Process for the preparation of multimodal polyethylene

Abstract

This invention provides a method for preparing multi-peak ethylene polymers in a multi-stage process in the presence of a catalyst comprising a complex of formula (Ix); wherein each X is a σ-donor ligand; each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N, or S; L is a divalent bridge based on carbon, silicon, or germanium, wherein one or two skeletal atoms connect the ligand; M is Ti, Zr, or Hf; each R1 is the same or different, and is a straight-chain C 1‑10 Alkyl or straight-chain C 1‑10 Alkyl groups, each n is 0 to 3; each R2 is the same or different, and is C 1‑10 Alkyl, C 1‑10 Alkoxy or -Si(R)3 group; each R may be the same or different, and is optionally surrounded by 1 to 3 Cs. 1‑6 Alkyl-substituted C 1‑10 Alkyl or phenyl; each p is 0 to 3.

Description

Technical Field

[0001] This invention relates to a method for preparing multimodal polyethylene polymers using specific metallocene catalysts. The invention also relates to certain novel metallocene complexes and catalysts prepared therefrom. In particular, the catalysts used in the methods of this invention are catalysts that can be prepared in one-step or two-step catalyst preparation methods. Background Technology

[0002] In multi-stage polymerization for preparing multimodal polymers, different polymer components are continuously generated in each reactor. Typically, a lower molecular weight polymer component is prepared in the first reactor, and a higher molecular weight polymer component is produced in subsequent reactors. Composition control can also be applied to comonomer content, branching, comonomer type, etc.

[0003] Using multiple reactors with different conditions (physical and chemical) places stringent requirements on the catalyst system employed, as the same catalyst system is typically used for all stages of polymerization. The catalyst often transitions from the first stage to the second, thus needing to function at all stages of the reaction. The catalyst needs to remain stable throughout the multi-stage process. Furthermore, the catalyst needs to operate under the different conditions offered, particularly in slurry and gas-phase polymerization.

[0004] The catalyst must be able to produce polymers with both low and high molecular weights. The catalyst must perform well in ethylene homopolymerization and / or polymerization with low and high comonomer concentrations (see AR. Albania, F. Prades and D. Jeremic, Ed., Multimodal Polymers with Supported Catalysts, Springer 2019, ISBN 978-3-030-03474-0).

[0005] Ziegler-Natta catalysts have typically been used in multi-stage systems with excellent results, but they fail to produce highly specific polymer structures. On the other hand, single-site catalysts, such as metallocenes, can generate very controllable polymer structures. However, combining the advantages of single-site catalysis with multi-stage approaches has been very challenging because it is difficult to find metallocene catalysts with the desired performance, i.e.:

[0006] - The catalyst must have good kinetic stability because it must remain under different reaction conditions for an average of several hours to polymerize;

[0007] - The catalyst must be able to produce polymers with both low and high molecular weights in a single reactor;

[0008] - The catalyst must have high catalytic activity in all reactors.

[0009] Therefore, the inventors seek metallocene catalysts for multi-stage polymerization that can provide multi-peak polymers with, for example, the following characteristics:

[0010] -High molecular weight;

[0011] - High comonomer content;

[0012] -Good catalyst activity; and

[0013] - Capable of producing components with lower and higher molecular weights in a cascade (promoted by hydrogen as a molecular weight modifier).

[0014] It is particularly preferred if the catalyst has a higher activity in the gas phase than in the slurry phase, i.e., a high gas phase activity / slurry phase activity ratio, for example, 1.8 or higher. Therefore, it is highly preferred if the catalyst has a higher activity in the gas phase than in the slurry phase, for example, a gas phase activity / slurry phase activity ratio of 1.8 to 10, especially 2 to 8, and more preferably 2.2 to 6.

[0015] Surprisingly, certain bridging dicyclopentadienyl complexes with heterocyclic substituents such as furan groups have been found to provide the desired properties, especially when supported on a support.

[0016] In particular, the complexes of the present invention exhibit enhanced activity with advanced molecular weight capability and excellent comonomer incorporation ability. When H2 is added during polymerization, M can be controlled... w While maintaining good catalyst activity, polymer morphology, and other key polymer properties, these catalysts are highly favored in Borstar multi-stage process settings due to their more stable kinetic profiles in the slurry phase, similar or higher activity in the gas phase, and, crucially, a much higher gas-to-slurry phase activity ratio.

[0017] Some of the metallocene catalysts used in this paper are known. US6326493 describes certain metallocene catalysts containing furanyl groups, but these catalysts have not been used to produce multimodal polyethylene polymers. Although this prior art discloses a large number of metallocene catalysts, it only illustrates the formation of unimodal polypropylene.

[0018] JP2016 / 183334 describes a multimodal polyethylene resin comprising two multimodal polyethylene resins (C) and (G). The multimodal polyethylene is prepared in a multi-stage process. Summary of the Invention

[0019] Therefore, from one perspective, the present invention provides a method for preparing multimodal polyethylene polymers, comprising:

[0020] (I) In a first stage, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized in the presence of a metallocene catalyst comprising:

[0021] (i) Complex of formula (I)

[0022]

[0023] Each X is a σ donor ligand;

[0024] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0025] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0026] M is Ti, Zr, or Hf;

[0027] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl, optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl; and / or

[0028] Two adjacent R 1 The groups, together with the atoms they are bonded to, form other rings, such as an indene ring with a Cp ring, which may optionally be substituted by up to four R3 groups;

[0029] Each R3 may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl, C 1-10 alkoxy or phenyl;

[0030] Each n is between 0 and 3;

[0031] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0032] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0033] Each p is between 0 and 3;

[0034] (ii) a co-catalyst of a compound containing a Group 13 element; and optionally...

[0035] (iii) Carrier;

[0036] To form a first polyethylene component (e.g., a lower molecular weight component);

[0037] (II) In the second stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form a second polyethylene component (e.g., a higher molecular weight component).

[0038] From another perspective, the present invention provides a method for preparing multimodal polyethylene polymers, comprising:

[0039] (I) In a first stage, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized in the presence of a racemic metallocene catalyst comprising:

[0040] (i) Complexes of formula (Ix)

[0041]

[0042] Each X is a σ donor ligand;

[0043] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0044] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0045] M is Ti, Zr, or Hf;

[0046] Each R1 is the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy;

[0047] Each n is between 0 and 3;

[0048] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0049] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0050] Each p is between 0 and 3;

[0051] (ii) a co-catalyst of a compound containing a Group 13 element; and optionally...

[0052] (iii) Carrier;

[0053] To form a first polyethylene component (e.g., a lower molecular weight component);

[0054] (II) In the second stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form a second polyethylene component (e.g., a higher molecular weight component).

[0055] Certain metallocene complexes are novel, forming other aspects of the invention. In another aspect, the invention provides metallocene complexes of formula (I').

[0056]

[0057] Each X is a σ donor ligand;

[0058] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0059] M is Ti, Zr, or Hf;

[0060] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0061] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl, optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl; and / or

[0062] Two adjacent R 1 The groups, together with the atoms they are bonded to, form other rings, such as an indene ring with a Cp ring, which may optionally be substituted by up to four R3 groups;

[0063] Each R3 may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl, C 1-10 alkoxy or phenyl;

[0064] Each n is between 0 and 3;

[0065] Each R2 may be the same or different, and is a -Si(RaRbRc) group;

[0066] Ra is arbitrarily divided by 1 to 3 Cs 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl;

[0067] Rb is arbitrarily divided by 1 to 3 Cs 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl;

[0068] Rc is arbitrarily divided by 1 to 3 Cs 1-6 Alkyl-substituted phenyl; and

[0069] Each p is 1 to 3.

[0070] From another perspective, the present invention provides metallocene complexes of formula (I”).

[0071]

[0072] Each X is a σ donor ligand;

[0073] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0074] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0075] M is Ti, Zr, or Hf;

[0076] Each R1 is the same or different, which is a branch C. 3-10 alkyl;

[0077] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0078] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0079] Each p is between 0 and 3.

[0080] From another perspective, the present invention provides metallocene complexes of formula (Ia).

[0081]

[0082] Each X is a σ donor ligand;

[0083] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0084] L is a (RdRe)Si group, (RdRe)Ge, or (RdRe)CH2;

[0085] Rd is C 1-10Alkyl, C 5-10 cycloalkyl, benzyl, or phenyl;

[0086] Re is C 2-10 alkenyl;

[0087] M is Ti, Zr, or Hf;

[0088] Each R1 is the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy;

[0089] Each n is between 0 and 3;

[0090] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0091] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0092] Each p is between 0 and 3.

[0093] From another perspective, the present invention provides metallocene complexes of formula (Ia').

[0094]

[0095] Each X is a σ donor ligand;

[0096] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0097] L is a (RdRe)Si group;

[0098] Rd is C 1-10 alkyl;

[0099] Re is C 2-10 alkenyl;

[0100] M is Ti, Zr, or Hf;

[0101] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl, optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl; and / or

[0102] Two adjacent R 1The groups, together with the atoms they are bonded to, form other rings, such as an indene ring with a Cp ring, which may optionally be substituted by up to four R3 groups;

[0103] Each R3 may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl, C 1-10 alkoxy or phenyl;

[0104] Each n is between 0 and 3;

[0105] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0106] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0107] Each p is between 0 and 3.

[0108] In another respect, the present invention provides the use of metallocene catalysts as defined above in the preparation of multimodal ethylene polymers in a method including a slurry phase step and a gas phase step.

[0109] definition

[0110] The following definitions are used throughout this specification.

[0111] Unless otherwise stated, the term "molecular weight" is used herein to refer to weight-average molecular weight M. w . Detailed Implementation

[0112] This invention relates to a method for preparing multimodal polyethylene polymers, as well as certain novel metallocene complexes and catalysts prepared therefrom.

[0113] Metallocene complexes

[0114] The metallocene catalyst complexes used in the methods of this invention can be symmetrical or asymmetrical. Asymmetry simply means that the two ligands forming the metallocene complex are different, i.e., each ligand carries a chemically distinct set of substituents. The term symmetry means that the two ligands in the metallocene complex are identical, i.e., they have the same substituent pattern.

[0115] The metallocene catalyst complexes of the present invention can be meso or racemic, or a mixture thereof. However, it is preferred if the metallocene catalyst complexes of the present invention are chiral racemic bridged dicyclopentadienyl metallocene complexes in their trans configuration. The metallocene complexes can be C2-symmetrical or C1-symmetrical. When they are C1-symmetrical, they still retain pseudo-C2 symmetry because they maintain C2 symmetry near the metal center, but not around the ligands. Depending on their chemical properties, meso and racemic enantiomer pairs (in the case of C2-symmetrical complexes) or trans and cis enantiomer pairs (in the case of C1-symmetrical complexes) are formed during the synthesis of the complexes. For the purposes of the present invention, racemic-trans refers to the two ligands being oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-cis refers to the two ligands being oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane.

[0116] Unless otherwise stated, the chemical formulas herein are intended to cover both cis and trans configurations. Preferred metallocene catalyst complexes are trans-configured or racemic.

[0117] In addition to racemic isomers, the metallocene catalysts of the present invention may also contain some meso or cis isomers. Due to the synthetic nature of metallocene complexes, these complexes may be produced in the form of mixtures. In such mixtures, there may be up to 60 mol% meso isomers, and therefore at least 40 mol% racemic isomers.

[0118] However, based on the overall weight of the complex, it is preferred if the content of the racemic isomer is 50 mol% or more, for example 60 mol% or more, especially 70 mol% or more, ideally 90 mol% or more.

[0119] The metallocene catalyst complexes of the present invention preferably comprise racemic-trans isomers. Therefore, ideally, at least 95 mol%, for example at least 98 mol%, and particularly at least 99 mol%, of the metallocene catalyst complexes are in the racemic-trans isomer form.

[0120] In the metallocene catalyst complexes of the present invention, the following are preferred. The complexes of the present invention may have the structure of formula (I):

[0121]

[0122] Each X is a σ donor ligand;

[0123] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0124] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0125] M is Ti, Zr, or Hf;

[0126] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl, optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl; and / or

[0127] Two adjacent R1 groups together with the atoms they are bonded to form other rings, such as an indene ring with the Cp ring, which may optionally be replaced by up to four R3 groups;

[0128] Each R3 may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl, C 1-10 alkoxy or phenyl;

[0129] Each n is between 0 and 3;

[0130] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0131] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0132] Each p is between 0 and 3.

[0133] The following preferred options apply to all general formulas in this document.

[0134] M is preferably Zr or Hf, and more preferably Zr.

[0135] Each X is an independent σ donor ligand. Therefore, each X can be the same or different, and is preferably a hydrogen atom, a halogen atom, a straight-chain or branched chain, or a cyclic or acyclic C atom. 1-20 -alkyl or C 1-20 -alkoxy group, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 -Arylalkyl.

[0136] In one embodiment, the X group may be a trialkylsilyl group, C 1-10 -alkoxy group, C 1-10 Alkoxy-C 1-10-alkyl- or amide group.

[0137] The term halogen includes fluorine, chlorine, bromine, and iodine groups, with chlorine groups being preferred.

[0138] The amide groups of interest are -NH2 and -NHC. 1-6 Alkyl or -N(C) 1-6 Alkyl)2.

[0139] More preferably, each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl, or benzyl.

[0140] More preferably, each X is independently a halogen atom, a straight-chain or branched C atom. 1-4 -alkyl or C 1-4 -alkoxy, phenyl, or benzyl.

[0141] Most preferably, each X is independently chlorine, benzyl, cyclohexyl or methyl.

[0142] Preferably, the two X groups are identical.

[0143] The most preferred options for the two X groups are two chlorides, two methyl groups, or two benzyl groups.

[0144] L is a bridge based on carbon, silicon, or germanium. There is one or two backbone connecting atoms between the two ligands, such as structures like ligand-C-ligand (one backbone atom) or ligand-Si-Si-ligand (two backbone atoms).

[0145] The bridging atom can carry other groups. For example, suitable bridging ligands L are selected from -R′2C-, -R′2C-CR′2-, -R′2Si-, -R′2Si-SiR′2-, and -R′2Ge-, wherein each R′ is independently a hydrogen atom or optionally contains one or more heteroatoms or fluorine atoms from groups 14-16 of the periodic table. 20 - A hydrocarbon group, or optionally two R′ groups together, can form a ring. In one embodiment, R′ can be an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms.

[0146] Heteratoms belonging to groups 14-16 of the periodic table include, for example, Si, N, O, or S.

[0147] Preferably, L is -R′2Si-, ethylene, or methylene.

[0148] In equation -R′2Si-, each R′ is preferably independently C1-C 20 -Hydrocarbon group. Therefore, the term C 1-20 - Hydrocarbon groups include C1-20 -alkyl, C 2-20 -Alkenyl, C 2-20 -Alynyl group, C 3-20 -cycloalkyl, C 3-20 -cycloalkenyl, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 -Arylalkyl groups or mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C is preferred. 1-20 -The hydrocarbon group is C 1-20 -alkyl, C 2-20 -Alkenyl, C 4-20 -cycloalkyl, C 5-20 -cycloalkyl-alkyl, C 7-20 -alkylaryl, C 7-20 -Arylalkyl or C 6-20 -Aryl.

[0149] In one embodiment, the formula -R′2Si- represents a silanediyl group, such as silane, silane, or 9-silanefluorene.

[0150] In one implementation, L is (RdRe)Si, and Rd is C. 1-10 Alkyl, C 5-10 -cycloalkyl, benzyl, or phenyl, Re is C 2-10 Alkenyl groups, for example, L is (RdRe)Si, and Rd is C. 1-4 Alkyl, cyclohexyl, benzyl, or phenyl, Re is C 4-8 Alkenyl. To avoid ambiguity, in the (RdRe)Si group, the Rd and Re groups are bonded to the Si atoms.

