of about 30° C. to about 200° C., preferably 60° C. to 195° C., preferably 75° C. to 190° C. The process can be carried out at a pressure of 0.05 MPa to 1500 MPa. In a preferred embodiment, the pressure is 1.7 MPa to 30 MPa, or in another embodiment, particularly under supercritical conditions, the pressure is 15 MPa to 1500 MPa.

[0226] monomer

[0227] Useful monomers herein include olefins having 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms (preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene and dodecene) and optionally also polyenes (such as dienes). Particularly preferred monomers include ethylene, and C2-C 10 Mixtures of alpha olefins such as ethylene-propylene, ethylene-hexene, ethylene-octene, propylene-hexene, etc.

[0228] The complexes described herein are also useful for the synthesis of ethylene alone or in combination with at least one other ethylenically unsaturated monomer, such as C3-C 20 α-olefins and especially C3-C 12 The polymerization of α-olefins is particularly effective. Similarly, the complexes of the present invention are also useful for the polymerization of propylene alone or with at least one other ethylenically unsaturated monomer such as ethylene or C4-C 20 α-olefins and especially C4-C 20 The polymerization of α-olefins is particularly effective. Examples of preferred α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl 1-pentene, 3-methyl 1-pentene, 3,5,5-trimethyl 1-hexene and 5-ethyl 1-nonene.

[0229] In some embodiments, the monomer mixture may further include one or more dienes up to 10 wt%, such as 0.00001-1.0 wt%, for example 0.002-0.5 wt%, such as 0.003-0.2 wt%, based on the monomer mixture. Non-limiting examples of useful dienes include cyclopentadiene, norbornadiene, dicyclopentadiene, 5-vinylidene-2-norbornene, 5-vinyl-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, and 9-methyl-1,9-decadiene.

[0230] When olefins that increase short chain branching, such as propylene, are used, the catalyst system can, under appropriate conditions, produce sterically regular polymers or polymers having a sterically regular order in the polymer chain.

[0231] Cleaners

[0232] In some embodiments, when the complexes described herein are used, especially when they are immobilized on a support, the catalyst system will additionally contain one or more scavenging compounds. Here, the term scavenging compound refers to a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability. Typically, the scavenging compound is an organometallic compound such as US 5,153,157; ​​US 5,241,025; WO-A-91 / 09882; WO-A-94 / 03506; WO-A-93 / 14132 Group 13 organometallic compounds; and WO 95 / 07941. Exemplary compounds include triethylaluminum, triethylborane, triiso-butylaluminum, methylaluminoxane, isobutylaluminum and tri-n-octylaluminum. These have bulky or C6-C ... 20 Scavenging compounds for linear hydrocarbyl substituents generally minimize adverse interactions with the activated catalyst. Examples include triethylaluminum, but more preferred are bulky compounds such as triisobutylaluminum, triisoprenylaluminum and long chain linear alkyl substituted aluminum compounds such as tri-n-hexylaluminum, tri-n-octylaluminum or tri-n-dodecylaluminum. When aluminoxane is used as an activator, any excess over that required for activation will scavenge impurities and no additional scavenging compounds may be required. Aluminoxane can also be used in scavenging amounts with other activators such as methylaluminoxane, [Me2HNPh] + [B(pfp)4] - Or B(pfp)3(perfluorophenyl=pfp=C6F5) are added together.

[0233] In a preferred embodiment, two or more complexes are combined with diethylzinc in the same reactor with the monomers. Alternatively, one or more complexes are combined with another catalyst (such as a metallocene) and a chain transfer agent, such as diethylzinc and / or tri-n-octylaluminum, in the same reactor with the monomers.

[0234] The chain transfer agent may be the same as or different from the scavenger.

[0235] Polymer products

[0236] Although the molecular weight of the polymers produced herein is affected by reactor conditions including temperature, monomer concentration and pressure, the presence of chain stoppers, etc., the homopolymer and copolymer products produced by the process of the present invention may have a Mw of about 1,000 to about 2,000,000 g / mol, alternatively about 30,000 to about 600,000 g / mol or alternatively about 100,000 to about 500,000 g / mol, as determined by GPC. Preferred polymers produced herein may be homopolymers or copolymers. In preferred embodiments, one or more comonomers are present at most 50 mol%, preferably 0.01-40 mol%, preferably 1-30 mol%, preferably 5-20 mol%. In some embodiments herein, a multimodal polyolefin composition is produced, which comprises a first polyolefin component and at least another polyolefin component having a molecular weight different from the first polyolefin component, preferably such that the GPC trace has more than one peak or inflection point.

