Preparation of supported catalyst systems

Abstract

The present disclosure relates to a process for preparing a supported catalyst system, wherein the supported catalyst system comprises: (i) a metallocene complex of formula (I); (ii) a promoter system comprising an aluminoxane promoter; and (iii) a porous inorganic support; wherein the process comprises: a) reacting the porous inorganic support with the aluminoxane promoter in a first hydrocarbon solvent to obtain a support treated with the aluminoxane promoter; b) contacting the aluminoxane co-catalyst treated support with a solution to obtain the supported catalyst system wherein the solution comprises the metallocene complex of formula (I) and a second hydrocarbon solvent and the solution does not comprise an aluminoxane co-catalyst; wherein the metallocene complex of formula (I) is represented by formula (I). (I)

Description

Technical Field

[0001] This disclosure relates to a method for preparing a supported catalyst system, particularly a silica-supported catalyst system, for propylene polymerization, especially for the production of isotactic polypropylene. The invention also relates to the supported catalyst system and its use. Background Technology

[0002] Metallocene catalysts have been used in the production of polyolefins for many years. Numerous academic and patent publications describe the applications of these catalysts in olefin polymerization. Metallocenes are now used industrially, particularly cyclopentadienyl catalyst systems with different substitution modes, to produce polyethylene and polypropylene.

[0003] Metallocene catalysts have been used in propylene polymerization to achieve certain desired polymer properties. A suitable metallocene catalyst should possess both high activity and high productivity.

[0004] WO2018 / 122134 specifically describes the complex racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, which is activated with MAO and loaded onto silica.

[0005] WO2019 / 179959 describes bisindenyl ligand complexes and catalysts comprising these complexes. It relates to improving the preparation of specific C1-symmetric bisindenyl complexes by modifying an indenyl ligand to improve the selectivity of complex synthesis to the desired trans isomer, increase yield, and simplify complex purification. It also relates to the use of novel bisindenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers.

[0006] Despite significant work in the field of metallocene catalysts for polypropylene, several challenges remain, primarily concerning catalyst productivity or activity. Furthermore, a simple and cost-effective catalyst preparation process is required. Improving the production efficiency of the metallocene component itself is crucial, as it has the highest cost impact on the overall manufacturing cost of the catalyst.

[0007] Therefore, there remains a desire to find metallocene-based catalyst systems that offer high activity and productivity, particularly in the copolymerization of propylene with 4- to 8-C α-olefins and / or ethylene to form propylene copolymers, while also exhibiting more favorable production economics and longer-lasting stability. The desired catalysts should also demonstrate improved performance in the production of high molecular weight polypropylene polymers, especially homopolymers. Summary of the Invention

[0008] One object of this disclosure is to provide an improved method for preparing a supported catalyst system, characterized as described in the independent claim. Preferred embodiments are disclosed in the dependent claims.

[0009] Supported catalyst systems for olefin polymerization can mitigate the aforementioned drawbacks. The characteristics of the supported catalyst systems are as described in the independent claims.

[0010] One advantage of this preparation method is that the supported catalyst system can be produced by a simpler method and with a lower total amount of aluminoxane co-catalyst, thereby reducing production costs. The supported catalyst system of this disclosure obtained by this method surprisingly exhibits improved storage life. The use of the supported catalyst system of this disclosure unexpectedly leads to higher catalyst productivity and improved performance in the production of high molecular weight polymers derived from propylene, such as propylene homopolymers or propylene copolymers. Propylene polymers produced using the supported catalyst system of this disclosure have high purity because the polymers contain a lower amount of catalyst residue. Attached Figure Description

[0011] In the following, the present disclosure will be described in more detail with reference to the accompanying drawings, in which:

[0012] Figures 1 to 3 The kinetic curves of the catalysts tested in the examples using two different H2 concentrations are shown (the curves for each concentration are labeled A. and B. in each figure).

[0013] Figure 4 The 40-minute productivity of the catalysts with two MFR values ​​tested in the examples is shown.

[0014] Figure 5 The relationship between catalyst productivity and its aging time is shown.

[0015] Figure 6 The relationship between the melting point of hPP produced by the catalyst and the catalyst aging time is shown.

[0016] Figure 7 The relationship between the bulk density of hPP produced by the catalyst and the catalyst aging time is shown.