[0151] In one implementation, each R′ is different. If an R′ is C 1-10 Alkyl, such as C 1-4 Alkyl groups, especially methyl groups, have an R′ that is C. 2-10 alkenyl groups, such as C 4-8 An alkenyl group is preferred. It is even more preferred if the double bond is located at the end of the alkenyl group, away from the Si bridge. Most preferably, the bridge is =Si(CH3)(-CH2CH2CH2CH=CH2).

[0152] Preferably, the two R′ groups are identical. If R′ is C1-C... 10 A hydrocarbon group, or an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, is preferred. Preferably, the R′ group is methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 2-10 alkenyl, C 3-8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, more preferably, each R′ is independently a C1-C6-alkyl, C 2-10 alkenyl, C 5-6 -Cycloalkyl or phenyl, and most preferably, both R′ are methyl, or one is methyl and the other is cyclohexyl. Most preferably, the bridge is -Si(CH3)2-.

[0153] The Het groups may be the same or different, but are preferably the same. The Het group is a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N, or S. If N is present in the ring, it may contain H or C, depending on the ring structure. 1-6 alkyl.

[0154] Preferably, the Het group is monocyclic. Preferably, the Het group is heteroaromatic. Preferably, the Het group is a monocyclic heteroaromatic group. Preferably, the Het group is a 5- or 6-membered heteroaromatic ring or a heterocyclic structure.

[0155] Preferred Het groups include furanyl, tetrahydrofuranyl, thiophenyl, pyridyl, piperidinyl, or pyrroleyl.

[0156] It is preferred if the Het ring contains one heteroatom. It is preferred if the heteroatom is O or S, preferably O. It is most preferred if the Het is a furanyl group. It is preferred if the connection from the Het group to the cyclopentadienyl ring is located on a carbon adjacent to the heteroatom. It is preferred if the connection from the Cp group to the Het ring is located on a carbon adjacent to the linking group L.

[0157] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl (i.e., OBz), C 6-10 Aryl, OC 6-10 Aryl, optionally coated with 1 to 3 C 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl;

[0158] and / or

[0159] Two adjacent R1 groups, together with the atoms they are bonded to, form other rings, such as an indenyl ring with the Cp ring, which may optionally be composed of up to four R groups. s Group substitution;

[0160] However, if there is no fused ring, then the ligand comprising two cyclopentadienyl rings is preferred.

[0161] Each R1 is preferably optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-6 Alkyl, C 1-6 Alkoxy, benzyl, phenyl.

[0162] More preferably, R1 is C 1-6 Alkyl groups, such as methyl, ethyl, or tert-butyl.

[0163] In one implementation, R1 is a straight-chain C 1-6 alkyl.

[0164] The subscript "n" is preferably 1 or 2, i.e., it is preferred if the ring is substituted. If n is 2, it is preferred if R1 is methyl. If n is 1, it is preferred if R1 is t-Bu.

[0165] If n = 2, the R1 group is preferably adjacent. If n ≠ 2, the R1 group is preferably attached to the carbon adjacent to the bridge L and the next carbon.

[0166] If n = 1, then the R1 group is preferably not adjacent to the linking group L or the Het group.

[0167] Whether each R2 is the same or different is C 1-10 -alkyl, C 1-10 -alkoxy or -Si(R)3 group. If R2 is -Si(R)3 group, it is preferred.

[0168] Each R is independently and optionally divided by 1 to 3 Cs. 1-s Alkyl-substituted C 1-6 Alkyl or phenyl. Therefore, each R group can be the same or different.

[0169] The R group is preferably phenyl or C. 1-4 Alkyl groups, especially methyl or phenyl. In one embodiment, one R is phenyl, and the other R groups are C. 1-4 Alkyl groups, such as methyl groups. In another embodiment, all R groups are C10. 1-4 Alkyl groups. -SiPhMe2 or SiMe3 are preferred.

[0170] Preferably, p is 0 or 1, and more preferably p = 1.

[0171] If p is not 0, the R2 substituent is preferably located on a carbon atom adjacent to the heteroatom. Preferably, the R2 group is not bonded to the same carbon atom attached to the Cp ring. If the Het group is a furanyl group, preferably the Het ring is connected to the Cp ring and the Het group (if present) via two carbon atoms adjacent to O.

[0172] The coordination compound used in this invention preferably has formula (II):

[0173]

[0174] Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0175] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0176] L is -R′2C- or -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0177] M is Ti, Zr, or Hf;

[0178] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl, optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl; and / or

[0179] Two adjacent R1 groups together with the atoms they are bonded to form other rings, such as an indene ring with the Cp ring, which may optionally be replaced by up to four R3 groups;

[0180] Each R3 may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-6 Alkyl, C 1-6 alkoxy or phenyl;

[0181] Each n is between 0 and 3;

[0182] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0183] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0184] Each p is between 0 and 3.

[0185] Ideally, in equation (II), R1 is a straight-chain C 1-6 alkyl.

[0186] The coordination compound used in this invention preferably has formula (III):

[0187]

[0188] Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0189] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0190] L is -R′2C- or -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0191] M is Ti, Zr, or Hf;

[0192] Whether each R1 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy, benzyl, O-benzyl, optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted phenyl or optionally with 1 to 3 carbon atoms 1-6 Alkyl-substituted O-phenyl;

[0193] Each n is between 0 and 3;

[0194] Whether each R2 is the same or different is C 1-6 Alkyl, C 1-6 Alkoxy or -Si(R)3 group;

[0195] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-6 Alkyl or phenyl; and

[0196] Each p is between 0 and 3.

[0197] Ideally, in equation (III), R1 is a straight-chain C 1-6 alkyl.

[0198] The coordination compound used in this invention preferably has formula (IV):

[0199]

[0200] Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0201] Each Het is independently a monocyclic heteroaromatic group containing at least one heteroatom selected from O, N or S;

[0202] L is -R′2C- or -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0203] M is Ti, Zr, or Hf;

[0204] Whether each R1 is the same or different is C 1-6 Alkyl or C 1-6 Alkoxy;

[0205] Each n is between 0 and 3;

[0206] Whether each R2 is the same or different is C 1-6 Alkyl, C 1-6 Alkoxy or -Si(R)3 group;

[0207] Each R is independently and optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-6 Alkyl or phenyl; and

[0208] Each p is between 0 and 3.

[0209] Ideally, in equation (IV), R1 is a straight-chain C 1-6 alkyl.

[0210] The coordination compound used in this invention preferably has formula (V):

[0211]

[0212] Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0213] Each Het is independently a monocyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O or S;

[0214] L is -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0215] M is Ti, Zr, or Hf;

[0216] Whether each R1 is the same or different is C 1-6 Alkyl or C 1-6 Alkoxy;

[0217] Each n is between 1 and 2;

[0218] Whether each R2 is the same or different is C 1-6 Alkyl, C 1-6 Alkoxy or -Si(R)3 group;

[0219] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0220] Each p is between 0 and 1.

[0221] Ideally, in equation (V), R1 is a straight-chain C 1-6 alkyl.

[0222] The coordination compound used in this invention preferably has formula (VI):

[0223]

[0224] Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0225] Each Het is independently a monocyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O or S;

[0226] L is -R′2Si-, where each R′ is independently C. 1-10 Alkyl, C 3-8 cycloalkyl or C 2-10 Alkenyl group.

[0227] M is Ti, Zr, or Hf;

[0228] Whether each R1 is the same or different is C 1-6 alkyl;

[0229] Each n is between 1 and 2;

[0230] Each R2 may be the same or different, and is a -Si(R)3 group;

[0231] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0232] Each p is between 0 and 1.

[0233] Ideally, in equation (VI), R1 is a straight-chain C 1-6 alkyl.

[0234] The coordination compound used in this invention preferably has formula (VII):

[0235]

[0236] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0237] L is a divalent bridge based on carbon, silicon, or germanium, where one or two framework atoms connect to a ligand, such as -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0238] Whether each R1 is the same or different is C 1-6 alkyl;

[0239] Each n is between 0 and 3;

[0240] Whether each R2 is the same or different is C 1-6 Alkyl or -Si(R)3 groups;

[0241] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0242] Each p is between 0 and 3.

[0243] Ideally, in equation (VII), R1 is a straight-chain C 1-6 alkyl.

[0244] The coordination compound used in this invention preferably has formula (VIII).

[0245]

[0246] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0247] L is a divalent bridge based on carbon, silicon, or germanium, where one or two framework atoms connect to a ligand, such as -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0248] Whether each R1 is the same or different is C1-6 alkyl;

[0249] Each n is between 1 and 2;

[0250] R2 is a -Si(R)3 alkyl group;

[0251] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl;

[0252] Each p is 1.

[0253] Ideally, in equation (VIII), R1 is a straight-chain C 1-6 alkyl.

[0254] The coordination compound used in this invention preferably has formula (IX).

[0255]

[0256] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0257] L is Me2Si- or (Me)C 2-10 -AlkenylSi;

[0258] Whether each R1 is the same or different is C 1-6 Alkyl groups, such as methyl or t-Bu;

[0259] Each n is between 1 and 2;

[0260] R2 is a -Si(R)3 alkyl group;

[0261] Whether each R is the same or different, it is C 1-6 Alkyl or phenyl;

[0262] Each p is 1; for example, it has the formula (IX′).

[0263]

[0264] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0265] L is Me2Si- or (Me)C 2-10 -AlkenylSi;

[0266] Whether each R1 is the same or different is C 1-6Alkyl groups, such as methyl or t-Bu;

[0267] Each n is between 1 and 2;

[0268] R2 is a -Si(R)3 alkyl group;

[0269] Whether each R is the same or different, it is C 1-6 Alkyl or phenyl.

[0270] Ideally, in equation (XI or XI′), R1 is a straight-chain C 1-6 alkyl.

[0271] As mentioned earlier, some coordination compounds are novel. Preferred novel coordination compounds are those of formula (X).

[0272]

[0273] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0274] L is a divalent bridge based on carbon, silicon, or germanium, where one or two framework atoms connect to a ligand, such as -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0275] M is Ti, Zr, or Hf;

[0276] Each Het is independently a monocyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0277] Whether each R1 is the same or different is C 1-10 alkyl;

[0278] Each n is between 1 and 3;

[0279] Each R2 may be the same or different, and is a Si(RaRbRc) group;

[0280] Ra is C 1-6 alkyl;

[0281] Rb is C 1-6 alkyl;

[0282] Rc is arbitrarily divided by 1 to 3 Cs 1-6 Alkyl-substituted phenyl; and

[0283] Each p is 1 to 3; for example, it has the formula (X′).

[0284]

[0285] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0286] L is a divalent bridge based on carbon, silicon, or germanium, where one or two framework atoms connect to a ligand, such as -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0287] Whether each R1 is the same or different is C 1-10 alkyl;

[0288] Each n is between 1 and 3;

[0289] Each R2 may be the same or different, and is a -Si(RaRbRc) group;

[0290] Ra is C 1-6 alkyl;

[0291] Rb is C 1-6 alkyl;

[0292] Rc is arbitrarily divided by 1 to 3 Cs 1-6 Alkyl-substituted phenyl groups.

[0293] Ideally, in equation (X or X′), R1 is a straight-chain C 1-6 alkyl.

[0294] More preferred new complexes are those of formula (XI).

[0295]

[0296] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0297] L is a divalent bridge based on carbon, silicon, or germanium, where one or two framework atoms connect to a ligand, such as -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0298] Each Het is independently a monocyclic heteroaromatic group containing at least one heteroatom selected from O, N or S;

[0299] M is Ti, Zr, or Hf;

[0300] Each R1 is the same or different, which is a branch C. 3-10 alkyl;

[0301] Each R2 may be the same or different, and is a -Si(R)3 group;

[0302] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0303] Each p is 1, for example, having equation (XI′).

[0304]

[0305] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0306] L is a divalent bridge based on carbon, silicon, or germanium, where one or two framework atoms connect to a ligand, such as -R′2Si-, where each R′ is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl;

[0307] Each R1 is the same or different, which is a branch C. 3-10 alkyl;

[0308] Each R2 may be the same or different, and is a -Si(R)3 group;

[0309] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl.

[0310] Even more preferred novel complexes are those of formula (XII).

[0311]

[0312] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0313] Each Het is independently a monocyclic heteroaromatic group containing at least one heteroatom selected from O, N or S;

[0314] L is a (RdRe)Si group;

[0315] Rd is C 1-10 alkyl;

[0316] Re is C 2-10 alkenyl;

[0317] M is Ti, Zr, or Hf;

[0318] Whether each R1 is the same or different is C 1-10 alkyl;

[0319] Each n is between 1 and 3;

[0320] Each R2 may be the same or different, and is a -Si(R)3 group;

[0321] Each R is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0322] Each p is between 0 and 3, for example, having equation (XII′).

[0323]

[0324] Each X is a σ donor ligand, for example, each X is independently a hydrogen atom, a halogen atom, a carbon atom, etc. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl;

[0325] L is a (RdRe)Si group;

[0326] Rd is C 1-10 alkyl;

[0327] Re is C 2-10 alkenyl;

[0328] Whether each R1 is the same or different is C 1-10 alkyl;

[0329] Each n is between 1 and 3;

[0330] Each R2 may be the same or different, and is a -Si(R)3 group;

[0331] Each R is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl.

[0332] Ideally, in equation (XII or XII′), R1 is a straight-chain C 1-6 alkyl.

[0333] The highly preferred complex is

[0334]

[0335] co-catalyst

[0336] In order to form an active catalytic substance, a co-catalyst known in the art is usually required.

[0337] According to the present invention, there is a need for co-catalysts containing Group 13 elements, such as boron-containing co-catalysts or Al-containing co-catalysts. Most preferably, the aluminoxane co-catalyst is used in combination with a metallocene catalyst complex as defined above.

[0338] The aluminoxane co-catalyst can be one of formula (A):

[0339]

[0340] Where n is between 6 and 20, and R has the following meanings.

[0341] Aluminoxanes are formed through the partial hydrolysis of organoaluminum compounds, such as those with the formulas AlR3, AlR2Y, and Al2R3Y3, where R can be, for example, C1-C2. 10 -alkyl, preferably C1-C5-alkyl, or C3-C 10 -Cycloalkyl, C7-C 12 -arylalkyl or -alkylaryl and / or phenyl or naphthyl, wherein Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 -alkoxy, preferably methoxy or ethoxy. The resulting oxyaluminoxane is usually not a pure compound, but a mixture of oligomers of formula (A).

[0342] The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxane used as a cocatalyst according to the present invention is not a pure compound due to its preparation method, the molar concentration of the aluminoxane solution in the following text is based on its aluminum content.

[0343] Boron-containing cocatalysts can also be used, optionally in combination with aluminum oxane cocatalysts. Boron-containing cocatalysts of interest include those of formula (B).

[0344] BY3

[0345] (B)

[0346] Wherein Y may be the same or different, and is a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, an aryl group having 6 to about 15 carbon atoms, an alkylaryl group, an arylalkyl group, a haloalkyl group, or a haloaryl group, or fluorine, chlorine, bromine, or iodine. Preferred examples of Y are fluorine, trifluoromethyl, or aromatic fluorinated groups, such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, tri(4-fluorophenyl)borane, tri(3,5-difluorophenyl)borane, tri(4-fluoromethylphenyl)borane, tri(2,4,6-trifluorophenyl)borane, tri(pentafluorophenyl)borane, tri(3,5-difluorophenyl)borane, and / or tri(3,4,5-trifluorophenyl)borane.

[0347] Tris(pentafluorophenyl)borane is particularly preferred.

[0348] However, borates, i.e. compounds containing borates, are preferred.

[0349] These compounds typically contain anion of formula (C):

[0350] (Z)4B -

[0351] (C)

[0352] Wherein Z is an optionally substituted phenyl derivative, and the substituent is a halogenated -C 1-6 -Alkyl or haloyl group. Preferred options are fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0353] Such ionic cocatalysts preferably contain weakly coordinating anions, such as tetra(pentafluorophenyl)borate or tetra(3,5-di(trifluoromethyl)phenyl)borate.