[0237] The term "multimodal" refers to "multimodal molecular weight distribution" when used to describe a polymer or polymer composition, and is understood to refer to a gel permeation chromatography (GPC) track, plotted as absorbance versus retention time (seconds), having more than one peak or inflection point." inflection point " is such a point, wherein the second derivative of the curve changes sign (e.g., from negative to positive or vice versa). For example, a polyolefin composition comprising a first relatively low molecular weight polymer component (e.g., a polymer with an Mw of 100,000 g / mol) and a second relatively high molecular weight polymer component (e.g., a polymer with an Mw of 300,000 g / mol) is considered as a "bimodal" polyolefin composition. Preferably, the Mw of a polymer or polymer composition differs from each other by at least 10%, preferably at least 20%, preferably at least 50%, preferably at least 100%, preferably at least 200%. Similarly, in preferred embodiments, the Mw of the polymers or polymer compositions differ relative to each other by 10%-10,000%, preferably 20%-1000%, preferably 50%-500%, preferably at least 100%-400%, preferably 200%-300%.

[0238] Unless otherwise stated, the weight average molecular weight (Mw), number average molecular weight (Mn) and z average molecular weight (Mz) were determined by gel permeation chromatography (GPC), as described in Macromolecules, 2001, Vol. 34, No. 19, pg. 6812, which is incorporated herein by reference in its entirety, including high temperature size exclusion chromatography (SEC, Waters Alliance 2000), equipped with a differential refractive index detector (DRI), which is equipped with three Polymer Laboratories PL gel 10 mm mixed B columns. The instrument was operated at a flow rate of 1.0 cm 3 / min and injection volume 300μL. Various transmission lines, columns and differential refractometers (DRI detectors) were contained in an oven maintained at 145°C. Polymer solutions were prepared by heating 0.75-1.5mg / mL polymer in filtered 1,2,4-trichlorobenzene (TCB) containing about 1000ppm BHT at 160°C for 2 hours and continuously stirring. Samples of the solution containing the polymer were injected into the GPC and eluted with filtered 1,2,4-trichlorobenzene (TCB) containing about 1000ppm BHT. The separation efficiency of the column set was corrected using a series of narrow MWD polystyrene standards that reflected the expected Mw range of the analyzed samples and the exclusion limit of the column set. Calibration curves were generated using 17 separate styrene standards (obtained from Polymer Laboratories (Amherst, MA) and with a peak molecular weight (Mp) range of about 580-10,000,000 g / mole). Each round of experiments was flow rate corrected before measuring the retention volume of each polystyrene standard to obtain the common peak position of the flow rate marker (taken as the positive injection peak). When analyzing the sample, the flow rate marker peak position was used to correct the flow rate. The retention volume at the peak of the DRI signal was recorded for each PS standard, and the group data was fitted to a 2nd order polynomial to generate a calibration curve (log (Mp) vs. retention volume). The equivalent polyethylene molecular weight was determined using the Mark-Houwink coefficient, which is shown in Table B.

[0239] Table B

[0240]

[0241] In preferred embodiments, the homopolymer and copolymer products produced by the present process may have a Mw of about 1,000 to about 2,000,000 g / mol, alternatively about 30,000 to about 600,000 g / mol or alternatively about 100,000 to about 500,000 g / mol, as determined by GPC, and have a multimodal, preferably bimodal, Mw / Mn.

[0242] End Use

[0243] Articles made using the polymers prepared herein may include, for example, molded articles (such as containers and bottles, e.g., household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks and storage vessels, toys, sheets, tubes, pipes), films, nonwovens, etc. It should be appreciated that the applications listed above are merely exemplary and are not intended to be limiting.

[0244] experiment

[0245] The spectral range was obtained at 250, 400 or 500 MHz using a solution prepared by dissolving approximately 10 mg of sample in approximately 0.75 mL of C6D6, CD2Cl2, CDCl3 or D8-toluene. 1 H NMR spectral data. Chemical shifts (δ) given are at 7.15, 5.32, 7.24 and 2.09 for C6D6, CD2Cl2, CDCl3 and D8-toluene, respectively, relative to residual protium in the deuterated solvent. For the purposes of the claims, 500 Mz and CD2Cl2 were used. Example

[0246] Complexes 1-5 were prepared by reaction of intermediate A with a small molecule containing a reactive double or triple bond. The dashed line to the metal center represents an optional coordination bond.

[0247] HfBn2Cl2(Et2O) was prepared by reacting one equivalent of HfBn4(Strem) with HfCl4(Strem) in ether for 5 hours, followed by filtering and crystallizing the product. (2,6-Diisopropylphenyl){mesityl[1-methyl-4-(2-methyl-1-benzothiophen-3-yl)-1H-imidazol-2-yl]methyl}amine (LH2) was prepared as described in [Diamond, GM; Hall, KA; LaPointe, AM; Leclerc, MK; Longmire, J.; Shoemaker, JAW; Sun, P. US Patent 7,256,296 for Symyx Technologies, Inc.; Diamond, GM; Hall, KA; LaPointe, AM; Leclerc, MK; Longmire, J.; Shoemaker, JAW; Sun, P. ACS Catalysis 2011, 1, 887.]. Benzene (Merck) and hexane (Merck) were dried over and retained on molecular sieves 4A. Dichloromethane (and CD2Cl2 for NMR measurements) was filtered through P4O 10 Distilled and maintained over molecular sieves 4A. Acetone (Merck), diisopropylcarbodiimide (Aldrich), dicyclohexylcarbodiimide (Aldrich), phenylisocyanate (Aldrich), and isobutyronitrile (Aldrich) were used as received.