[0017] definition

[0018] The following definitions are used throughout this description:

[0019] The term "C1-C" 20 "-hydrocarbon group" includes C1-C 20 -alkyl, C2-C 20 -Alkenyl, C2-C 20 -Alynyl group, C3-C 20 -Cycloalkyl, C3-C 20 -cycloalkenyl, C6-C 20 -Aryl, C7-C 20 -alkylaryl and C7-C 20 -Arylalkyl, or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C1-C1 is preferred. 20 -The hydrocarbon group is C1-C 20 -alkyl, C4-C 20 -Cycloalkyl, C5-C 20 -cycloalkyl-alkyl, C7-C 20 -alkylaryl, C7-C 20 -Arylalkyl and C6-C 20 -Aryl, especially C1-C 10 -alkyl, C6-C 10 -Aryl and C7-C 12 -Arylalkyl, such as C1-C8-alkyl. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0020] The term "C1-C" 10 "-hydrocarbon group" includes C1-C 10 -alkyl, C2-C 10 -Alkenyl, C2-C 10 -Alynyl group, C3-C 10 -Cycloalkyl, C3-C 10 -cycloalkenyl, C6-C 10 -Aryl, C7-C 10 -alkylaryl and C7-C 10-Arylalkyl, or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C1-C1 is preferred. 10 -The hydrocarbon group is C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -alkylaryl, C7-C 10 -Arylalkyl and C6-C 10 -Aryl, especially C1-C 10 -alkyl, C6-aryl and C7-C 10 -Arylalkyl, such as C1-C6-alkyl. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0021] The term "C1-C8-alkyl" includes C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, C6-C8-aryl, C7-C8-alkylaryl, and C7-C8-arylalkyl, or of course, mixtures of these groups, such as alkyl-substituted cycloalkyl groups. Unless otherwise specified, preferred C1-C8-alkyl groups are C1-C8-alkyl, C4-C8-cycloalkyl, C5-C8-cycloalkyl-alkyl, C7-C8-alkylaryl, C7-C8-arylalkyl, and C6-C8-aryl, especially C1-C6-alkyl, C6-aryl, and C7-C8-arylalkyl, such as C1-C6-alkyl. The most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0022] The term "C1-C6-alkyl" includes C1-C6-alkyl, C2-C6-alkenyl, C2-C6-ynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C6-aryl (e.g., phenyl), or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, preferred C1-C6-alkyl groups are C1-C6-alkyl, C4-C6-cycloalkyl, C5-C6-cycloalkyl-alkyl, and C6-aryl, especially C1-C6-alkyl and C6-aryl, such as C1-C6-alkyl. Most particularly preferred alkyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, and phenyl.

[0023] The term “halo” or “halogen” includes fluorine, chlorine, bromine, and iodine groups, especially chlorine or fluorine groups, particularly when it comes to the definition of metallocene complexes.

[0024] The oxidation state of a metal ion is mainly determined by the properties of the metal ion under discussion and the stability of the individual oxidation state of each metal ion.

[0025] It should be understood that in the coordination compounds of the present invention, metal ions are coordinated by ligand X to satisfy the valence of the metal ion and fill its available coordination sites. The properties of these σ ligands can vary considerably.

[0026] In this application, catalyst activity is defined as the amount of polymer produced per gram of catalyst per hour. Metallocene activity is defined herein as the amount of polymer produced per gram of metal per hour. The term productivity is sometimes used to describe catalyst activity, although herein it refers to the amount of polymer produced per unit weight of catalyst.

[0027] The term “molecular weight” as used in this article refers to weight-average molecular weight Mw, unless otherwise stated.

[0028] The term “consistently composed of” as used herein refers to the presence of other components that do not substantially affect the essential characteristics of the compound or composition, such as trace amounts of impurities. Detailed Implementation

[0029] This disclosure relates to an improved method for preparing supported catalyst systems.

[0030] This article provides a method for preparing a supported catalyst system. The supported catalyst system comprises:

[0031] (i) Metallocene complexes of formula (I);

[0032] (ii) A cocatalyst system containing an aluminoxane cocatalyst; and

[0033] (iii) Porous inorganic carrier.