[0354] Suitable cationic counterions include triphenylcarbium and are protonated amines or aniline derivatives, such as methylammonium, phenylammonium, dimethylammonium, diethylammonium, N-methylphenylammonium, diphenylammonium, N,N-dimethylphenylammonium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylphenylammonium, or p-nitro-N,N-dimethylphenylammonium.

[0355] Preferred ionic compounds that can be used according to the present invention include:

[0356] Tributylammonium tetra(pentafluorophenyl)borate,

[0357] Tributylammonium tetra(trifluoromethylphenyl)borate

[0358] Tributylammonium tetra(4-fluorophenyl)borate,

[0359] N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate,

[0360] N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate,

[0361] N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate,

[0362] N,N-Di(propyl)ammonium tetra(pentafluorophenyl)borate,

[0363] Di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate,

[0364] Triphenylcarbium tetra(pentafluorophenyl)borate,

[0365] Or ferrocene tetra(pentafluorophenyl)borate.

[0366] Triphenylcarbium tetra(pentafluorophenyl)borate is preferred.

[0367] N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate,

[0368] N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate or

[0369] N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate.

[0370] Therefore, the preferred borates used in this invention contain a triphenylcarbazide radical, i.e., a triphenylcarbazide ion. Consequently, the use of Ph3CB(PhF5)4 and its analogues is particularly favored.

[0371] The appropriate amount of co-catalyst is well known to those skilled in the art.

[0372] Preferably, the amount of co-catalyst is selected to achieve a molar ratio below the defined range.

[0373] The molar ratio of boron (B) to metallocene metal ions (M) (preferably zirconium) can be in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, and especially 0.3:1 to 5:1 mol / mol.

[0374] Even more preferably, the molar ratio of boron (B) to metallocene metal ions (M) (preferably zirconium) is 0.3:1 to 3:1.

[0375] The molar ratio of Al in the aluminoxane to the metal ion (M) (preferably zirconium) in the metallocene, Al / M, can be in the range of 1:1 to 2000:1 mol / mol, preferably 10:1 to 1000:1, and more preferably 50:1 to 600:1 mol / mol.

[0376] catalyst system

[0377] The metallocene complexes described above are used in combination with suitable cocatalysts as described above.

[0378] The catalyst system of the present invention can be used in a solid but unsupported form according to the scheme in WO03 / 051934. The catalyst system of the present invention is preferably used in a solid supported form. The particulate support material used is preferably an inorganic porous support, such as silica, alumina, or mixed oxides, such as silica-alumina, especially silica.

[0379] Silica carrier is preferred.

[0380] Particularly preferably, the carrier is a porous material, allowing the complex to be loaded into the pores of the particulate carrier, for example using methods similar to those described in WO94 / 14856, WO95 / 12622, WO2006 / 097497 and EP1828266.

[0381] The average particle size of the carrier, such as a silica carrier, can typically be 10 to 100 μm.

[0382] The carrier, such as a silica carrier, can have an average pore size in the range of 10 to 100 nm and a pore volume of 1 to 3 mL / g.

[0383] Examples of suitable support materials are, for example, ES757 manufactured and marketed by PQ, Sylopol 948 manufactured and marketed by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech. The support may optionally be calcined prior to its use in catalyst preparation to achieve optimal silanol group content.

[0384] The catalyst may contain 5 to 500 μmol of transition metal per gram of support (e.g., silica), such as 10 to 100 μmol, and 3 to 15 mmol of Al per gram of support (e.g., silica).

[0385] One-step preparation of catalysts

[0386] To prepare the catalyst used in this invention, it is necessary to combine a metallocene complex, a co-catalyst, and a support. In a preferred embodiment, the combination of all these components occurs in a single step.

[0387] Therefore, it is preferable to prepare the solution in a temperature range of -20 to 75°C, preferably 10 to 60°C, wherein the metallocene complex and the co-catalyst are combined in a solvent, typically under an inert atmosphere, with a pre-contact time ranging from just a few minutes to several days. Preferred solvents are hydrocarbons, such as toluene and xylene.

[0388] The resulting solution is then added to a carrier, such as a silica carrier.

[0389] It is preferred to use a "dry mix", "pore fill" or "initial wet" impregnation method, wherein the total volume of the impregnation solution is close to (e.g., in the range of slightly below to slightly above) the pore volume of the dry carrier.

[0390] The volume of the impregnating liquid may be much larger than the pore volume of the carrier, causing the mixture to appear as a slurry or suspension by the time the liquid is added to the dried carrier. This is less than desirable.

[0391] Alternatively, the carrier can be suspended in a suitable hydrocarbon solvent before adding the impregnation solution, but this is not preferred.

[0392] The resulting crude catalyst is then gently mixed and allowed to stand before drying. A washing step may be used if necessary.

[0393] The solution of the metallocene complex and the co-catalyst is preferably added dropwise to the support. The contact step is carried out at a temperature of -20 to 60°C, ideally between 10 and 30°C. This step is typically exothermic.

[0394] Therefore, from one perspective, the present invention provides a method for preparing multimodal polyethylene polymers, comprising:

[0395] (I) Contacting a solid support with a co-catalyst containing a group 13 element and a solution of a racemic metallocene complex of formula (Ix).

[0396]

[0397] Each X is a σ donor ligand;

[0398] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0399] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0400] M is Ti, Zr, or Hf;

[0401] Each R1 is the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy

[0402] Each n is between 0 and 3;

[0403] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0404] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0405] Each p is between 0 and 3;

[0406] To form a supported catalyst;

[0407] (II) In the first stage, in the presence of the supported catalyst, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized to form a first polyethylene component (e.g., a lower molecular weight component).

[0408] (III) In the second stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form a second polyethylene component (e.g., a higher molecular weight component).

[0409] When we prepare supported catalysts using this one-step method, we find that we can observe some surprising technical effects.

[0410] • Compared to classic non-bridged bis-Cp metallocene catalysts (prepared in the same manner), such as those based on bis(1-methyl-3-n-butylcyclopentadienyl)zirconia, the preferred furanyl-substituted metallocene catalysts exhibit up to two times the activity in the slurry phase and up to five times the activity in the gas phase.

[0411] The catalysts of this invention exhibit high activity in the gas phase.

[0412] • Compared with classic non-bridging bis-Cp metallocene catalysts (regardless of the catalyst preparation method), such as those based on bis(1-methyl-3-n-butylcyclopentadienyl)zirconia, the preferred furanyl-substituted metallocene catalysts exhibit significantly higher comonomer response.

[0413] • Preferred furanyl-substituted metallocene catalysts have much higher molecular weight capabilities.

[0414] • Adjusting the MFR with hydrogen gas without causing a significant loss of catalyst activity.

[0415] • Excellent polymer particle morphology (good polymer packing density)

[0416] • The density of the polymer is significantly reduced.

[0417] Stable slurry phase dynamics curves are suitable for multi-stage methods.

[0418] • The level of long-chain branching in copolymers is relatively low.

[0419] The key here is to combine comonomer sensitivity, molecular weight capability, and higher overall multi-stage polymerization activity with, crucially, a higher gas-to-slurry phase activity ratio.

[0420] Two-step preparation of catalysts

[0421] In the second embodiment, the contact between the support, the metallocene complex, and the cocatalyst is carried out in a stepwise manner. In the first step, the support, such as a silica support, is contacted with the cocatalyst. Therefore, typically a solution of the cocatalyst in a solvent is contacted with a support suspended in the solvent. The solvent of interest is also a hydrocarbon solvent, such as toluene and xylene. The ideal temperature for carrying out this contact step is room temperature or lower, for example, -10 to 25°C. Any step can be carried out under an inert atmosphere.

[0422] Once the co-catalyst is allowed to impregnate the carrier (e.g., after stirring the mixture for a period of time), it is preferable to heat the system to at least 70°C, for example, 70 to 120°C, while continuing the impregnation process. However, impregnation can of course be carried out at any temperature, such as ambient temperature.

[0423] Once impregnation is complete, allow the system to settle (preferably while still at elevated temperature) and remove the supernatant.

[0424] The impregnated carrier can then be washed with more solvent, ideally again at an elevated temperature, before removing the solvent. The washing steps can be repeated, perhaps each time at a lower temperature than the previous one, followed by drying.

[0425] The resulting dried impregnated support (which is also the activated support from here on, such as SiO2 / MAO) is then contacted with the metallocene complex. This can be conveniently provided as a solution, ideally in the same solvent used to prepare the impregnated support. The metallocene complex is allowed to impregnate the support before the solvent is removed to leave the dried catalyst.

[0426] In either step of the two-step process, it is possible to use a "dry mixing," "pore-filling," or "initial wetting" impregnation method, wherein the total volume of the impregnation solution is close to (e.g., in the range of slightly below to slightly above) the pore volume of the dry support or the dry activated support. Particularly preferred is that this "dry mixing" is used in the second step of the two-step catalyst preparation process.

[0427] In the second step of the two-step catalyst preparation process, the volume of the impregnating liquid may be much larger than the pore volume of the dried activated support, resulting in the mixture appearing as a slurry or suspension at the end of the liquid addition step. This is less than desirable.

[0428] In the second step of the two-step catalyst preparation method using an activated support, the support can also be suspended in a suitable hydrocarbon solvent before adding the impregnation solution, but this is not preferred.

[0429] A washing step can be performed again. This second step can be carried out at a temperature of -10 to 90°C, preferably at a temperature of 20 to 60°C.

[0430] Therefore, from one perspective, the present invention provides a method for preparing multimodal polyethylene polymers, comprising:

[0431] (I) Contact a solid support with a solution of a cocatalyst containing a compound of Group 13 elements to form a cocatalyst-impregnated support;

[0432] (II) Contact the catalyst-impregnated support with the racemic metallocene complex of formula (Ix).

[0433]

[0434] Each X is a σ donor ligand;

[0435] Each Het is independently a monocyclic or polycyclic heteroaromatic group or heterocyclic group containing at least one heteroatom selected from O, N or S;

[0436] L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand;

[0437] M is Ti, Zr, or Hf;

[0438] Each R1 is the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy

[0439] Each n is between 0 and 3;

[0440] Whether each R2 is the same or different is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0441] Each R is the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and

[0442] Each p is between 0 and 3;

[0443] To form a supported catalyst;

[0444] (III) In the first stage, in the presence of the supported catalyst, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized to form a first polyethylene component (e.g., a lower molecular weight component).

[0445] (IV) In the second stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form a second polyethylene component (e.g., a higher molecular weight component).

[0446] When preparing supported catalysts using this distinctly different two-step method, we observed some surprising technical effects:

[0447] • Compared to classic non-bridged bis-Cp metallocene catalysts (prepared in the same manner), such as those based on bis(1-methyl-3-n-butylcyclopentadienyl)zirconia, the activity in the slurry phase is up to twice that of the gas phase in some cases, and up to five times that of the gas phase.

[0448] The catalysts of this invention exhibit high activity in the gas phase.

[0449] • Compared with classic non-bridged bis-Cp metallocene catalysts (regardless of the catalyst preparation method), such as those based on bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, the comonomer response is significantly higher.

[0450] The catalyst of this invention has a much higher molecular weight capability.

[0451] • The molecular weight can be adjusted using hydrogen gas without causing a significant loss of activity.

[0452] • The polymer particles have excellent morphology.

[0453] This method can prepare polymers with lower density.

[0454] Stable slurry phase dynamics curves, suitable for multi-stage methods.

[0455] • The level of long-chain branching in copolymers is relatively low.

[0456] The key here is to combine comonomer sensitivity, molecular weight capability, and higher overall multi-stage polymerization activity with, crucially, a higher gas-to-slurry phase activity ratio.

[0457] Multi-peak polyethylene polymer

[0458] This invention relates to the preparation of multimodal polyethylene homopolymers or copolymers. The density of the multimodal ethylene homopolymers or copolymers can be between 900 and 980 kg / m³. 3 between.

[0459] Preferably, the multimodal polyethylene polymer is a copolymer. More preferably, the multimodal polyethylene copolymer is LLDPE. Its density can be 905 to 940 kg / m³. 3 Preferably, it is 910 to 935 kg / m 3 More preferably 915 to 930 kg / m 3 Especially 916 to 928 kg / m 3 In one embodiment, 910 to 928 kg / m³ is preferred. 3 The term LLDPE refers to linear low-density polyethylene in this document. The LLDPE used in this invention is multimodal.

[0460] The term "multimodal" includes polymers that are multimodal in terms of MFR, and therefore also includes bimodal polymers. The term "multimodal" can also refer to the multimodality of the "comonomer distribution".

[0461] Polymers containing at least two polyethylene fractions are typically referred to as "multimodal" because these fractions are produced under different polymerization conditions, resulting in different (weight-average) molecular weights and molecular weight distributions. The prefix "multimodal" refers to the number of different polymer fractions present in the polymer. Thus, for example, the term multimodal polymer includes so-called "bimodal" polymers composed of two fractions. The molecular weight distribution curve (MWD) of multimodal polymers such as LLDPE, i.e., the appearance of the graph showing the polymer weight fraction as a function of its molecular weight, may show two or more maximum values, or be significantly wider than the curve for a single fraction. Typically, the final MWD curve will be wider, sloping, or show shoulders.

[0462] Ideally, the molecular weight distribution curve of the multimodal polymer of the present invention will show two distinct maximum values. Alternatively, the polymer fractions have similar MFRs and are bimodal in terms of comonomer content. Polymers comprising at least two polyethylene fractions produced under different polymerization conditions, resulting in different comonomer contents in the fractions, are also referred to as “multimodal” polymers.

[0463] For example, if a polymer is produced in a continuous multi-stage process using reactors in series and different conditions in each reactor, the polymer fractions produced in each reactor will each have their own molecular weight distribution and weight-average molecular weight. When recording the molecular weight distribution curves of this polymer, superimposing the individual curves of these fractions onto the overall molecular weight distribution curve of the resulting polymer product typically produces a curve with two or more distinct maximum values.

[0464] In any multimodal polymer, there may be a lower molecular weight component (LMW) and a higher molecular weight component (HMW). The molecular weight of the lower molecular weight component is lower than that of the higher molecular weight component. This difference is preferably at least 5000 g / mol.

[0465] The multimodal polyethylene polymer used in this invention preferably contains at least one C4-10 comonomer. The comonomer may be present in the HMW component (or the second component) or the LMW component (or the first component), or both. From this point forward, the term LMW / HMW component will be used, but the described embodiments apply to the first and second components, respectively.

[0466] Preferably, the HMW component comprises at least one C4-10 comonomer. Then, the LMW component can be an ethylene homopolymer, or it may also contain at least one C4-10 comonomer. In one embodiment, the multimodal polyethylene polymer contains a single comonomer. In a preferred embodiment, the multimodal polyethylene polymer contains at least two, for example, exactly two, C4-10 comonomers.

[0467] In one embodiment, the multimodal polyethylene polymer is a terpolymer comprising at least two C4-10 comonomers. In this case, the HMW component can be a copolymer component or a terpolymer component, and the lower molecular weight (LMW) component can be an ethylene homopolymer component or a copolymer component. Alternatively, both the LMW and HMW components can be copolymers, thus containing at least two C4-10 comonomers.

[0468] Therefore, the multimodal polyethylene polymer may be wherein the HMW component comprises ethylene and at least two other C4 components. 4-10 α-olefin monomers such as 1-butene and a C 6-10 Repeating units of α-olefin monomers. Ethylene preferably constitutes the majority of the LMW or HMW component. In the most preferred embodiment, the LMW component may include an ethylene-1-butene copolymer, and the HMW component may include an ethylene-1-hexene copolymer.

[0469] The total monomer content in the multimodal polyethylene polymer may be, for example, 0.5 to 8.0 mol%, preferably 0.7 to 6.5 mol%, more preferably 1.0 to 5.0 mol%, and most preferably 1.5 to 5.0 mol%.

[0470] The content of 1-butene can be from 0.2 to 2.5 mol%, for example, from 0.4 to 2 mol%, more preferably from 0.4 to 1.5 mol%, and most preferably from 0.4 to 1 mol%.