[0248] Intermediate A

[0249]

[0250] A mixture of (2,6-diisopropylphenyl){mesityl[1-methyl-4-(2-methyl-1-benzothiophene-3-yl)-1H-imidazol-2-yl]methyl}amine (LH2) (1.06 g, 1.98 mmol) and HfCl2Bn2(Et2O) (1.0 g, 1.98 mmol) was dissolved in 300 ml of benzene and the resulting solution was stirred in a pressure bottle at 80°C for 3 days. The solvent was then evaporated and the residue was washed with hexane (20 ml) and dichloromethane (2 x 10 ml). 850 mg (55%) of intermediate A was obtained as a white solid.

[0251] C 35 H 39 Anal. Calcd. for Cl2HfN3S: C, 53.68; H, 5.02; N, 5.37. Found: C, 53.79; H, 5.29; N, 5.22.

[0252] 1 H NMR (CD2Cl2): δ8.45 (m, 1H, 7-H, in benzothiophene), 7.80 (m, 1H, 5-H, in benzothiophene), 7.34 (m, 1H, 6-H, in benzothiophene), 7.34 (s, 1H, 5-H, in imidazole), 7.20 (m, 2H, 3,5-H in 2,6-diisopropylphenyl), 6.97 (m, 1H, 4-H, in 2,6-diisopropylphenyl), 6.80 (m, 1H, 3-H, in mesityl), 6.67 (m, 1H, 5-H, in mesityl), 6.13 (s, 1H, mesityl-CH), 3.22 (m, 1H, CHMe2), 3. 21 (s, 3H, NMe, in imidazole), 3.20 (m, 1H, CHMe2), 2.79 (s, 3H, 2-Me, in benzothiophene), 2.18 (s, 3H, 2-Me, in mesityl), 2.00 (s, 3H, 6-Me, in mesityl), 1.57 (s, 3H, 4-Me, in mesityl), 1.39 (d, J = 6.65 Hz, 3H, CHMeMe'), 1.34 (d, J = 6.85 Hz, 3H, CHMeMe'), 1.15 (d, J = 6.65 Hz, 3H, CHMeMe'), 0.10 (d, J = 6.65 Hz, 3H, CHMeMe').

[0253] Example 1. Synthesis of Complex 1 (Cat ID = 1)

[0254]

[0255] A mixture of 200 mg (0.255 mmol) of intermediate A and 15 mg (0.258 mmol) of acetone in 15 ml of dichloromethane was stirred at room temperature for 5 min. Afterwards, the solvent was evaporated and the residue was washed with 2 x 15 ml of hexane and dried in vacuo. This procedure gave 185 mg (86%) of complex 1 as a white solid.

[0256] C 38 H 45 Anal. Calcd. for Cl2HfN3OS: C, 54.25; H, 5.39; N, 4.99. Found: C, 54.40; H, 5.61; N, 4.75.

[0257] 1 H NMR (CD2Cl2): δ 7.77 (m, 1H, 7-H, in benzothiophene), 7.48 (m, 1H, 5-H, in benzothiophene), 7.27, (m, 1H, 6-H, in benzothiophene), 7.15 (m, 2H, 3, 5-H, in 2,6-diisopropylphenyl), 6.92 (m, 1H, 4-H, in 2,6-diisopropylphenyl), 6.86 (s, 1H, 5-H, in imidazole), 6.81 (m, 1H, 3-H, in mesityl), 6.64 (m, 1H, 5-H, in mesityl), 5.96 (s, 1H, mesityl-CH), 3.47 (m, 1H, CHMe2), 3.21 (m, 1H, CH (s, 3H, 4-Me in mesityl), 1.47 (s, J = 6.24 Hz, 3H, 4-Me in mesityl), 1.12 (d, J = 6.83 Hz, CHMeMe'), 0.10 (d, J = 6.83 Hz, 3H, CHMeMe').

[0258] 13 C{ 1H}NMR (CD2Cl2): δ155.50, 147.99, 147.53, 144.80, 143.85, 142.88, 141.56, 140.46, 139.03, 138.66, 136.74, 135.51, 132.35, 131.08, 130.03, 126.10, 12 4.13, 123.80, 123.68, 123.44, 122.97, 122.53, 84.76, 66.41, 33.59, 33.35, 31.19, 28.86, 28.25, 26.98, 25.65, 25.08, 22.53, 21.29, 20.76, 20.55, 16.83.