[0034] The metallocene complex of formula (I) is

[0035]

[0036] (I)

[0037] in:

[0038] Mt is either Zr or Hf;

[0039] X is a monoanion ligand;

[0040] R 1 Same or different, where each R 1 Independently selected from H and C1-C8-alkyl groups, wherein the C1-C8 alkyl group optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms;

[0041] R 2 and R 2 Each is independently CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6 alkyl, C3-C8 cycloalkyl, or C6-C 10 Aryl;

[0042] R 3 Same or different, and R 4 Same or different, where each R 3 and each R 4 Independently selected from H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl, OY and NY2 groups (where each Y is independently C1-C) 10 - hydrocarbon group) and / or two adjacent R 3 Or two adjacent R 4 Together with the two carbon atoms of the benzene ring they are bonded to, they form a 4- to 7-atom ring;

[0043] Each R 5 R 6 and R 7 Independently selected from hydrogen and C1-C 20 -hydrocarbon group (where the C1-C 20 - The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms, or an OY group (where Y is C1-C). 10 - hydrocarbon group), and / or R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7 One of the C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4- to 7-atom ring, provided that (i) when R 7 When it is H, then R 5 and R 6 Neither of them is H, and (ii) only if R 7 When it is not H, R 5 and R 6 Only then can it be hydrogen;

[0044] R 5 'and R 6 Each is independently C1-C 20 -hydrocarbon group (where the C1-C 20 -The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms or an OY group (where Y is C1-C). 10-hydrocarbon group), and optionally wherein R 5 'C1-C 20 - Hydrocarbon group and R 6 'C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring.

[0045] Methods for preparing supported catalyst systems include:

[0046] a) Reacting a porous inorganic support with an aluminoxane co-catalyst in a first hydrocarbon solvent to obtain a support treated with the aluminoxane co-catalyst; and

[0047] b) Contacting a support treated with an aluminoxane cocatalyst with a solution to obtain a supported catalyst system, wherein the solution contains a metallocene complex of formula (I) and a second hydrocarbon solvent, and the solution does not contain an aluminoxane cocatalyst.

[0048] When preparing supported catalyst systems, the solution in contact with the support treated with aluminoxane co-catalyst (see b above) includes an additional amount of aluminoxane co-catalyst (e.g., MAO). This second impregnation of the support can be problematic.

[0049] Typically, the solutions used for the second impregnation are chemically unstable. Components in the solution (e.g., MAO, TMA, and metallocene complexes) react with each other, which can lead to deactivation of the metallocenes over time and poor batch-to-batch reproducibility. When the solution containing metallocene complexes also contains a borate cocatalyst, the additional presence of the aluminoxane cocatalyst can cause loss and leaching of the borate. Furthermore, in cases of incomplete impregnation of the support or overfilling of pores, the solution can leave an active catalyst layer on the particle surface, which can result in poor morphology.

[0050] Unexpectedly, it was discovered that the second aluminum oxane co-catalyst is unnecessary for the specific metallocene complexes of this disclosure. One reason for including the aluminum oxane co-catalyst in the solution containing the metallocene complex is to facilitate the dissolution of the metallocene. However, the metallocene complexes of this disclosure have relatively high solubility in a second hydrocarbon solvent (e.g., toluene), which is part of the solution used to contact the support treated with the aluminum oxane co-catalyst.

[0051] There are several advantages to avoiding further treatment of the aluminum oxane co-catalyst after the support has been pre-treated with it (e.g., when contacting the treated support with the metallocene complex). When the aluminum oxane co-catalyst is used a second time in the support treatment step, approximately 10% of the total aluminum oxane catalyst used in the entire process is used for this second treatment step. By excluding the aluminum oxane catalyst from the second treatment step, cost savings are achieved by eliminating the 10% of aluminum oxane catalyst typically used in catalyst production. Therefore, the supported catalyst system has a lower aluminum content. This method also avoids the potential negative impacts associated with the presence of trimethylaluminum (TMA) in catalyst polymerization. However, the greatest benefit is the simpler catalyst preparation procedure, as the metallocene solution without the aluminum oxane co-catalyst eliminates a step involving sampling and treatment of the aluminum oxane co-catalyst.

[0052] This disclosure also provides supported catalyst systems obtained or obtainable by methods for preparing supported catalyst systems. Supported catalyst systems with high activity and productivity can be obtained by preparing the catalyst system according to the invention. The supported catalyst system is infinitely stable at room temperature, unlike when an aluminoxane co-catalyst is present.

[0053] This disclosure also provides a method for preparing polypropylene homopolymers or polypropylene copolymers of one or more C2 to 8 α-olefin comonomers. The method comprises polymerizing propylene and optionally one or more C2 to 8 α-olefin comonomers in the presence of the supported catalyst system of this disclosure. The polypropylene homopolymers or copolymers produced using the supported catalyst system of this disclosure have high purity because the polymers contain low levels of catalyst residues.