[0471] The content of C6 to C10 α-olefins can be from 0.3 to 5.5 mol%, preferably from 0.4 to 4.5 mol%, more preferably from 0.7 to 4.5 mol%.

[0472] Preferably, the LMW component has a lower amount (mol%) of comonomer than the HMW component. For example, the comonomer in the LMW component is preferably 0.05 to 0.9 mol% of 1-butene, more preferably 0.1 to 0.8 mol%, while the comonomer in the HMW component (B) is preferably 1.0 to 8.0 mol% of 1-hexene, more preferably 1.2 to 7.5 mol%.

[0473] If necessary, the comonomer content (mol%) in the HMW component = (comonomer content (mol%) in the final product - (weight fraction of LMW component × comonomer content (mol%) in LMW component) / (weight fraction of HMW component).

[0474] Therefore, the multimodal polyethylene copolymer can be formed from ethylene together with at least one of 1-butene, 1-hexene, or 1-octene. The multimodal polyethylene polymer can be an ethylene-butene-hexene terpolymer, for example, wherein the HMW component is an ethylene-butene-hexene terpolymer and the LMW is an ethylene homopolymer component. Terpolymers of ethylene with 1-butene and 1-octene comonomers, or terpolymers of ethylene with 1-octene and 1-hexene comonomers, can also be considered.

[0475] In a further embodiment, the multimodal polyethylene copolymer may comprise two ethylene copolymers, such as two ethylene-butene copolymers, or an ethylene-butene copolymer (e.g., as an LMW component) and an ethylene-hexene copolymer (e.g., as an HMW component). Alternatively, the ethylene copolymer component and the ethylene terpolymer component may be combined, for example, an ethylene-butene copolymer (e.g., as an LMW component) and an ethylene-butene-hexene terpolymer (e.g., as an HMW component).

[0476] The MFR2 of the LMW component of the multimodal polyethylene polymer can be from 0.5 to 3000 g / 10 min, more preferably from 1.0 to 1000 g / 10 min. In some embodiments, the MFR2 of the LMW component can be from 50 to 3000 g / 10 min, more preferably from 100 to 1000 g / 10 min, for example when the target is a cast film. In some embodiments, the MFR2 of the LMW component can be from 0.5 to 50 g / 10 min, more preferably from 1.0 to 10 g / 10 min, preferably from 1.5 to 9.0 and more preferably from 2.0 to 8.5, for example when the target is a blown film.

[0477] The molecular weight of the low molecular weight component should preferably be in the range of 20,000 to 90,000, for example, 60,000 to 90,000.

[0478] Its density is likely at least 925 kg / m³ 3 For example, at least 940 kg / m 3 The density is likely between 930 and 950, preferably between 935 and 945 kg / m³. 3 Within the range.

[0479] For example, the MFR2 of the HMW component of the multimodal polyethylene polymer may be less than 1 g / 10 min, for example, 0.2 to 0.9 g / 10 min, preferably 0.3 to 0.8 g / 10 min, and more preferably 0.4 to 0.7 g / 10 min. Its density may be less than 915 kg / m³. 3 For example, less than 910 kg / m 3 Preferably less than 905 kg / m 3 The Mw of higher molecular weight components can be in the range of 100,000 to 1,000,000, for example, 250,000 to 500,000.

[0480] The LMW component can constitute 30 to 70 wt% of the multimodal polyethylene polymer, for example 40 to 60 wt%, especially 45 to 55 wt%.

[0481] The HMW component can constitute 30 to 70 wt% of the multimodal polyethylene polymer, for example 40 to 60 wt%, especially 45 to 55 wt%.

[0482] In one embodiment, there are 40 to 45 wt% LMW component and 60 to 55 wt% HMW component.

[0483] In one embodiment, the polyethylene polymer consists of HMW and LMW components as the sole polymer components.

[0484] The MFR2 of the multimodal polyethylene polymer of the present invention can be from 0.01 to 50 g / 10 min, preferably from 0.05 to 25 g / 10 min, and especially from 0.1 to 10 g / 10 min.

[0485] The density of the multi-peak polyethylene polymer of the present invention can be 900 to 960 kg / m³. 3 Preferably, it is 905 to 940 kg / m 3 Especially 910 to 935 kg / m 3 .

[0486] The molecular weight distribution (MWD, M) of the polyethylene terpolymer of the present invention w / M nThe value is in the range of 2.0 to 15.0, preferably in the range of 2.2 to 10.0, and more preferably in the range of 2.4 to 4.6.

[0487] Multimodal (e.g., bimodal) polyethylene polymers are prepared by in-situ blending in a multi-stage polymerization process. Specifically, this method requires...

[0488] (I) In a first stage, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized in the presence of a metallocene catalyst to form a first polyethylene component; and

[0489] (II) In the second stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form the second component.

[0490] Multimodal polyethylene polymers can be produced in any suitable polymerization method known in the art, wherein polymerization is typically carried out in solution, slurry, bulk, or gas phase. Preferably, multimodal polymers are produced using, for example, two slurry reactors or two gas-phase reactors or any combination thereof in at least two-stage polymerization, and the order can be any. However, it is preferable to prepare multimodal polymers using, for example, slurry polymerization in a circulating reactor, followed by gas-phase polymerization in a gas-phase reactor.

[0491] The circulating reactor-gas phase reactor system is sold by Borealis as a BORSTAR reactor system. Therefore, any existing multimodal polyethylene polymer is preferably formed using a two-stage process comprising a first slurry circulating polymerization followed by gas phase polymerization.

[0492] The conditions used in this method are well-known. For slurry reactors, the reaction temperature is typically in the range of 60 to 110°C (e.g., 85 to 110°C), the reactor pressure is typically in the range of 5 to 80 bar (e.g., 50 to 65 bar), and the residence time is typically in the range of 0.3 to 5 hours (e.g., 0.5 to 2 hours). The diluent used is typically an aliphatic hydrocarbon with a boiling point in the range of -70 to +100°C, such as propane. In such reactors, polymerization can be carried out under supercritical conditions if desired. Slurry polymerization can also be carried out in bulk, where the reaction medium is formed from the monomers being polymerized.

[0493] The ethylene content in the liquid phase of the slurry can be from 2 to about 50 mol%, preferably from about 2 to about 20 mol%, especially from about 3 to about 12 mol%. As is known in the art, hydrogen can be introduced into the reactor to control the molecular weight of the polymer.

[0494] For gas-phase reactors, the reaction temperature is typically in the range of 60 to 115°C (e.g., 70 to 110°C), the reactor pressure is typically in the range of 10 to 25 bar, and the residence time is typically 1 to 8 hours. The gases used are typically non-reactive gases, such as nitrogen, or low-boiling hydrocarbons, such as propane and monomers (e.g., ethylene).

[0495] Preferably, a lower molecular weight polymer fraction is produced in a continuously operating circulating reactor, wherein ethylene and any comonomer are polymerized in the presence of the aforementioned polymerization catalyst and chain transfer agent such as hydrogen. The diluent is typically an inert aliphatic hydrocarbon, preferably isobutane or propane.

[0496] The same catalyst can then be used to form higher molecular weight components in a gas-phase reactor.

[0497] Further polymerization steps, such as further gas-phase steps, can also be used.

[0498] It is generally preferred to remove the reactants from the polymer from the previous polymerization stage before introducing the polymer into the subsequent polymerization stage. This is preferably done when transferring the polymer from one polymerization stage to another.

[0499] The catalyst can be transferred to the first reactor by any means known in the art. For example, the catalyst can be suspended in a diluent and kept as a slurry, the catalyst can be mixed with a viscous mixture of grease and oil and the resulting paste can be fed into the polymerization zone, or the catalyst can be allowed to settle and a portion of the resulting catalyst slurry can be introduced into the polymerization.

[0500] If a higher molecular weight component is produced a second time in a multi-stage polymerization process, its properties cannot be directly measured. However, technicians are able to use... equation( The Polymer Processing Society, Europe / Africa Region Meeting, Gothenburg, Sweden, August 19-21, 1997, determined the density, MFR2, etc. of higher molecular weight components.

[0501]

[0502] According to the above In equation (eq.3), for MFR2, a = 5.2, b = 0.7. Furthermore, w is the weight fraction of other ethylene polymer components with higher MFRs, such as component (A). Therefore, the LMW component can be considered component 1, and the HMW component can be considered component 2. MIb is the MFR2 of the final polyethylene.

[0503] The method of the present invention may also involve a prepolymerization step. This prepolymerization step is a conventional step routinely used in polymer synthesis.

[0504] The prepolymerization step can be carried out in a slurry or gas phase. Preferably, prepolymerization is carried out in a slurry, more preferably in a circulating reactor. Prepolymerization is then preferably carried out in an inert diluent, preferably a low-boiling-point hydrocarbon or a mixture of such hydrocarbons having 1 to 4 carbon atoms. The temperature in the prepolymerization step is typically 0 to 90°C, preferably 20 to 80°C, more preferably 25 to 70°C.

[0505] Pressure is not critical, typically ranging from 1 to 150 bar, preferably from 10 to 100 bar.

[0506] Preferably, all the catalyst is introduced into the prepolymerization step. Preferably, the reaction products of the prepolymerization step are then introduced into the first reactor.

[0507] If present, the prepolymer component is considered part of the LMW component.

[0508] Typically, the amount of catalyst used depends on the properties of the catalyst, the type and conditions of the reactor, and the desired performance of the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of polymers in any reactor.

[0509] Polymers prepared by the method of this invention can be used in a variety of applications, such as films, like blown films or cast films. They can also be used in molding applications.

[0510] The catalyst system prepared according to the present invention exhibits particularly excellent catalytic activity throughout the multi-stage polymerization process, while also providing polymers with high weight-average molecular weight (Mw) and high comonomer content.

[0511] The invention will now be described with reference to the following non-limiting embodiments and accompanying drawings.

[0512] Figure 1 shows the ethylene uptake of IC3-1 and CC1 in the slurry phase during polymerization in Experiment 1 (Examples IE3-1 and CE1-1).

[0513] Figure 2 shows the ethylene uptake of IC3-1 and CC1 in the gas phase during polymerization in Experiment 1 (Examples IE3-1 and CE1-1).

[0514] Figure 3 The catalyst activities of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the slurry phase during the polymerization in Experiment 1 are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0515] Figure 4 The catalyst activities of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the gas phase during polymerization in Experiment 1 are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0516] Figure 5 The gas phase separation achieved by IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 is shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0517] Figure 6 The gas-phase to slurry-phase activity ratios of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0518] Figure 7 A graph showing the relationship between the gas phase activity and the slurry phase activity of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0519] Figure 8 The relationship between the gas phase and slurry phase activity ratio and the slurry phase activity of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0520] Figure 9 The relationship between the gas phase and slurry phase activity ratio and the gas phase activity of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0521] Figure 10 MFR2 data for IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in Experiment 1 polymerization are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0522] Figure 11 The relationship between the gas phase and slurry phase activity ratios of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 and MFR2 in the polymerization of Experiment 1 was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0523] Figure 12 The calculated butene incorporation amounts in the slurry phase material for IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1, and CC4-1 in the polymerization of Experiment 1 are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1, and CE4-1).

[0524] Figure 13 The calculated hexene incorporation amounts in the gas phase material for IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1, and CC4-1 in the polymerization of Experiment 1 are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1, and CE4-1).

[0525] Figure 14 A graph showing the relationship between the slurry phase activity of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 and the calculated amount of butene incorporated into the slurry phase material was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0526] Figure 15 A graph showing the relationship between the gas-phase activity of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 and the calculated amount of hexene incorporated into the gas-phase material was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0527] Figure 16 The final polymer densities of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in the polymerization of Experiment 1 are shown (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0528] Figure 17The relationship between the gas phase to slurry phase activity ratio and the final polymer density of IC1-1, IC2-1, IC3-1, CC1, CC2-1, CC3-1 and CC4-1 in Experiment 1 polymerization was plotted (Examples IE1-1, IE2-1, IE3-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0529] Figure 18 The catalyst activity in the slurry phase of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2, CC4-2 and CC5-2 in the polymerization of Experiment 2 is shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2, CE4-2 and CE5-2).

[0530] Figure 19 The gas-phase catalyst activities of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 are shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0531] Figure 20 The gas phase separation achieved by IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 is shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0532] Figure 21 The gas-phase to slurry-phase activity ratios of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2, and CC4-2 in the polymerization of Experiment 2 are shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2, and CE4-2).

[0533] Figure 22 A graph showing the relationship between the gas-phase activity and the slurry-phase activity of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0534] Figure 23The relationship between the gas phase and slurry phase activity ratio and the slurry phase activity of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0535] Figure 24 The relationship between the gas phase and slurry phase activity ratio and the gas phase activity of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0536] Figure 25 MFR2 data for IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in Experiment 2 polymerization are shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0537] Figure 26 The relationship between the gas phase and slurry phase activity ratios of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 and MFR2 in the polymerization of Experiment 2 was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0538] Figure 27 The calculated butene incorporation amounts in the slurry phase material for IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2, and CC4-2 in the polymerization of Experiment 2 are shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2, and CE4-2).

[0539] Figure 28 The calculated hexene incorporation amounts in the gas phase material for IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2, and CC4-2 in the polymerization of Experiment 2 are shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2, and CE4-2).

[0540] Figure 29A graph showing the relationship between the slurry phase activity of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 and the calculated amount of butene incorporated into the slurry phase material was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0541] Figure 30 A graph showing the relationship between the gas-phase activity of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in the polymerization of Experiment 2 and the calculated amount of hexene incorporated into the gas-phase material was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0542] Figure 31 The final polymer densities of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in Experiment 2 polymerization are shown (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0543] Figure 32 The relationship between the gas phase to slurry phase activity ratio and the final polymer density of IC1-2, IC2-2, IC3-2, CC1, CC2-2, CC3-2 and CC4-2 in Experiment 2 polymerization was plotted (Examples IE1-2, IE2-2, IE3-2, CE1-2, CE2-2, CE3-2 and CE4-2).

[0544] experimental

[0545] Analytical methods

[0546] Catalyst Analysis

[0547] The Al and Zr contents of the solid catalyst were determined by ICP-OES.

[0548] In a glove box, an aliquot of the catalyst (approximately 40 mg) was weighed into a glass weighing boat using an analytical balance. The sample was then exposed to air overnight while being placed in a steel secondary container equipped with an air inlet. The contents of the boat were then rinsed into a 20 mL Xpress microwave oven container using 5 mL of concentrated (65%) nitric acid. The sample was then subjected to microwave-assisted acid digestion using a MARS6 laboratory microwave unit, with the temperature increased to 150 °C over 20 minutes and maintained at 150 °C for 35 minutes. The digested sample was cooled to room temperature and then transferred to a 100 mL plastic volumetric flask. A standard solution containing 1000 mg / L yttrium (0.4 mL) was added. The flask was then filled with distilled water and agitated. The solution was filtered through a 0.45 μm nylon syringe filter and analyzed using a Thermo iCAP6300 ICP-OES system and iTEVA software.

[0549] The instrument was calibrated for Al and Zr using a blank (5% HNO3 solution prepared from concentrated nitric acid) and six standard solutions of Al and Zr at concentrations of 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L. These solutions contained 5% HNO3 (from concentrated nitric acid) and 4 mg / L Y standard in distilled water. Plastic volumetric flasks were used. Curve fitting and 1 / concentration weighting were used for the calibration curve. Just before analysis, the calibration was validated and adjusted using a blank and 10 mg / L Al and Zr standards (4 mg / L Y in distilled water from concentrated nitric acid and 5% HNO3) (instrument recalibration function). The quality control samples (QV: 1 mg / L Al, 2 mg / L Zr, and 4 mg / L Y in distilled water from concentrated nitric acid) were run to confirm the recalibration. The QV samples were also run at the end of the scheduled analytical set.

[0550] Zr content was monitored using the 339.198 nm line. Al content was monitored using the 394.401 nm line. Y at 371.030 nm was used as an internal standard. Reported values ​​were calculated back to the original catalyst sample using the original mass and dilution volume of the aliquoted catalyst sample.