[0259] Example 2. Synthesis of Complex 2 (Cat ID = 2)

[0260]

[0261] A mixture of 200 mg (0.255 mmol) of intermediate A and 33 mg (0.261 mmol) of diisopropylcarbodiimide in 15 ml of dichloromethane was stirred at room temperature for 5 min. Afterwards, the solvent was evaporated and the residue was washed with 2 x 15 ml of hexane and dried in vacuo. This procedure gave 206 mg (89%) of complex 2 as a white solid.

[0262] C 42 H 53 Anal. Calcd. for Cl2HfN5S: C, 55.47; H, 5.87, N, 7.70. Found: C, 55.39; H, 6.06; N, 7.50.

[0263] 1H NMR (CD2Cl2): δ7.81 (m, 1H, 7-H, in benzothiophene), 7.38 (m, 1H, 5-H, in benzothiophene), 7.24 (m, 2H, 3-H, in 2,6-diisopropylphenyl), 7.13 (m, 1H, 6-H, in benzothiophene), 6.90 (m, 1H, 4-H, in 2,6-diisopropylphenyl), 6.76 (m, 1H, 3-H, in mesitylene), 6. 69 (m, 1H, 5-H, in imidazole), 6.57 (s, 1H, 3-H, in mesityl), 6.09 (s, 1H, mesityl-CH), 4.12 (m, 1H, CHMe2), 3.97 (m, 1H, Me2CH-N), 3.57 (m, 1H, CHMe2), 2.89 (s, 3H, NMe, in imidazole), 2.63 (s, 3H, 2-Me, in benzothiophene), 2.4 2 (m, 1H, Me2CH-N) 2.17, (s, 3H, 2-Me, in mesityl), 2.15 (s, 3H, 6-Me, in mesityl), 1.45 (d, J = 6.60 Hz, 3H, CHMeMe'), 1.43 (d, J = 6.61 Hz, 3H, CHMeMe'), 1.42 (s, 3H, 4-Me, in mesityl), 1.25 (d, J = 6.61 Hz, 3H, N-CHMeMe'), 1.10 (d, J=6.97Hz, 3H, CHMeMe'), 1.08 (d, J=6.60Hz, 3H, N-CHMeMe'), 0.65 (d, J =6.24Hz, 3H, N-CHMeMe'), 0.59 (d, 3H, J = 6.60Hz, N-CHMeMe'), 0.03 (d, J = 6.97Hz, 3H, CHMeMe').

[0264] 13 C{ 1 H}NMR (CD2Cl2): δ174.81, 159.68, 149.43, 149.11, 145.32, 143.06, 139.95, 139.81, 1 38.73, 138.22, 137.37, 133.15, 132.99, 132.72, 129.71, 129.39, 126.89, 125.81, 125. 57, 124.97, 123.97, 123.87, 122.76, 122.72, 65.14, 52.15, 50.76, 33.61, 29.16, 28.35, 28.09, 26.49, 26.10, 25.52, 25.26, 22.28, 22.03, 21.33, 20.89, 20.70, 17.35, 14.29.

[0265] Example 3. Synthesis of Complex 3 (Cat ID=3)

[0266]

[0267] A mixture of 200 mg (0.255 mmol) of intermediate A and 53 mg (0.257 mmol) of dicyclohexylcarbodiimide in 15 ml of dichloromethane was stirred at room temperature for 5 min. Afterwards, the solvent was evaporated and the residue was washed with 2 x 15 ml of hexane and dried in vacuo. This procedure gave 214 mg (85%) of complex 3 as a white solid.

[0268] C 48 H 61 Anal. Calcd. for Cl2HfN5S: C, 58.26; H, 6.21; N, 7.08. Found: C, 58.43; H, 6.39; N, 6.85.

[0269] 1H NMR (CD2Cl2): δ7.81 (m, 1H, 7-H, in benzothiophene), 7.38 (m, 1H, 6-H, in benzothiophene), 7.22, (m, 2H, 3, 5-H, in 2,6-diisopropylphenyl), 7.12 (m, 1H, 5-H, in benzothiophene), 6.89 (m, 1H, 4-H, in 2,6-diisopropylphenyl), 6.76 (m, 1H, 3-H, in mesityl ), 6.66 (s, 1H, 5-H, in imidazole), 6.56 (s, 1H, 3-H, in mesityl), 6.08 (s, 1H, mesityl-CH), 3.93 (m, 1H, CHMe2), 3.67 (m, 1H, 1-H, in cyclohexyl), 3.56 (m, 1H, CHMe2), 2.90 (s, 3H, NMe, in imidazole), 2.60 (s, 3H, 2-Me, in benzene thiophene), 2.15, (s, 3H, 2-Me, in mesityl), 2.14 (s, 3H, 6-Me, in mesityl), 1.98 (m, 1H, 1-H, in cyclohexyl), 1.88 (m, 2H, cyclohexyl), 1.52-1.70 (m, 5H, cyclohexyl), 1.48 (d, J = 6.84 Hz, 3H, CHMeMe'), 1.45 (d, J = 7.04 Hz, 3H, =CHMeMe'), 1.44 (s, 3H, 4-Me, in mesitylene), 1.12-1.39 (m, 6H, cyclohexyl), 1.07 (d, J = 6.46 Hz, 3H, CHMeMe'), 0.63-1.02 (m, 5H, cyclohexyl), 0.43 (m, 1H, cyclohexyl), 0.30 (m, 1H, cyclohexyl), 0.01 (d, J = 6.84 Hz, 3H, CHMeMe').