[0551] The volatile content of the solid catalyst was determined by GC-MS.

[0552] Under an inert atmosphere, accurately weigh 50 to 80 mg of catalyst powder into a 20 mL headspace vial. Cap the vial with an aluminum cap fitted with a PTFE / silicone diaphragm. Using a precision microsyringe, add 1 mL of internal standard solution (50 mg toluene-d8 and 50 mg n-nonane dissolved in 100 mL n-dodecane) to the vial through the diaphragm cap. The same ISTD solution is used for both the sample and calibration standard solutions.

[0553] For calibration, the standard stock solutions are prepared by accurately weighing 40 mg of each analyte component (n-pentane, n-heptane, and toluene) into a 20 mL volumetric flask and then filling it to the mark with ISTD stock solution. Calibration solutions for different analyte concentrations are prepared by accurately dispensing six incremental aliquots (0.1 to 1 mL) of the analyte standard stock solution into 20 mL headspace vials, and then adding ISTD solution in decreasing volumes until the total ISTD stock solution volume in each vial reaches 1.0 mL. The final calibrated sample contains analyte concentrations in the range of 0.2 mg / mL to 2 mg / mL. For the blank, 1 mL of ISTD stock solution is transferred to a 20 mL headspace vial.

[0554] Measurements were performed using an Agilent 7890B gas chromatograph equipped with an Agilent 7697A headspace sampler and an Agilent 5977A mass spectrometer detector. The carrier gas was 99.9996% helium. The headspace sampler column oven temperature was set to 80°C, and the circulation and transfer line temperatures were set to 120°C. The vial equilibration time was 15 minutes. For injection, the headspace vials were filled in flow-pressure mode and pressurized to 172 kPa at a flow rate of 20 mL / min. The circulation was injected at a rate of 138 kPa / min, with a final pressure of 34 kPa. The carrier gas flow rate in the 0.53 mm diameter DB-ProSteel transfer line was 54 mL / min.

[0555] The gas chromatograph injection port was operated in split mode. The injection port temperature was set to 280°C, the pressure to 18.236 psi, the total flow rate to 111.9 mL / min, the diaphragm purge flow rate to 3 mL / min, and the split flow rate to 108 mL / min. The split ratio was 120:1. An ultra-inert split liner with glass wool was used as the injection port liner.

[0556] Separation was achieved using a ZB-XLB-HT Inferno 60m×250μm×0.25μm column (Phenomenex) and a 3m×250μm×0μm pre-column flow-limiting capillary. The carrier gas flow rate in the analytical column was 1.1 mL / min. The initial column oven temperature was 40℃, held for 0.1 min. The column oven temperature ramp-up consisted of a first stage of 5℃ / min to 60℃, a second stage of 10℃ / min to 120℃, and a third stage of 40℃ / min to 250℃.

[0557] The transfer line of the MS detector was maintained at 300°C. The MSD was operated in electron bombardment mode at 70 eV, with a scan range of 33 to 175 m / z and a step size of 0.1 m / z. The ion source temperature was set to 230°C, and the quadrupole temperature was set to 150°C. The threshold was set to 50 counts, and the electron multiplier gain factor was set to 1. The detector was turned off after 11.40 minutes.

[0558] Signal characteristics were determined by retention times (pentane 4.5, heptane 6.3, toluene 7.8, toluene-d8 7.7, and n-nonane 10.0) and target ion m / z (pentane 55.0, heptane 100.0, toluene 91.0, toluene-d8 98.0, and n-nonane 98.0). Additionally, qualitative ions were used for confirmatory identification (heptane, toluene). Target ion signals for each analyte and internal standard were integrated and compared with calibration curves established at the start of each run using six calibration samples. The calibration curves for response ratios were linear; sample concentration weighting was applied to pentane. Standardization was validated using quality control samples at the start of each run. The sample mass was used to calculate the analyte concentrations in two replicates within the sample, and the results were reported as an average value expressed in wt%.

[0559] Polymer analysis and characterization

[0560] Polymer melt flow rate (MFR)

[0561] Melt flow rate (MFR) is determined according to ISO 1133 and expressed in g / 10 min. The MFR of PE is determined at 190°C. The load used to determine the melt flow rate is usually expressed with a subscript; for example, MFR2 is determined at a load of 2.16 kg.

[0562] Polymer density

[0563] The polymer density was determined according to ISO 1183-1:2012 (Method A) using the immersion method (Archimedes' principle). The test was performed on a disc die-cut from a compression molding sheet. The compression molding process parameters used were:

[0564]

[0565] After compression molding, the samples were placed at 23±2℃ and 50±10% humidity for 24±2 hours. Based on Archimedes' principle, the samples were then weighed in air and immersed in a liquid (isododecane) with a density lower than that of the samples. The tests were conducted without the buoyancy correction recommended in the standards.

[0566] Quantitative analysis of microstructure using nuclear magnetic resonance spectroscopy

[0567] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the comonomer content of polymers.

[0568] Use for 1 H and 13 A Bruker Avance III 500 NMR spectrometer, operating at 500.13 and 125.76 MHz respectively, recorded quantitative data in the molten state.13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 150°C. 13 All spectra were recorded using a C-optimized 7mm magic angle rotation (MAS) probe. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. Standard single-pulse excitation was employed with a short 3s cycle delay using NOE (pollard, klimke, 06) and an RS-HEPT decoupling scheme (fillip, griffin, 07). A total of 1024 (1k) transient signals were acquired for each spectrum.

[0569] Quantitative 13 C{ 1 The H NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined from the integration. All chemical shifts were internally referenced at 30.00 ppm, showing a large amount of methylene signal (δ+) {randall89}.

[0570] The characteristic signal {randall89} corresponding to the incorporation of 1-butene was observed, and the comonomer fraction was calculated as the fraction of 1-butene in the polymer relative to all monomers in the polymer.

[0571] Used at 39.8 ppm * B2 site [I] *B2 The integral of ] quantifies the amount of isolated 1-butene incorporated into the EEBEE sequence, taking into account the number of reporter sites for each comonomer:

[0572] B = I *B2

[0573] In the absence of observed signals indicating the incorporation of other comonomer sequences, i.e., continuous comonomers, the total 1-butene comonomer content was calculated solely based on the amount of isolated 1-butene sequences:

[0574] B total = B

[0575] Therefore, the total mole fraction of 1-butene in the polymer is calculated as follows:

[0576] fB = B_total / (E_total + B_total + H_total)

[0577] The characteristic signal {randall89} corresponding to the incorporation of 1-hexene was observed, and the comonomer fraction was calculated as the fraction of 1-hexene in the polymer relative to all monomers in the polymer.

[0578] Used at 38.2 ppm * B4 site [I] *B4 The integral of ] quantifies the amount of isolated 1-hexene incorporated into the EEHEE sequence, taking into account the number of reporter sites for each comonomer:

[0579] H = I *B4

[0580] In the absence of observed signals indicating the incorporation of other comonomer sequences, i.e., continuous comonomers, the total 1-hexene comonomer content was calculated solely based on the amount of isolated 1-hexene sequences:

[0581] H_total = H

[0582] Therefore, the total mole fraction of 1-hexene in the polymer is calculated as follows:

[0583] fH = H_total / (E_total + B_total + H_total)

[0584] The amount of ethylene was quantified using an integral of numerous methylene (δ+) sites at 30.00 ppm. This integral included γ sites as well as the 3B4 site of 1-hexene. The total ethylene content was calculated based on the volume integral and compensated for by the observed 1-butene and 1-hexene sequences and end groups.

[0585] E = I δ+ / 2

[0586] Characteristic signals generated by saturated end groups were observed. Using 22.8[I] saturated end groups assigned to the 2s and 3s sites respectively... 2s ] and 32.2 ppm [I 3S The content of such saturated end groups is quantified by the average value of the signal integral at the [location].

[0587] S=(1 / 2)×(I 2S +I 3S )

[0588] The presence of isolated comonomer units is corrected based on the number of existing comonomer units and saturated end groups:

[0589] Etotal = E + (3 / 2) × B + (2 / 2) × H + (3 / 2) × S

[0590] The molar percentage of comonomer incorporated is calculated from the mole fraction:

[0591] B[mol%]=100×fB

[0592] H[mol%]=100×fH

[0593] The weight percentage of comonomer incorporated is calculated as a mole fraction:

[0594] B[wt%]=100×(fB×56.11) / ((fB×56.11)+(fH×84.16)+((1-(fB+fH))×28.05))

[0595] H[wt%]=100×(fH×84.16) / ((fB×56.11)+(fH×84.16)+((1-(fB+fH))×28.05))

[0596] randall89

[0597] J.Randall,Macromol.Sci.,ReV.Macromol.Chem.Phys.1989,C29,201.

[0598] klimke06

[0599] Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006;207:382.

[0600] parkinson07

[0601] Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007;208:2128.

[0602] pollard04

[0603] Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.

[0604] filip05

[0605] Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

[0606] griffin07

[0607] Griffin, JM, Tripon, C., Samoson, A., Filip, C., and Brown, SP, Mag.Res.inChem.2007 45, S1, S198

[0608] castignolles09

[0609] Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer50(2009)2373

[0610] raw material

[0611] The pretreated silica was commercially synthesized amorphous silica ES757 obtained from PQ Corporation. Pretreatment refers to the commercial calcination of silica at 600°C using conventional PO catalyst technology.

[0612] Methylaluminoxane (30 wt% MAO solution in toluene, Axion CA 1330) was purchased from Lanxess.

[0613] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride (MC4) is commercially available as a toluene stock solution.

[0614] Preparation of metallocene complexes

[0615] Racemic-dimethylsilanediylbis[2-(5-trimethylsilylfuran-2-yl)-4,5-dimethylcyclopentadiene- 1-[1-[2 ...

[0616] According to the published synthesis procedure (US6326493), the complex was prepared in the form of a pure stereoisomer.

[0617] The following novel metallocenes were prepared:

[0618] trans- and cis-methyl(pent-4-en-1-yl)silanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furan [4,5-Dimethylcyclopentadienyl]zirconium dichloride (MC1 of the present invention and MC5 of the comparative invention)

[0619] Multi-step coordination compound preparation method:

[0620] bis[2-(2-(5-trimethylsilyl)furanyl)-4,5-dimethylcyclopentan-2,4-dien-1-yl](methyl)pentanyl 4-En-1-ylsilane

[0621]

[0622] Add 34.7 mL (84.3 mmol) of 2.43 M sodium hydroxide to 200 mL of a 19.6 g (84.3 mmol) THF solution of 1-(2-(5-trimethylsilyl)furanyl)-3,4-dimethylcyclopentane-1,3-diene cooled to -78 °C. nBuLi was dissolved in hexane. The resulting red solution was stirred at room temperature for 4 hours, then cooled to -50°C, and 300 mg of CuCN was added. The resulting mixture was stirred at -25°C for 15 minutes, and then 7.72 g (42.2 mmol) of dichloro(methyl)pent-4-en-1-ylsilane was added in a single batch. The mixture was stirred at room temperature overnight. The solvent was removed by rotary evaporation; 600 mL of dichloromethane was added to the dark red residue, and the resulting mixture was washed with 600 mL of water. The organic layer was separated, dried with Na2SO4, filtered through a silica gel 60 (40 to 63 μm) filter, and washed again with 2 × 50 mL of dichloromethane. The combined filtrates were evaporated under reduced pressure and dried under vacuum to give 21.9 g (90%, purity: about 75%) of a dark red oily target product (a mixture of about 60:40 of the two stereoisomers).

[0623] trans- and cis-methyl(pent-4-en-1-yl)silanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furan [4,5-dimethylcyclopentadienyl]zirconium dichloride

[0624]

[0625] Add 31.3 mL (76.1 mmol) of 2.43 M diethyl ether to a 250 mL solution of 21.85 g (approximately 28.5 mmol) of bis[2-(2-(5-trimethylsilyl)furanyl)-4,5-dimethylcyclopentan-2,4-dien-1-yl](methyl)pentan-4-en-1-ylsilane cooled to -78 °C. nA hexane solution of BuLi was prepared. The mixture was stirred at room temperature for 4 hours, and then the resulting red solution was cooled to -78°C and 8.86 g (38.02 mmol) of ZrCl4 was added. The mixture was stirred at room temperature for 20 hours (resulting in a dark red solution with a yellow precipitate), and then evaporated to dryness. The residue was stirred with 100 mL of hot toluene, and the resulting suspension was filtered through a glass frit (G4). According to the NMR spectrum, the filtrate contained a mixture of isomeric complexes, namely the trans complex and two isomeric cis-zirconia in a ratio of 2:1:1. The filtrate was evaporated to dryness, and the residue was dissolved in a mixture of 25 mL of n-hexane and 100 mL of n-pentane. The yellow solid precipitated in this solution overnight at -30°C was filtered off (G4) and dried under vacuum. This step yielded 3.90 g of the trans complex contaminated with the cis mixture. The sample was recrystallized from a mixture of 10 mL of toluene and 30 mL of n-hexane to give 3.00 g of pure trans-zirconia. The mother liquor (obtained after separating 3.90 g of sample) was evaporated to dryness, and the residue was dissolved in 100 mL of n-pentane. The yellow solid precipitated in the resulting solution after being left at -30 °C overnight was filtered off (G4) and dried under vacuum to give 1.85 g of the trans isomer containing trace amounts of one of the two cis complexes. Finally, the mother liquor was evaporated to dryness until a dark foam was formed, and then the foam was dissolved in 150 mL of n-pentane. The yellow precipitate precipitated in this solution after being left at -30 °C for 2 days was filtered off (G4), washed with 5 mL of toluene, and dried under vacuum to give 2.10 g of a mixture of trans and cis complexes in a ratio of 45:55. This mixture was recrystallized from the mixture of n-hexane and n-pentane to give 0.23 g of one of the two cis complexes contaminated with approximately 6% trans isomer. Therefore, the total yield of the trans and cis complexes was 7.85 g (37.5%). It should be noted that only one of the two cis isomers is isolated in this reaction.

[0626] trans-methyl(pent-4-en-1-yl)silanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furanyl)-4,5- [Dimethylcyclopentadienyl]zirconium dichloride (MC1)

[0627] Anal.calc.for C 34 H 48 Cl2O2Si3Zr: C, 55.55; H, 6.58. Found: C, 55.81; H, 6.70.

[0628] 1H NMR(CDCl3):δ6.71(2s,2H),6.61(d,J=3.2Hz,2H),6.56(d,J=3.2Hz,1H),6.52(d,J=3.2Hz,1H),5.90-5.77(m,1H),5.04(dm,J=17.1Hz,1H),4.98(dm,J=10.2Hz,1H),2.28-2.10(m,2H),2.19(s,6H),1.85-1.59(m,2H),1.48(s,3H),1.46(s,3H),1.21(t,J=8.4Hz,2H),0.73(s,3H),0.29(s,9H),0.28(s,9H). 13 C{ 1 H}NMR(CDCl3):δ159.81,159.56,153.28,153.20,138.54,138.31,138.02,129.57,129.13,128.51,127.78,123.06,122.11,121.82,121.74,114.96,110.30,110.17,99.93,99.75,37.22,22.79,16.84,14.47,14.31,14.25,14.00,0.42,-1.24,-1.39.

[0629] cis-methyl(pent-4-en-1-yl)silanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furanyl)-4,5- [Dimethylcyclopentadienyl]zirconium dichloride (MC5)

[0630] Anal.calc.for C 34 H 48 Cl2O2Si3Zr:C,55.55;H,6.58.Found:C,55.69;H,6.76.

[0631] 1 H NMR(CDCl3):δ6.63(s,2H),6.31(d,J=3.2Hz,2H),6.11(d,J=3.2Hz,2H),5.93-5.80(m,1H),5.09(dm,J=17.1Hz,1H),5.04(dm,J=10.2Hz,1H),2.31-2.23(m,2H),2.28(s,6H),2.00(s,6H),1.85-1.73(m,2H),1.53-1.45(m,2H),0.40(s,3H),0.22(s,18H). 13 C{ 1H}NMR (CDCl3): δ158.57, 152.38, 138.09, 138.06, 131.29, 129.02, 122.74, 12 1.42, 115.44, 110.23, 99.49, 37.28, 22.76, 16.54, 15.17, 14.32, 0.34, -1.40.

[0632] Racemic-dimethylsilanediyl-bis[η] 5 -2-(2-(5-dimethylphenylsilyl)furanyl)-4,5-dimethyl Cyclopentadienyl] Zirconium dichloride (MC2 of this invention)

[0633] Preparation of multi-step coordination compounds:

[0634] 2-Furanyl(dimethyl)phenylsilane

[0635]

[0636] To a 165 mL solution of 25.0 g (367 mmol) furan in ether cooled in an ice bath, add 123.5 mL (300 mmol) of 2.43 M sodium hydroxide solution dropwise. n The hexane solution of BuLi was stirred for approximately 40 minutes. The resulting mixture was stirred at room temperature for 3.5 hours, and then the resulting suspension was cooled to -78°C, and 50.0 mL (51.6 g, 302 mmol) of chloro(dimethyl)phenylsilane was added in a single batch. The resulting mixture was stirred at room temperature for 40 hours. The resulting suspension was filtered through a silica gel 60 (40 to 63 μm) filter and washed with 3 × 50 mL of dichloromethane. The combined filtrates were evaporated under reduced pressure, and the residue was distilled under vacuum (boiling point: 79°C / 3-4 mmHg) to give 56.6 g (93%) of a colorless liquid containing 2-furanyl(dimethyl)phenylsilane.

[0637] 1 HNMR (CDCl3): δ7.67 (d, J=1.6Hz, 1H), 7.58-7.53 (m, 2H), 7.38-7.33 (m, 3H), 6.67 (d, J=3.2Hz, 1H), 6.38 (dd, J=3.2Hz, J=1.6Hz, 1H), 0.54 (s, 6H). 13 C{ 1 H} NMR (CDCl3): δ158.14, 147.11, 136.95, 133.91, 129.37, 127.85, 121.02, 109.41, -2.91.

[0638] 1-[2-(5-dimethylphenylsilyl)furanyl]-3,4-dimethylcyclopent-1,3-diene

[0639]

[0640] Add 41.2 mL (100.1 mmol) of 2.43 M sodium hydroxide solution dropwise to 150 mL of a 20.2 g (100 mmol) THF solution of 2-furanyl(dimethyl)phenylsilane cooled to -78 °C. n BuLi's hexane solution. The resulting mixture was stirred at room temperature for 20 hours, then cooled to -30°C, and 11.0 g (100 mmol) of 60 mL of 3,4-dimethylcyclopent-2-en-1-one in THF was added dropwise with vigorous stirring. The resulting solution was stirred at room temperature overnight, then cooled in an ice bath, and 200 mL of 5N HCl was added. The mixture was transferred to a separatory funnel, 600 mL of diethyl ether was added, and the resulting mixture was shaken for 1 minute. The organic layer was separated, washed with 3 × 150 mL of water, dried over Na2SO4, and then evaporated to dryness. The residue was purified by rapid column chromatography (40 to 63 μm; eluent: hexane) on silica gel 60 to give 25.9 g (88%, purity: about 90%) of the target product as a faint red oily liquid.

[0641] 1 H NMR (CDCl3): δ7.59-7.56 (m, 2H), 7.38-7.33 (m, 3H), 6.62 (d, J=3.2Hz, 1H), 6.57 (b rs, 1H), 6.21 (d, J=3.2Hz, 1H), 3.21 (s, 2H), 1.94 (s, 3H), 1.87 (s, 3H), 0.54 (s, 6H). 13 C{ 1 H}NMR (CDCl3): δ157.01, 156.14, 137.36, 135.34, 135.14, 133.97, 132.8 9, 131.37, 129.24, 127.80, 122.95, 104.15, 44.75, 13.35, 12.54, -2.75.

[0642] bis[2-(2-(5-dimethylphenylsilyl)furanyl)-4,5-dimethylcyclopent-2,4-dien-1-yl]dimethyl silane

[0643]

[0644] Add 36.2 mL (88.0 mmol) of 2.43 M sodium hydroxide solution to 200 mL of a 25.9 g (84.9 mmol) THF solution of 1-(2-(5-dimethylphenylsilyl)furanyl)-3,4-dimethylcyclopentane-1,3-diene cooled to -78 °C. nBuLi was dissolved in hexane. The resulting dark red solution was stirred at room temperature for 3 hours, then cooled to -50°C, and 300 mg of CuCN was added. The resulting mixture was stirred at -25°C for 15 minutes, and then 5.67 g (55.56 mmol) of dichlorodimethylsilane was added in one batch. The mixture was stirred overnight at room temperature. The solvent was removed by rotary evaporation, and 700 mL of dichloromethane was added to the dark red residue. The resulting mixture was washed with 800 mL of water. The organic layer was separated, dried with Na2SO4, and filtered through a silica gel 60 (40 to 63 μm) filter, which was then washed with 2 × 50 mL of dichloromethane. The combined filtrates were evaporated under reduced pressure, and the residue was dried under vacuum to give 25.6 g (90%, purity: about 80%) of a dark red oily target protoligand (a mixture of about 1:1 of the two stereoisomers).

[0645] 1 H NMR (CDCl3): δ7.57-7.46 (m, 4H), 7.39-7.26 (m, 6H), 6.59 (d, J = 3.2Hz), 6.57 (br.s) and 6.57 (d, J = 3.2Hz) {sum 4H}, 6.24 (d, J = 3.2Hz) and 6.07(d, J=3.2Hz){sum2H}, 4.07(s)and 3.70(s){sum 2H}, 2.13(s), 1.98(s), 1.88(s)and 1.87(s){sum 12H}, 0.51(s), 0.50(s), 0.48(s)and 0.46(s){sum 12H}, -0.45(s), -0.72(s)and-0.78(s){sum6H}.

[0646] Racemic-dimethylsilanediyl-bis[η] 5 -2-(2-(5-dimethylphenylsilyl)furanyl)-4,5-dimethyl Cyclopentadienyl] Zirconium dichloride (MC2)

[0647]

[0648] Add 32.6 mL (79.2 mmol) of 2.43 M dimethylsilyl ether solution of 25.6 g (approximately 39.7 mmol) cooled to -78 °C to 300 mL of bis[2-(2-(5-dimethylphenylsilyl)furanyl)-4,5-dimethylcyclopentan-2,4-dien-1-yl]dimethylsilane. nA hexane solution of BuLi. The mixture was stirred overnight at room temperature, and the resulting brown suspension with a large amount of white precipitate was cooled to -78°C, and 9.25 g (39.7 mmol) of ZrCl4 was added. The reaction mixture was stirred at room temperature for 24 hours to give a dark red solution with a yellow precipitate. The precipitate was filtered off. The filtrate was evaporated to about 30 mL, and then 30 mL of n-hexane was added. The yellow powder precipitated from this mixture (a mixture of the target complex and LiCl) was filtered off, washed with n-hexane, and then added to the separated precipitate. The resulting solid was stirred with 50 mL of hot toluene (almost under reflux), and the resulting suspension was filtered through a glass frit (G4). The filtrate was evaporated to about 25 mL, heated to about 60°C, and then 30 mL of n-hexane was added. The yellow powder precipitated from this solution overnight at room temperature (G4) was filtered off and dried under vacuum to give 4.82 g of the target complex. The mother liquor was evaporated to about 5 mL, and 25 mL of n-hexane was added. The yellow solid (G4) precipitated from the resulting mixture after being left overnight at room temperature was collected and then dried under vacuum. This step yielded an additional 0.7 g of title zirconium dicene. Therefore, the total yield of the target racemic complex was 5.52 g (17%).

[0649] Anal.calc.for C 40 H 46 Cl2O2Si3Zr: C, 59.67; H, 5.76. Found: C, 59.95; H, 5.81.

[0650] 1 H NMR (CDCl3): δ7.58-7.52 (m, 2H), 7.41-7.31 (m, 3H), 6.69 (s, 1H), 6.65 (d, J=3.3Hz, 1H), 6.55(d, J=3.3Hz, 1H), 2.16(s, 3H), 1.35(s, 3H), 0.56(s, 3H), 0.55(s, 3H), 0.54(s, 3H). 13 C{ 1 H} NMR (CDCl3): δ157.60, 154.01, 138.23, 136.56, 134.06, 129.42, 128.77, 128. 18, 127.80, 123.41, 122.01, 110.19, 100.06, 14.22, 14.18, 3.34, -2.65, -3.05.

[0651] Racemic- and meso-dimethylsilanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furanyl)-4-tert- [Butylcyclopentadienyl]zirconium dichloride (compared to MC6 and MC7)

[0652] Preparation of multi-step coordination compounds:

[0653] Ethyl 2-acetyl-5,5-dimethyl-4-oxohexanoate

[0654]

[0655] 12.5 g (544 mmol, 1.66 equivalents) of sodium was added to 360 mL of toluene, followed by 132 mL (1.04 mol, 3.16 equivalents) of ethyl acetoacetate. A vigorous exothermic reaction occurred after one minute, releasing molecular hydrogen, which subsided after approximately 10 minutes. The reaction mixture was then stirred at room temperature for 2 hours. 58.8 g (329 mmol) of 1-bromo-3,3-dimethylbut-2-one was added dropwise to the resulting heterogeneous mixture, and the reaction mixture was stirred overnight at room temperature. The resulting mixture was cooled in an ice bath and then treated with 400 mL of water. Another 400 mL of water was added, the organic layer was separated, and the aqueous layer was extracted with 400 mL of diethyl ether. The combined organic extracts were dried over Na₂SO₄, evaporated, and excess ethyl acetoacetate was removed by vacuum distillation (boiling point ≤65℃ / 6 mmHg) to give 79.3 g (approximately 100%) of the target product, which could be used further without additional purification.

[0656] 1 H NMR (CDCl3): δ4.19 (q, J=7.2Hz, 2H), 4.01 (dd, J=8.3Hz, J=5.6Hz, 1H), 3.23 (dd, J=18.5Hz, J=8 .3Hz, 1H), 3.02 (dd, J=18.5Hz, J=5.6Hz, 1H), 2.37 (s, 3H), 1.28 (t, J=7.2Hz, 3H), 1.17 (s, 9H). 13 C{ 1 H} NMR (CDCl3): δ213.36, 202.49, 168.92, 61.57, 53.67, 43.77, 35.70, 30.18, 26.39, 13.95.

[0657] 3-tert-butylcyclopent-2-en-1-one

[0658]

[0659] 1 L of hot water was added to 37.5 g (164.3 mmol) of ethyl 2-acetyl-5,5-dimethyl-4-oxohexanoate (prepared above). Under reflux, 110 g (1.96 mol) of a 500 mL aqueous solution of KOH was added dropwise to the mixture over 1 hour. The reaction mixture was refluxed for 8 hours, cooled to room temperature, and then extracted with 3 × 400 mL of diethyl ether. The combined extracts were dried over Na₂SO₄, filtered through a silica gel 60 (40 to 63 μm) filter, and then evaporated to dryness to give 18.0 g of crude product contaminated with about 15% 6,6-dimethylheptane-2,5-dione. The crude products obtained from four similar syntheses were combined and vacuum distilled to obtain fractions of 3-tert-butylcyclopent-2-en-1-one with varying purities, including a fraction of 3-tert-butylcyclopent-2-en-1-one with a purity of approximately 95%, whose boiling point is higher than that of 6,6-dimethylheptane-2,5-dione. Therefore, the calculated yield of the target product (given the purity of 3-tert-butylcyclopent-2-en-1-one) is... 1 The H NMR data showed that 52.0 g (57%) was obtained, while 8.77 g (8.5%) was obtained for 6,6-dimethylheptane-2,5-dione. The results indicate that a mixture of 3-tert-butylcyclopent-2-en-1-one and dione can be used for the subsequent synthesis of substituted cyclopentadiene.

[0660] 1 H NMR (CDCl3): δ5.95 (t, J=1.7Hz, 1H), 2.67-2.63 (m, 2H), 2.44-2.40 (m, 2H), 1.2 (s, 9H). 13 C{ 1 H} NMR (CDCl3): δ210.54, 191.11, 127.21, 35.41, 35.11, 28.68, 27.58.

[0661] 1-tert-butyl-3-[2-(5-trimethylsilyl)furanyl]cyclopent-1,3-diene

[0662]

[0663] Add 65.2 mL (158 mmol) of 2.43 M sodium hydroxide solution dropwise to 230 mL of a 22.2 g (158 mmol) THF solution of 2-trimethylsilylfuran cooled to -78 °C. nBuLi's hexane solution. The resulting mixture was stirred at room temperature for 7.5 hours, then cooled to -35°C, and 20.0 g of 89% pure 3-tert-butylcyclopent-2-en-1-one was added in one go [containing about 11% 6,6-dimethylheptane-2,5-dione, so the added mixture contained 17.55 g (127 mmol) of 3-tert-butylcyclopent-2-en-1-one and 2.45 g (15.68 mmol) of 6,6-dimethylheptane-2,5-dione]. The resulting solution was stirred at room temperature overnight, then cooled in an ice bath, and 200 mL of 4N HCl was added. The mixture was transferred to a separatory funnel, 500 mL of diethyl ether was added, and the resulting mixture was shaken for 1 minute. The organic layer was separated, washed with 3 × 200 mL of water, dried with Na2SO4, and then evaporated to dryness. The residue was purified by rapid column chromatography (40 to 63 μm; eluent: hexane) on silica gel 60 to give 27.5 g (83%, based on 3-tert-butylcyclopent-2-en-1-one in the mixture) of the target product (a mixture of two double bond position isomers in a ratio of approximately 88:12), as an orange oily liquid that spontaneously solidifies at room temperature.

[0664] 1 H NMR (CDCl3): δ 6.83 (m, 1H), 6.59 (d, J=3.2Hz, 1H), 6.27 (d, J=3.2Hz, 1H), 5.89 (“q”, J=1.7Hz, 1H), 3.27 (“t”, J=1.4Hz, 2H), 1.2 (s, 9H), 0.28 (s, 9H). 13 C{ 1 H} NMR (CDCl3): δ158.86, 157.62, 156.36, 137.02, 127.12, 121.29, 121.01, 104.93, 40.01, 32.20, 29.70, -1.48.

[0665] bis[2-(2-(5-trimethylsilyl)furanyl)-4-tert-butylcyclopent-2,4-dien-1-yl]dimethylsilane

[0666]

[0667] Add 40.3 mL (97.9 mmol) of 2.43 M sodium hydroxide to 200 mL of a 25.5 g (97.9 mmol) THF solution of 1-tert-butyl-3-[2-(5-trimethylsilyl)furanyl]cyclopent-1,3-diene cooled to -50 °C. nBuLi's hexane solution. The resulting dark red solution was stirred at room temperature for 3.5 hours, then cooled to -50°C, and 300 mg of CuCN was added. The resulting mixture was stirred at -25°C for 15 minutes, and then 6.32 g (49.0 mmol) of dichlorodimethylsilane was added in one go. The mixture was stirred overnight at room temperature. The solvent was removed on a rotary evaporator, and 600 mL of dichloromethane was added to the dark red residue. The resulting mixture was washed with 800 mL of water. The organic layer was separated, dried with Na2SO4, filtered through a silica gel 60 (40 to 63 μm) filter, and washed with 2 × 50 mL of dichloromethane. The combined filtrates were evaporated under reduced pressure. The resulting dark red oily substance was dissolved in 500 mL of n-hexane, and the resulting suspension was filtered through a silica gel 60 (40 to 63 μm) filter and washed with 3 × 50 mL of n-hexane. The filtrate was evaporated and dried under vacuum to obtain 25.4 g (90%, purity: about 90%) of bis[2-(2-(5-trimethylsilyl)furanyl)-4-tert-butylcyclopent-2,4-dien-1-yl]dimethylsilane (a mixture of two stereoisomers in a ratio of about 1:1), which was a light red oil.