[0270] Example 4. Synthesis of Complex 4 (Cat ID = 4)

[0271]

[0272] A mixture of 200 mg (0.255 mmol) of intermediate A and 31 mg (0.260 mmol) of phenyl isocyanate in 15 ml of dichloromethane was stirred at room temperature for 5 min. Afterwards, the solvent was evaporated and the residue was washed with 2 x 15 ml of hexane and dried in vacuo. This procedure gave 180 mg (78%) of complex 4 as a white solid.

[0273] C 42 H 44 Anal. Calcd. for Cl2HfN4OS: C, 55.91; H, 4.92; N, 6.21. Found: C, 56.24; H, 5.17; N, 6.08.

[0274] 1 H NMR (CD2Cl2): δ7.72 (m, 1H, 7-H, in benzothiophene), 7.24 (m, 2H, 5,6-H, in benzothiophene), 7.11-7.17 (m, 3H, 2,4,6-H, in Ph-N=C), 7.04-7.07 (m, 2H, 3,5-H, in 2,6-diisopropylphenyl), 6.92 (m, 2H, 5,6-H, in benzothiophene). m, 1H, 4-H, in 2,6-diisopropylphenyl), 6.86, (m, 1H, 5-H, in imidazole), 6.83 (m, 1H, 3-H, in mesityl), 6.60 (m, 1H, 5-H, in mesityl), 6.48 (m, 2H, 3,5-H, in Ph-N=C), 6.08 (s, 1H, mesityl- CH), 3.45 (m, 1H, CHMe2), 3.07 (s, 3H, NMe, in imidazole), 3.02 (m, 1H, CHMe2), 2.72 (s, 3H, 2-Me, in benzothiophene), 2.21 (s, 3H, 2-Me, in mesityl), 2.17 (s, 3H, 6-Me, in mesityl), 1.43 (s, 3H, 4-Me, in mesityl), 1.16 (d, J = 6.65 Hz, 3H, CHMeMe'), 0.89 (d, J = 6.85 Hz, 3H, CHMeMe'), 0.74 (d, J = 6.65 Hz, 3H, CHMeMe'), 0.09 (d, J = 6.65 Hz, 3H, CHMeMe').

[0275] 13 C{ 1 H}NMR (CD2Cl2): δ179.47, 159.09, 148.52, 146.06, 145.49, 144.93, 144.15, 139.4 3, 139.36, 138.80, 138.44, 138.28, 132.90, 132.66, 131.64, 130.01, 129.26, 126. 96, 126.73, 126.14, 124.97, 124.89, 124.00, 123.94, 123.80, 123.55, 122.25, 65.50, 34.07, 28.34, 28.30, 27.53, 25.82, 25.14, 24.84, 22.22, 21.39, 20.72, 17.04.

[0276] Example 5. Synthesis of Complex 5 (Cat ID = 5)

[0277]

[0278] A mixture of 200 mg (0.255 mmol) of intermediate A and 18 mg (0.261 mmol) of isobutyronitrile in 15 ml of dichloromethane was stirred at room temperature for 5 min. Afterwards, the solvent was evaporated and the residue was washed with 2 x 15 ml of hexane and dried in vacuo. This procedure gave 163 mg (75%) of complex 5 as a white solid.

[0279] C 39 H 46 Anal. Calcd. for Cl2HfN4S: C, 54.96; H, 5.44; N, 6.57. Found: C, 55.25; H, 5.30; N, 6.43.

[0280] 1 H NMR (CD2Cl2): δ7.79 (m, 1H, 5-H, in benzothiophene), 7.37 (m, 1H, 7-H, in benzothiophene), 7.30 (m, 1H, 6-H, in benzothiophene), 7.13-7.21 (m, 2H, 3,5-H, in 2,6-diisopropylphenyl), 6.92 (m, 1H, 4-H, in 2,6-diisopropylphenyl), 6 .77 (m, 1H, 3-H, in mesityl), 6.76 (s, 1H, 5-H, in imidazole), 6.61 (s, 1H, 3-H, in mesityl), 6.05 (s, 1H, mesityl-CH), 3.80 (m, 1H, N=CCHMe2), 3.37 (m, 1H, CHMe2), 3.21 (m, 1H, CHMe2), 3.10 (s, 3H, NMe, in imidazole), 2.42 (s, 3H, 2-Me, in benzothiophene), 2.16, (s, 3H, 2-Me, in mesityl), 2.09 (s, 3H, 6-Me, in mesityl), 1.65 (s, 3H, 4-Me, in mesityl), 1.50 (d, J = 6.88 Hz, 3H, CHMeMe'), 1.4 0(d, J=6.69Hz, 3H, CHMeMe'), 1.22 (d, J=6.48Hz, 3H, N=CCHMeMe'), 1,13 (d, J=6.69Hz , 3H, CHMeMe'), 0.83 (d, J=6.89Hz, 3H, N=CCHMeMe'), 0.18 (d, J=6.69Hz, 3H, CHMeMe').