[0668] 1 H NMR (CDCl3): δ6.85-6.82 (m, 2H), 6.58 (d, J = 3.2Hz) and 6.57 (d, J = 3.2Hz) {sum 2H}, 6.29 (d, J = 3.2Hz) and 6.27 (d, J = 3.2Hz) {sum 2H}, 6.17 (m) and 6.11(m){sum2H}, 3.87(d, J=1.2Hz)and 3.66(d,J=1.2Hz){sum2H}, 1.24(s)and 1.19(s){sum 18H}, 0.23(s)and 0.22(s){sum 18H}, -0.36(s), -0.44(s)and-0.50(s){sum 6H}. 13 C{ 1 H} NMR (CDCl3): δ158.41, 158.40, 156.50, 156.43, 156.09, 155.78, 138.14, 138.03, 126.69, 126.59, 124.53, 123.75, 121.37 (two resonances), 104.90, 104.82, 48.75, 47.78, 32.30, 32.24, 30.41, 30.38, -1.43, -1.46, -4.29, -6.52, -6.76.

[0669] Racemic- and meso-dimethylsilanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furanyl)-4-tert- [Butylcyclopentadienyl]zirconium dichloride

[0670]

[0671] Add 36.2 mL (88.0 mmol) of 2.43 M dimethylsilyl)furanyl)-4-tert-butylcyclopentan-2,4-dien-1-yl]dimethylsilane to a 350 mL diethyl ether solution cooled to -78 °C. n A hexane solution of BuLi was prepared. The mixture was stirred overnight at room temperature, and the resulting red solution was cooled to -78°C and 10.3 g (44.2 mmol) of ZrCl4 was added. The reaction mixture was stirred at room temperature for 24 hours to give a dark red solution with a yellow precipitate. The mixture was evaporated to dryness. The residue was stirred with 200 mL of hot toluene, and the resulting suspension was filtered through a glass frit (G4). The filtrate was evaporated to about 100 mL. The light orange precipitate that formed in the solution after standing at room temperature for 3 hours was washed with 10 mL of toluene and then dried under vacuum. This step yielded 9.70 g (30%) of pure racemic complex. The mother liquor was evaporated to about 10 mL, the resulting solution was heated to about 60°C, and then 30 mL of n-hexane was added. The yellow powder (a meso complex contaminated with 5% racemic isomer) and red crystals (a mixture of racemic and meso compounds of approximately 4:1) precipitated in the solution overnight at room temperature were filtered off (G4), yielding 9.30 g of racemic zirconium decene contaminated with approximately 15% racemic complex. The mother liquor was almost evaporated to dryness, and the residue was dissolved in 40 mL of n-pentane. The yellow solid precipitated in the resulting mixture overnight at room temperature (G4) was filtered off, and then dried under vacuum. This step yielded 3.50 g of a mixture of meso / racemic complexes in a ratio of 67:43. Therefore, the total yield of racemic and racemic zirconium decene was 22.5 g (69%). 120 mL of n-hexane was added to the yellow powder (9.30 g, yellow powder with red crystals) from the second fraction; the yellow powder dissolved rapidly, and the red crystals were immediately filtered off (G3). The filtrate was evaporated to dryness, and the residue was recrystallized from a mixture of 7 mL toluene and 15 mL n-hexane to give 4.50 g (14%) of pure meso-dimethylsilanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furanyl)-4-tert-butylcyclopentadienyl]zirconium dichloride.

[0672] Racemic-dimethylsilanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furanyl-4-tert-butylcyclopentadiene [Alkenyl] Zirconium dichloride (MC6)

[0673] Anal.calc.for C 34 H 50 Cl2O2Si3Zr: C, 55.40; H, 6.84. Found: C, 55.64; H, 7.02.

[0674] 1 H NMR (CDCl3): δ6.75 (d, J=2.5Hz, 2H), 6.67 (d, J=3.3Hz, 2H), 6.54 (d, J=3.3Hz, 2H), 5.54 (d, J=2.5Hz, 2H), 1.26 (s, 18H), 0.84 ((s, 6H), 0.33 (s, 18H). 13 C{ 1 H} NMR (CDCl3): δ159.89, 153.94, 153.36, 124.98, 123.70, 122.07, 111.58, 109.47, 103.22, 33.89, 30.16, -0.09, -1.31.

[0675] Meso-dimethylsilanediyl-bis[η] 5 -2-(2-(5-trimethylsilyl)furanyl-4-tert-butylcyclopentadiene [Alkenyl] Zirconium dichloride (MC7)

[0676] Anal.calc.for C 34 H 50 Cl2O2Si3Zr: C, 55.40; H, 6.84. Found: C, 55.77; H, 7.09.

[0677] 1 HNMR (CDCl3): δ6.82 (d, J=2.5Hz, 2H), 6.25 (d, J=3.3Hz, 2H), 6.07 (d, J=3.3Hz, 2 H), 5.69 (d, J=2.5Hz, 2H), 1.35 (s, 18H), 1.04 (s, 3H), 0.74 (s, 3H), 0.28 (s, 18H). 13 C{ 1 H} NMR (CDCl3): δ158.44, 152.94, 152.89, 127.08, 124.46, 122.28, 111.97, 108.47, 101.59, 34.10, 30.35, 1.77, -1.36, -2.89.

[0678] Catalyst preparation

[0679] All catalyst examples (except for CE1 used as is) were prepared based on the described metallocene complexes MC1 to MC7 using two distinct catalyst preparation methods. Experiment 1 describes the one-step catalyst preparation method, while Experiment 2 describes the two-step method. The MC7 complex was used only in the two-step method.

[0680] The catalyst of this invention

[0681] The catalysts IC1-1 and IC1-2 of this invention are based on the trans or racemic form of MC1:

[0682]

[0683] The catalysts IC2-1 and IC2-2 of this invention are based on the racemic form of MC2:

[0684]

[0685] The catalysts IC3-1 and IC3-2 of this invention are based on the racemic form of MC3:

[0686]

[0687] Comparison of catalysts

[0688] Comparative catalyst CE1 is an aluminum oxane-based silica-supported catalyst containing metallocene bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride (MC4), based on an enhanced catalyst from Grace. Activation technology, using ready-made mineral oil slurry.

[0689]

[0690] Catalysts CE2-1 and CE2-2 are compared because they are based on the same bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride complex MC4, similar to catalyst CE1, but their preparation steps are the same as those of other prepared catalyst examples.

[0691] Comparison of catalysts CE3-1 and CE3-2 based on cis or meso form of MC5:

[0692]

[0693] Comparison of catalysts CE4-1 and CE4-2 based on racemic MC6:

[0694]

[0695] Comparing catalyst CE5-2 with MC7 in its meso form:

[0696]

[0697] Aggregate Examples

[0698] All of the present invention and comparative catalysts were tested on a laboratory scale for ethylene copolymerization under identical conditions with a specific gas-phase separation (58%) target. This means that once a certain amount of ethylene was consumed in the slurry-phase polymerization stage, the reactor transitioned to the gas-phase stage and stopped when the total target ethylene consumption was reached. In cases where gas-phase separation could not be achieved due to low catalyst activity, the gas-phase stage was terminated prematurely due to limitations in the total experimental time (see values ​​marked with an asterisk * in Tables 1 and 2).

[0699] General-purpose, laboratory-scale, multi-stage ethylene copolymerization method

[0700] All polymerizations were carried out in a 5.3 L stirred autoclave. The evacuated autoclave was filled with 700 g of propane. 0.12 mmol of triethylaluminum scavenger (0.62 mol / L heptane solution) was added using an additional 100 g propane stream. 16 g of ethylene and 2.7 g of 1-butene were added, and the reactor was heated to the desired prepolymerization temperature of 60 °C. Approximately 100 mg of catalyst was weighed into a cylinder inside the glove box and suspended in 3 mL of heptane (8 mL if the catalyst was a slurry). The cylinder was then connected to the polymerization autoclave, and the suspension was flushed into the reactor with 200 g of propane.

[0701] For prepolymerization, the reactor was stirred at 60°C. Ethylene was fed in using a flow meter, maintaining a constant pressure of 21.1 barg. After 10 g of ethylene was consumed or the running time exceeded 45 minutes, the temperature was raised to 85°C. Subsequently, 12 mg of hydrogen and 5.4 g of 1-butene were fed into the reactor. Ethylene was fed in simultaneously until the desired polymerization pressure of 36.9 barg was reached.

[0702] For slurry-phase polymerization, the reactor was stirred at 85°C. The pressure was maintained constant by feeding ethylene, 1-butene, and hydrogen at fixed ratios (butene / ethylene = 0.035 g / g and hydrogen / ethylene = 0.000068 g / g). The reaction was stopped by venting and evacuating the reactor after consuming 200 g of ethylene.

[0703] For gas-phase polymerization, the reactor temperature is set to 75°C. The reactor is refilled with propane until a pressure of 10 barg is reached. 1.3 mg of hydrogen and 10.5 g of 1-hexene are fed into the reactor. Ethylene is fed simultaneously until the reactor pressure reaches 20 barg. During polymerization, the pressure is maintained constant by feeding ethylene, 1-hexene, and hydrogen in a fixed ratio (hexene / ethylene = 0.064 g / g and hydrogen / ethylene = 0.000038 g / g). The reaction is stopped by venting the reactor after 278 g of ethylene has been consumed. If the activity is too low (e.g., <1 kg / (g·h)), the reaction is stopped before the desired ethylene consumption is reached.

[0704] Experiment 1: One-step catalyst preparation and polymerization examples

[0705] The metallocene complexes MC1 to MC6 in this experiment were prepared using a single-step catalyst preparation process, including the mixing of metallocene and aluminoxane during impregnation. Therefore, the catalysts IC1-1 to IC3-1 of this invention and the comparative catalysts CC2-1 to CC4-1 were prepared using the following one-step catalyst preparation method.

[0706] One-step preparation method for general catalysts

[0707] 140 μmol of metallocene was dissolved in a methylaluminoxane solution (14 mmol of Al as a 30 wt% MAO solution in toluene) and an additional 1.6 to 2.0 mL of toluene, and stirred at room temperature in a glass flask under a nitrogen atmosphere for 1 to 2 hours to obtain a pre-contact mixture. The resulting solution was then added dropwise over 5 minutes to a 2 g pretreated silica support in a glass reactor with gentle mechanical stirring at 10 to 30 °C. The crude catalyst was then gently mixed for another 1 hour and allowed to stand for 17 hours. The catalyst was then vacuum dried at 60 °C for 30 to 60 minutes.

[0708] Table 1: Bimodal multistage copolymers of the present invention and comparative catalyst examples obtained using a one-step catalyst preparation method

[0709]

[0710]

[0711] All catalysts of the present invention, IC1-1 to IC3-1, and comparative catalysts CC1, CC2-1 to CC4-1, were used for copolymerization in a multi-stage configuration including prepolymerization, slurry-phase polymerization, and gas-phase polymerization. The polymerization conditions were as described above in “General Laboratory-Scale Multi-Stage Ethylene Copolymerization Method,” and the corresponding copolymerization examples of the present invention, IE1-1 to IE3-1, and comparative examples, CE1-1 to CE4-1, are disclosed in Table 1. Comparative catalyst CC1 was used for polymerization in the form of the received slurry.

[0712] discuss

[0713] From the kinetic curves in Table 1 and Figure 1-2, and Figure 3 , 4As can be seen from the performance graphs of the corresponding polymerization examples in 6-9, compared with comparative examples CC1 and CC2-1 to CC4-1, the catalysts IC1-1, IC2-1, and IC3-1 of the present invention surprisingly exhibit (when prepared using the one-step method) a better gas-phase activity to slurry-phase activity ratio, as well as higher and more stable gas-phase performance. A major challenge in multi-stage polymerization is ensuring sufficient catalytic activity in the gas phase relative to the slurry phase. Circulating / gas-phase processes are multi-stage processes with two or more reactors in series; therefore, in the event of premature catalyst deactivation, this process cannot produce multi-peak polymers with high fractions (splits) in later reactor stages. Alternatively, catalysts that remain highly active in the gas phase stage can produce polymers with larger fractions in the gas-phase reactor, generally resulting in superior product performance. The catalysts of the present invention described herein also exhibit high comonomer sensitivity, reflected in the polymer, higher comonomer content relative to comparative catalysts, lower density of the polymerization examples of the present invention, and higher polymer molecular weight capacity.

[0714] A comparison between IE1-1 and IE3-1 shows that, compared to simply substituting short alkyl groups, the importance of replacing the metallocene backbone bridge with an alkenyl moiety (the MCl complex in IE1-1) lies in the improvement of catalyst performance.

[0715] A comparison of IE2-1 and IE3-1 revealed a surprising effect: the gas-phase activity was slightly improved by introducing phenyl substitution into the peripheral trimethylsilyl moiety (the MC2 complex in IC2-1).

[0716] The comparison between IE1-1 and CE3-1 demonstrates the importance of selectively utilizing pure stereoisomers (in most cases, racemic forms) to obtain optimal performance (MC1 complex in IE1-1 versus MC5 complex in CC3-1).

[0717] The comparison of IE1-1, IE2-1 and CE4-1 (the negative impact of tert-butyl substitution in the MC6 complex on the performance of its catalyst CC4-1) highlights the importance of careful selection of metallocene structures, such as substitution patterns in the same metallocene type (here, a bridging furanyl-substituted bis-Cp complex) when high performance is involved.

[0718] In the slurry phase, in terms of catalyst activity, IC1-1 and IC3-1 have activities comparable to but slightly lower than CC1. Figure 3 However, the opposite was observed in the gas phase. All three catalysts of this invention, IC1-1 to IE3-1, exhibited superior catalytic activity in the gas phase compared to catalysts CC1 and CC2-1 to CC4-1. Figure 4 ).

[0719] Except for two embodiments (CE2-1 and CE4), all other embodiments achieved the target gas-phase separation of 58%, where the catalyst activity in the slurry was low, requiring a long slurry stage time to reach the desired ethylene consumption, which in turn limited the duration of the gas-phase stage. Figure 5 ).

[0720] For IC1-1 to IC3-1, high gas-phase performance was clearly achieved as expressed by the "gas-to-slurry phase activity ratio" parameter (referred to as GP / SP activity ratio from this point onwards). This ratio was found to be relatively high, and in the case of IC2-1, it was significantly higher than that of CC1, especially CC2-1 to CC4-1. Figure 6-9 ).

[0721] IC2-1 exhibits lower performance in the slurry phase than IC1-1 and IC3-1, but its performance in the gas phase is improved, even slightly exceeding the activity levels of IC1-1 and IC3-1.

[0722] The high activity of IC1-1 under both slurry and gas phase conditions can be attributed to the presence of alkenyl chains in the metallocene backbone. As demonstrated by CC3-1, which is based on MC5 (otherwise identical to the MC1 structure in IC1-1), its advantage is diminished by its more open meso compound form.

[0723] The poor performance of CC2-1 in Comparative Example CE2-1 highlights the overall strong advantage of furanyl-substituted bridging bis-Cp complexes compared to classical non-bridging bis-Cp complexes that are activated and heterogenized in the same manner.

[0724] The performance of CC4-1 in Example CE4-1 is reduced, even though the furanyl moiety of its metallocene MC6 is identical to that in the MC1 or MC3 complexes of IC1-1 and IC3-1. This indicates that introducing a large substituent at the 4 position of the Cp ring, rather than introducing two small substituents at the 4 and 5 positions, spatially hinders access to the metal center, thus reducing the complex's role in polymerization.

[0725] Figure 10 and 11 The low MFR2 levels in IE1-1 to IE3-1 clearly indicate the high molecular weight capacity of the corresponding metallocenes. In CC4-1, the introduction of a tert-butyl group at the 4-position of the Cp ring, instead of two methyl groups, leads to a significant loss of molecular weight capacity.