[0281] 13 C{ 1H} NMR (CD2Cl2): δ183.34, 157.61, 148.49, 146.11, 145.91, 143.52, 142.15, 139. 50, 139.01, 138.92, 138.45, 136.96, 132.81, 132.57, 131.28, 129.86, 126.51, 12 4.80, 123.86, 123.59, 123.49, 123.37, 122.96, 122.51, 65.96, 39.30, 33.51, 28.70, 28.07, 26.72, 26.61, 25.41, 22.35, 21.80, 20.71, 20.55, 20.28, 20.11, 15.84.

[0282] Polymerization Example

[0283] Solutions of the procatalysts (complexes 1 to 5, prepared as above) were prepared using toluene (ExxonMobil Chemical-anhydrous, stored in N2) (98%). The procatalyst solution was typically 0.5 mmol / L. Solvents, polymerization grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and filtered through columns connected in series: two 500 cc Oxyclear cylindrical cans in series, from Labclear (Oakland, Calif.), followed by two cans in series filled with dry Molecular sieves (8-12 mesh; Aldrich Chemical Company) and two 500 cc columns in series filled with dry A 500 cc column of molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0284] 1-Octene (98%) (Aldrich Chemical Company) was dried by stirring with NaK overnight and then filtered through basic alumina (Aldrich Chemical Company, Brockman Basic 1).

[0285] Polymerization grade ethylene was used and further purified by passing it through a series of columns: 500 cc Oxyclear cylindrical cans from Labclear (Oakland, Calif.) were then filled with dry A 500 cc column of molecular sieves (8-12 mesh; Aldrich Chemical Company) and a column filled with dry A 500 cc column of molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0286] Polymer grade propylene was used and further purified by passing it through a series of columns: 2250cc Oxiclear cylindrical cans from Labclear, then filled with A 2250 cc column of molecular sieves (8-12 mesh; Aldrich Chemical Company) was then connected in series to form a column filled with molecular sieves (8-12 mesh; Aldrich Chemical Company), a 500 cc column packed with Selexsorb CD (BASF) and finally a 500 cc column packed with Selexsorb COS (BASF).

[0287] Activation of the procatalyst was performed by methylaluminoxane (MAO, 10 wt% in toluene, Albemarle Corp.). MAO was used as a 0.5 wt% or 0.75 wt% solution in toluene. The micromoles of MAO reported in the experimental section are based on the micromoles of aluminum in MAO. The formula weight of MAO is 58.0 g / mole.

[0288] Reactor Description and Preparation:

[0289] The polymerization was carried out in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (the internal volume of the reactor was 23.5 mL for C2 and C2 / C8 experiments; 22.5 mL for C3 experiments), a septum inlet, regulated nitrogen, ethylene and propylene supplies and equipped with a disposable PEEK mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours and then at 25°C for 5 hours.

[0290] Ethylene polymerization (PE) or ethylene / 1-octene copolymerization (EO):

[0291] The reactor was prepared as described above and then purged with ethylene. For experiments with MAO activation, toluene, 1-octene (100 μL when used) and activator (MAO) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (80°C) and ethylene was added to process pressure (75 psig = 618.5 kPa or 200 psig = 1480.3 kPa) while stirring at 800 RPM. The precatalyst solution was then added to the reactor via syringe under process conditions. Ethylene was allowed to enter (by using a computer-controlled solenoid valve) the reactor during polymerization to maintain the reactor gauge pressure (+ / -2 psig). The reactor temperature was monitored and typically maintained within + / -1°C. The polymerization was stopped by adding approximately 50 psi O2 / Ar (5 mol% O2) gas mixture to the reactor for approximately 30 seconds. After a predetermined cumulative amount of ethylene had been added or a maximum polymerization time of 30 minutes, the polymerization was quenched. The reactor was cooled and vented. After the solvent was removed in vacuo, the polymer was isolated. The final conversion of ethylene added / consumed (quench value in psi) and the quench time for each experiment are reported in Tables 1 (PE) and 2 (EO). The reported yields include the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr).