[0726] The combination of higher comonomer sensitivity and higher activity (especially in the gas phase) brings particular value to the embodiments of the present invention for the multi-stage method. Figure 12-15The combination of high comonomer incorporation capacity and higher productivity enables more economical polymerization processes and unlocks higher GP separation and lower density materials in gas-phase reactors. Figure 16 , 17 ).

[0727] Experiment 2: Two-step preparation of catalyst and polymerization examples

[0728] The metallocene complexes MC1 to MC7 in this experiment employed significantly different catalyst preparation processes, comprising two steps—preparing an aluminoxane-impregnated "activated" silica support (hereafter referred to as SiO2 / MAO) and subsequent metallocene impregnation as a separate step. Therefore, the catalysts IC1-2 to IC3-2 of this invention, as well as the comparative catalysts CC2-2 to CC5-2, were prepared using the following two-step method.

[0729] Two-step preparation method for general catalysts

[0730] Step A: Preparation of the activation support (SiO2 / MAO)

[0731] Under a nitrogen atmosphere, 20 g of pretreated silica and 100 mL of anhydrous toluene were placed in a multi-necked glass reactor equipped with a mechanical stirrer. Gentle mixing was initiated, and the slurry was cooled to -10 to 0 °C. Then, a methylaluminoxane solution (233 mmol of Al as a 30 wt% MAO toluene solution) was slowly added over 30 minutes while maintaining the temperature of the reaction mixture below 25 °C. The slurry was then stirred at room temperature for another 30 minutes. Afterward, the stirred reaction mixture was heated to 90 °C over 20 minutes and stirred at this temperature for 2 hours. The slurry was then allowed to settle at 90 °C for 15 minutes, and the hot supernatant was aspirated. 100 mL of anhydrous toluene was added, and the SiO2 / MAO support was washed at 90 °C with stirring for 30 minutes. The support settled, and the supernatant was aspirated. A second washing of the support was performed in the same manner as above, except that the washing temperature was between 50 and 70 °C. The support settled, and the supernatant was aspirated. Additional washing with heptane at room temperature could be performed to promote drying. Remove the supernatant, and dry the activated SiO2 / MAO support in a nitrogen stream at 60°C until no free liquid is observed. Then, dry it thoroughly in a vacuum at 60°C for at least 2 hours.

[0732] Step B: Catalyst Preparation

[0733] Under a nitrogen atmosphere, 52.5 μmol of metallocene was dissolved in 2.0 mL of anhydrous toluene in a glass flask and stirred at 20–60 °C for 1 hour. Then, under gentle mechanical stirring at 10–30 °C, the resulting solution was added dropwise over 5 minutes to 2 g of activated support (SiO2 / MAO prepared in step A) in a glass reactor. The crude catalyst was then gently mixed for another hour and allowed to stand for 17 hours. Finally, the catalyst was vacuum dried at 60 °C for 30–60 minutes.

[0734] Table 2: Bimodal multistage copolymers of the present invention and comparative catalyst examples obtained using a one-step catalyst preparation method

[0735]

[0736]

[0737]

[0738] All catalysts of the present invention, IC1-2 to IC3-2, and comparative catalysts CC1, CC2-2 to CC5-2, are used for copolymerization in a multi-stage configuration including prepolymerization, slurry-phase polymerization, and gas-phase polymerization. The polymerization conditions are as described above. General laboratory size Staged ethylene copolymerization method The corresponding copolymerization embodiments IE1-2 to IE3-2 and comparative embodiments CE1-2 to CE5-2 of the present invention are disclosed in Table 2. The comparative catalyst CC1 was used for polymerization in the form of the received slurry.

[0739] discuss

[0740] Although the two-step catalyst preparation method described in this paper and the metallocene and aluminoxane loadings used are significantly different from those in Experiment 1, surprisingly similar results and observations were obtained, indicating that both methods are feasible alternatives for catalyst preparation.

[0741] From Table 2 and Figure 18 , 19 As can be seen from the performance graphs of the corresponding polymerization examples in 21-24, compared with comparative examples CC1 and CC2-2 to CC4-2, the catalysts of the present invention IC1-2, IC2-2, and IC3-2 surprisingly exhibit (when prepared using the two-step method) a much better gas-phase activity to slurry-phase activity ratio, as well as higher gas-phase performance. The catalysts of the present invention described herein also exhibit high comonomer sensitivity, which is reflected in the polymer, with higher comonomer content, lower density, and higher polymer molecular weight capacity compared to comparative catalysts.

[0742] A comparison of IE1-2 and IE3-2 shows that the importance of partially substituting the metallocene backbone bridge with an alkenyl group compared to simply substituting with a short alkyl group lies in providing enhanced catalytic activity, especially in the slurry phase.

[0743] Paired comparisons of IE1-2 and CE4-2 with CE3-2 and CE5-2 (the latter two based on their respective meso forms MC5 and MC7) demonstrate the importance of selectively utilizing pure stereoisomer forms (in most cases, racemic forms) to obtain optimal performance.

[0744] A comparison of IE1-2, IE2-2, and CE4-2 (the negative impact of tert-butyl substitution in MC6 on the performance of CC4-2) highlights the importance of choosing a metallocene structure, such as the substitution pattern in the same metallocene type (here, a bridging furanyl-substituted bis-Cp complex) when high performance is involved. Even though the furanyl moiety of the metallocene is exactly the same as MC1 of IC1-2 and MC3 of IE3-2, the performance of CC4-2 is very low. This indicates that introducing a large substituent at position 4 of the Cp ring, rather than two small substituents at positions 4 and 5, spatially hinders access to the metal center, thus reducing the complex's role in polymerization. The performance of its meso-form (MC7) catalyst, CC5-2, is even lower, almost negligible.

[0745] In the slurry phase, only IC1-2 matches CC1 activity better in terms of catalyst activity, but in the gas phase, the performance is different: IC1-2 to IC3-2 have better catalyst activity compared to catalyst examples CC1 and CC2-2 to CC4-2.

[0746] Except for CC2-2, CC4-2, and CC5-2, all other catalysts achieved 58% gas-phase separation. Figure 20 For CC5-2, the low catalyst activity in the slurry phase means that the gas phase phase must be stopped and not carried out.

[0747] The key to this invention is the high gas-phase performance expressed as a "gas-to-slurry phase activity ratio" parameter. For polymerization examples IE1-2 to IE3-2, it was found that this ratio was significantly to overwhelmingly higher than that of CE1-2 to CE4-2. Figure 21 A high gas-to-slurry phase activity ratio is beneficial because it is an indicator of catalyst effectiveness in multi-stage processes, especially in the later gas-phase steps.

[0748] Catalyst IC1-2 exhibits extremely high activity in both the slurry and gas phases, which explains why its calculated GP / SP activity ratio is slightly lower compared to IC2-2 and IC3-2. The superior activity of IC1-2 under both slurry and gas phase conditions is particularly pronounced, clearly due to the presence of long alkenyl chains in the metallocene backbone (alkenyl chain interactions and reversible coordination with the active metal center). Interestingly, this effect disappears in the more open meso compound form, as demonstrated by CC3-2, whose metallocene MC5 structure is otherwise identical to the MC1 structure in IC1-2.

[0749] The slurry phase properties of IC2-2 and IC3-2 are moderate compared to those of IC1-2, and are significantly improved in the gas phase.

[0750] When MC4 in CC2-2 is prepared using the same catalyst platform (significantly different from that in CC1), When using a platform, a fair performance comparison can be made between the furanyl-based metallocenes (MC1 to MC3) and the bis(1-methyl-3-n-butylcyclopentadienyl)zirconia metallocene MC4 in the catalyst of this invention. The poor performance of CC2-2 highlights the overall strong advantage of furanyl-substituted bridging bisCp complexes compared to classical non-bridging bisCp complexes that are activated and heterogenized in the same manner.

[0751] The lower MFR2 levels in polymerization examples IE1-2 to IE3-2 clearly indicate that the corresponding metallocenes MC1 to MC3 have higher molecular weight capabilities. Figure 25 , 26 In CC4-2, the introduction of a tert-butyl group at the 4-position of the Cp ring of the MC6 complex, instead of two methyl groups, results in a significant loss of molecular weight capacity (and activity, see CE4-2). The MFRs in CE2-2 and CE4-2 are somewhat exaggerated because these examples did not achieve GP separation (low MFR polymer fractions are typically produced under the GP conditions used) and are not entirely representative.

[0752] The combination of higher comonomer sensitivity and higher activity (especially in the gas phase) brings particular value to the embodiments of the present invention for the multi-stage method. Figure 27-30 The combination of high comonomer incorporation capacity and higher productivity enables more economical polymerization processes and unlocks higher GP separation and lower density materials in gas-phase reactors. Figure 31 , 32 ).

[0753] It is worth noting that, as mentioned above, the performance of the present invention and the comparative metallocenes heterogeneous prepared using a one-step catalyst preparation method (Experiment 1) and a two-step catalyst preparation method (Experiment 2) is largely similar.

Claims

1. A method for preparing a multimodal polyethylene polymer, comprising: (I) In the first slurry phase stage, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized in the presence of a racemic metallocene catalyst comprising: (i) Complexes of formula (Ix) ， Each X is a σ donor ligand; Each Het is independently a monocyclic or polycyclic heterocyclic group containing at least one heteroatom selected from O, N or S; L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand; M is Ti, Zr, or Hf; Each R1 may be the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy Each n is between 0 and 3; Each R2 is either the same or different, and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group; Each R may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 3; (ii) a co-catalyst of a compound containing a Group 13 element; and optionally... (iii) Carrier; To form the first polyethylene component; (II) In the second gas phase stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form the second component.

2. The method of claim 1, wherein the first polyethylene component forms 30 to 70 wt% of the multimodal polyethylene polymer; The second component constitutes 30 to 70 wt% of the multimodal polyethylene polymer. The density of the multi-peaked polyethylene polymer is 900 to 980 kg / m³. 3 MFR2 was measured at 190°C and 2.16 kg load in the range of 0.01 to 50 g / 10 min, according to ISO 1133.

3. A method for preparing a multimodal polyethylene polymer, comprising: (I) Contacting a solid support with a co-catalyst containing a group 13 element and a solution of a racemic metallocene complex of formula (Ix). ， Each X is a σ donor ligand; Each Het is independently a monocyclic or polycyclic heterocyclic group containing at least one heteroatom selected from O, N or S; L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand; M is Ti, Zr, or Hf; Each R1 may be the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy Each n is between 0 and 3; Each R2 is either the same or different, and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group; Each R is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 3; To form a supported catalyst; (II) In the first slurry phase stage, in the presence of the supported catalyst, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized to form the first polyethylene component; (III) In the second gas phase stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form a second polyethylene component.

4. A method for preparing a multimodal polyethylene polymer, comprising: (I) Contacting a solid support with a co-catalyst solution containing a compound of Group 13 elements; To form a catalyst impregnation support; (II) Contact the catalyst-impregnated support with the racemic metallocene complex of formula (Ix). ， Each X is a σ donor ligand; Each Het is independently a monocyclic or polycyclic heterocyclic group containing at least one heteroatom selected from O, N or S; L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand; M is Ti, Zr, or Hf; Each R1 may be the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy Each n is between 0 and 3; Each R2 is either the same or different, and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group; Each R may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 3; To form a supported catalyst; (III) In the first slurry phase stage, in the presence of the supported catalyst, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized to form the first polyethylene component; (IV) In the second gas phase stage, in the presence of the product of step (I), ethylene and optionally at least one C4-10α olefin comonomer are polymerized to form a second polyethylene component.

5. The method according to any one of claims 1-4, wherein the co-catalyst is an aluminoxane.

6. The method according to any one of claims 1-4, wherein the carrier is a porous inorganic carrier.

7. The method according to any one of claims 1-4, wherein the complex of formula (Ix) is C2 symmetrical.

8. The method according to any one of claims 1-4, wherein each X is independently a hydrogen atom, a halogen atom, a carbon atom, or a hydrogen atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl, or benzyl.

9. The method according to any one of claims 1-4, wherein L is -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or optionally contains one or more heteroatoms or fluorine atoms from groups 14-16 of the periodic table. 20 - A hydrocarbon group, or optionally two R' groups together, can form a ring.

10. The method of any one of claims 1-4, wherein L is -R'2Si-, and each R' is independently C. 1-10 -alkyl, C 2-10 -Alkenyl, C 5-6 -cycloalkyl, C 1-10 -alkyl-OC 1-10 -alkyl, benzyl, or phenyl.

11. The method according to any one of claims 1-4, wherein R1 is a linear C 1-6 -alkyl.

12. The method of any one of claims 1-4, wherein the pre-polymerization step precedes the first polymerization stage.

13. The method according to any one of claims 1-4, wherein at least one comonomer is present in the first slurry phase stage or the second gas phase stage.

14. The method according to any one of claims 1-4, wherein the multimodal polyethylene polymer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.

15. The method according to any one of claims 1-4, wherein the complex has formula (Ia): ， Each X is a σ donor ligand; Each Het is independently a monocyclic or polycyclic heterocyclic group containing at least one heteroatom selected from O, N or S; L is a (RdRe)Si group, (RdRe)Ge, or (RdRe)C; Rd is C 1-10 Alkyl, C 5-10 cycloalkyl, benzyl, or phenyl; Re is C 2-10 alkenyl; M is Ti, Zr, or Hf; Each R1 may be the same or different, and is a straight chain C. 1-10 Alkyl or straight-chain C 1-10 Alkoxy; Each n is between 0 and 3; Each R2 is either the same or different, and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group; Each R may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 3.

16. The method according to any one of claims 1-4, wherein the complex has formula (V): ， Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl; Each Het is independently a monocyclic heterocyclic group containing at least one heteroatom selected from O or S; L is -R'2Si-, where each R' is independently C. 1-20 The C group is either a hydrocarbon group or a C group substituted with an alkoxy group having 1 to 10 carbon atoms. 1-10 alkyl; M is Ti, Zr, or Hf; Each R1 may be the same or different, and is a straight chain C. 1-6 Alkyl or straight-chain C 1-6 Alkoxy; Each n is between 1 and 2; Each R2 is either the same or different, and is C 1-6 Alkyl, C 1-6 Alkoxy or -Si(R)3 group; Each R may be the same or different, and is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 1.

17. The method according to any one of claims 1-4, wherein the complex has formula (VI): ， Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkyl, C 1-6 -alkoxy, amide, phenyl or benzyl; Each Het is independently a monocyclic heterocyclic group containing at least one heteroatom selected from O or S; L is -R'2Si-, where each R' is independently C. 1-10 Alkyl, C 3-8 cycloalkyl or C 2-10 alkenyl; M is Ti, Zr, or Hf; Each R1 may be the same or different, and is a straight chain C. 1-6 alkyl; Each n is between 1 and 2; Each R2 may be the same or different, and is a -Si(R)3 group; Each R is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 1.

18. The method according to any one of claims 1-4, wherein the complex has formula (VII): ， Each X is a σ donor ligand; L is a divalent bridge based on carbon, silicon, or germanium, in which one or two framework atoms connect to the ligand; Each R1 may be the same or different, and is a straight chain C. 1-6 alkyl; Each n is between 0 and 3; Each R2 is either the same or different, and is C 1-6 Alkyl or -Si(R)3 group; Each R is optionally divided by 1 to 3 Cs. 1-6 Alkyl-substituted C 1-10 Alkyl or phenyl; and Each p is between 0 and 3.

19. The method according to any one of claims 1-4, wherein the complex is , ,or .

20. The method of any one of claims 1-4, wherein the catalyst has a higher activity in the gas phase than in the slurry phase, and the gas phase activity / slurry phase activity ratio is 1.8 or higher.

21. The method according to any one of claims 1-4, wherein each Het is independently a monocyclic or polycyclic heteroaromatic group containing at least one heteroatom selected from O, N or S.

22. Use of a metallocene catalyst of formula (Ix) as defined in claim 1 in the preparation of a multimodal polyethylene polymer in a method comprising a first slurry circulation polymerization followed by a gas-phase polymerization, wherein the metallocene catalyst is used simultaneously in both the slurry circulation polymerization and the gas-phase polymerization.

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