[0292] Propylene polymerization:

[0293] The reactor was prepared as described above, then heated to 40°C and then purged with propylene gas at atmospheric pressure. For experiments with MAO activation, toluene, MAO and liquid propylene (1.0 mL) were added via a syringe. The reactor was then heated to the process temperature (70°C or 100°C) while stirring at 800 RPM. With the reactor under process conditions, the precatalyst solution was added via a syringe. The reactor temperature was monitored and typically maintained within + / -1°C. The polymerization was stopped by adding approximately 50 psi O2 / Ar (5 mol % O2) gas mixture to the reactor for approximately 30 seconds. The polymerization was quenched based on a predetermined pressure loss of approximately 8 psi or a maximum polymerization time of 30 minutes. The reactor was cooled and vented. After the solvent was removed by vacuum, the polymer was isolated. The quenching time (s) and quenching value (psi) for each experiment are reported in Table 3. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr).

[0294] Polymer characterization

[0295] For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, from Sigma-Aldrich) containing 2,6-dibutyl-4-methylphenol (BHT, 99%, from Aldrich) at 165°C in a shaking oven for approximately 3 hours. Typical concentrations of polymer in solution were 0.1-0.9 mg / mL with a BHT concentration of 1.25 mg BHT / mL of TCB. Samples were cooled to 135°C for testing.

[0296] High temperature size exclusion chromatography was performed using an automated "Fast GPC" system, as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molar weight distribution (MWD = Mw / Mn), sometimes referred to as the polydispersity (PDI) of a polymer, were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Set SM-10: Mp (peak Mw) 5000-3,390,000). Using three Polymer Laboratories: PL Gel 10 μm Mixed B 300x7.5 mm columns in series, the sample (250 μL of polymer solution in TCB injected into the system) was run at an eluent flow rate of 2.0 mL / min (135°C sample temperature, 165°C oven / column). No column spreading calibration was used. A 10 μm HPLC-MS / MS column available from Symyx Technologies was used. Quantitative analysis was performed using the Automation Studio software or the Automation Studio software available from Freeslate. The molecular weights obtained were relative to linear polystyrene standards. The molecular weight quantitative data are reported in Tables 1, 2 and 3.

[0297] Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The sample was pre-tempered at 220°C for 15 minutes and then cooled to room temperature overnight. The sample was then heated to 220°C at a rate of 100°C / min and then cooled at a rate of 50°C / min. The melting point was collected during the heating period. The results are reported in Tables 1, 2 and 3 as Tm (°C).

[0298] Samples for IR analysis were prepared by depositing stabilized polymer solutions onto silanized disks (Part No. S10860, Symyx). In this way, approximately 0.12-0.24 mg of polymer was deposited into the disk chamber. The samples were then analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with a Pikes' MappIR specular reflectance sample accessory. -1 The spectral range was covered by 32 scans at a resolution of 5000 cm -1 -500cm -1 spectrum.

[0299] For ethylene-1-octene copolymers, the -1 The methyl deformation band is used to determine the wt% copolymer. The peak height of this band is determined by the peak at about 4321 cm -1 The combination of the and fold spectra leads to normalization, which corrects for path length differences. The normalized peak heights are compared with those from 1 A separate calibration curve for the H NMR data was correlated to predict the octene content of the wt% copolymers in the concentration range of about 2-35 wt%. Typically, R values ​​of 0.98 or greater were achieved. 2 These figures are reported in Table 2 under the heading C8 wt%. Values ​​reported below 4.1 wt% are outside the calibration range.

[0300] The polymerization results are collected in Tables 1, 2 and 3 below. "Ex#" indicates the example number. "Cat ID" identifies the procatalyst used for the experiment. The corresponding number for the procatalyst is given in the synthetic experiment section. "Catalyst (μmol)" is the amount of procatalyst added to the reactor. "Yield" is the polymer yield and is not corrected for catalyst residues. "Quenching time (s)" is the actual duration of polymerization in seconds. The "Quenching value (psi)" for ethylene-based polymerization is the set maximum ethylene uptake (conversion) for the experiment. If the polymerization quenching time is 30 minutes or less, the polymerization occurs until the set ethylene uptake maximum value is reached. For propylene-based polymerization, the quenching value represents the pressure loss (conversion) of propylene during polymerization.

[0301] Table 1. Summary of conditions and polymer characterization data for ethylene homopolymerizations with complexes 1-5.

[0302]

[0303] Reactor conditions: procatalyst used at 0.025 μmol and activated with 500 equivalents of MAO; 80°C reactor temperature; 75 psid ethylene; 5.0 ml toluene; 800 rpm agitation speed; reactor quenched at 20 psid ethylene (quenching value) uptake or at a maximum time limit of 30 minutes.

[0304] Table 2. Summary of conditions and polymer characterization data for ethylene-octene copolymerizations with complexes 1-5.

[0305]

[0306] Reactor conditions: procatalyst used at 0.025 μmol and activated with 500 equivalents of MAO; 80°C reactor temperature; 100 μL 1-octene; 4.9 ml toluene; 800 rpm agitation speed; the reactor was quenched at 20 psid ethylene (quenching value) uptake for experiments with 75 psid ethylene or at 15 psid ethylene uptake for experiments with 200 psid ethylene or at a maximum time limit of 30 minutes.

[0307] * The wt% octene, less than 4.1 wt%, is outside the calibration range of the FTIR.

[0308] Table 3. Summary of conditions and polymer characterization data for propylene polymerizations with complexes 1-5.

[0309]

[0310] Procatalyst activated with 500 equivalents of MAO; 5.1 ml toluene; 1.0 ml C3; 800 rpm stirring speed; reactor quenched at 8 psid pressure loss (quench value) or at a maximum time limit of 30 minutes. Catalysts 4 and 5 produced isotactic polypropylene.

[0311] All documents described herein are incorporated herein by reference to the extent that they are not inconsistent with this article, including any priority documents and / or test procedures. It is apparent from the general description above and in the specific embodiments that, although the form of the present invention has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present invention. Therefore, the present invention is not intended to be limited thereto. Similarly, the term "comprising" is synonymous with the term "including". Similarly, whenever there is a transitional term "comprising" before a composition, an element or a group of elements, it is understood that it is also possible to imagine that the same composition or element group has a transitional term "essentially consisting of," "consisting of," "selected from or "is" before the composition, element or a group of elements, and vice versa.

Claims

1. Heterocyclic amino transition metal complex represented by formula (E): in: M is zirconium or hafnium; R 1 is selected from a phenyl group substituted with 0, 1, 2, 3, 4 or 5 substituents selected from an alkyl group having 1 to 10 carbons; R 2 -E(R 12 )(R 13 )-, where E is carbon, and R 12 and R 13 One of them is hydrogen and the other is 2,4,6-trimethylphenyl; L is an anionic leaving group, wherein the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group; L' is a neutral Lewis base; n is 1, 2 or 3; w is 0, 1, 2, or 3; Where n + w is not greater than 4; Y is CH2, CH(R 18 )、C(R 18 )2、C(O) or C(NR 18 ), where R 18 is selected from methyl, isopropyl and phenyl; Q 2 is a group that forms an anionic bond with M, wherein Q 2 The group is selected from O, S, CH2 or NR 17 , where each R 17 independently selected from isopropyl and cyclohexyl; E 2 NR 9 , where R 9 is methyl; E 3 is S; Each R 7 are independently selected from hydrogen and methyl; Each R 8 For hydrogen.

2. A heterocyclic amino transition metal complex represented by formula (H): M.R 1 , R 2 , L, L', n, w and R 18 、E 2 and E 3 , R 7 and R 8 As defined in claim 1; Y' is CH or C(R 18 );Q 2' is N.

3. The complex according to claim 1, wherein Q 2 is CH2, O, N(isopropyl) or N(cyclohexyl).

4. The complex according to claim 1, wherein Q 2 is N(isopropyl) or N(cyclohexyl) and Y is CH2.

5. The complex according to claim 1 or 2, wherein R 2 It is expressed by the following formula: Where R 12 and R 13 One of them is hydrogen and the other is 2,4,6-trimethylphenyl.

6. The complex of claim 2, wherein Q 2' is N and Y' is CH.

7. The complex of claim 1 or 2, wherein M is zirconium or hafnium, L is a hydrocarbon group containing 1 to 6 carbon atoms, n is 2, w is 0, and R 1 It is a 2,6-dialkylphenyl group containing 8 to 20 carbon atoms.

8. A catalyst system comprising an activator and the heterocyclic amino transition metal complex according to any one of claims 1 to 7.

9. The catalyst system of claim 8, wherein the activator comprises a non-coordinating anion and / or an aluminoxane.

10. The catalyst system of claim 8, wherein the catalyst system is supported.

11. A polymerization process for preparing polyolefins comprising contacting one or more olefin monomers with a catalyst system according to any one of claims 8 to 10 and recovering the olefin polymer.

12. The method of claim 11, wherein the monomer comprises ethylene.

13. The method of claim 11, wherein the monomer comprises propylene.

14. The method of claim 11, wherein the method is a solution method.

15. The process of claim 11, wherein the process is a gas phase or slurry process.

16. A polymerization process for preparing polyolefins comprising contacting one or more olefin monomers with a catalyst system comprising an activator and the heterocyclic amino transition metal complex of claim 1 or 2, wherein the process is a gas phase or slurry process.

17. The method of claim 16, wherein R 2 It is expressed by the following formula: Where R 12 and R 13 One of them is hydrogen and the other is 2,4,6-trimethylphenyl.

18. The method of claim 16, wherein Q 2' is N and Y' is CH or C(R 18 ).

19. The method of claim 16, wherein M is zirconium or hafnium, L is a hydrocarbon group containing 1 to 6 carbon atoms, n is 2, w is 0 and R 1 It is a 2,6-dialkylphenyl group containing 8 to 20 carbon atoms.

20. The method of claim 16, wherein Q 2 is CH2, O, N(isopropyl) or N(cyclohexyl).

21. The method of claim 16, wherein Q 2 is N(isopropyl) or N(cyclohexyl) and Y is CH2.

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