[0054] This disclosure also provides the use of supported catalyst systems for the production of propylene polymers, such as propylene homopolymers or polypropylene copolymers of one or more C2 to 8 α-olefin comonomers.

[0055] Furthermore, this disclosure provides a polypropylene homopolymer or a polypropylene copolymer of one or more C2 to 8 α-olefin comonomers. The polypropylene homopolymer or polypropylene copolymer is obtained by the method of preparing the polypropylene homopolymer or the polypropylene copolymer of one or more C2 to 8 α-olefin comonomers disclosed herein.

[0056] Supported catalyst system

[0057] The supported catalyst system comprises, preferably substantially, the following components, and more preferably, the following components:

[0058] (i) Metallocene complexes of formula (I) as described herein;

[0059] (ii) A cocatalyst system containing an aluminoxane cocatalyst; and

[0060] (iii) Porous inorganic carrier.

[0061] Metallocene complexes (i)

[0062] The metallocene suitable for the catalyst of this invention is a racemic trans-configured bridged asymmetric bis-indenyl metallocene. For the purposes of this invention, racemic-trans refers to the two indenyl ligands being oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-cis refers to the two indenyl ligands being oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the figure below.

[0063]

[0064] In this invention, metallocene complexes of formula (I) and any subform are intended to cover both cis and trans configurations. Preferably, metallocene complexes of formula (I) and any subform are in the trans configuration.

[0065] The metallocene complexes of the present invention are preferably used in the form of racemic trans isomers. Therefore, ideally, at least 95 mol%, for example at least 98 mol%, and especially at least 99 mol%, of the metallocene complexes are in the racemic trans isomer form.

[0066] The metallocene complexes of the present invention are preferably C1-symmetrical.

[0067] Therefore, the present invention utilizes the metallocene complex of formula (I).

[0068]

[0069] (I)

[0070] in:

[0071] Mt is either Zr or Hf;

[0072] X is a monoanion ligand;

[0073] R 1 Same or different, where each R 1 Independently selected from H and C1-C8-alkyl groups, wherein the C1-C8 alkyl group optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms;

[0074] R 2 and R 2 Each is independently CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6 alkyl, C3-C8 cycloalkyl, or C6-C10 Aryl;

[0075] R 3 Same or different, and R 4 Same or different, where each R 3 and each R 4 Independently selected from H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl, OY and NY2 groups (where each Y is independently C1-C) 10 - hydrocarbon group) and / or two adjacent R 3 Or two adjacent R 4 Together with the two carbon atoms of the benzene ring they are bonded to, they form a 4- to 7-atom ring;

[0076] Each R 5 R 6 and R 7 Independently selected from hydrogen and C1-C 20 -hydrocarbon group (where the C1-C 20 - The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms, or an OY group (where Y is C1-C). 10 - hydrocarbon group), and / or R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7 One of the C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4- to 7-atom ring, provided that (i) when R 7 When it is H, then R 5 and R 6 Neither of them is H, and (ii) only if R7 is not H, R 5 and R 6 Only then can it be hydrogen;

[0077] R 5 'and R 6 Each is independently C1-C 20 -hydrocarbon group (where the C1-C 20 - The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms, or an OY group (where Y is C1-C). 10 -hydrocarbon group), and optionally wherein R 5 'C1-C 20 - Hydrocarbon group and R 6 'C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring.

[0078] For the metallocene complex of formula (I) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0079] In the complex of formula (I), Mt is preferably Zr or Hf, with Zr being more preferred.

[0080] Each X is a monoanion ligand. Preferably, each X is independently identical or different from one another, and is H, a halogen, or a C1-C ligand. 10 -Hydrocarbon group (where C1-C) 10 - The hydrocarbon group optionally contains up to two Si, O, S, N or P atoms, an OY' group or an NY'2 group, wherein each Y' is independently identical or different, preferably identical, and is C1-C 10 -Hydrocarbon group. In other words, each monoanion ligand is selected from H, halogens, and C1-C. 10 -Hydrocarbon group.

[0081] C1-C 10 The hydrocarbon group optionally contains up to two Si, O, S, N or P atoms, an OY' group or an NY'2 group, preferably a C1-C6-alkoxy or an R' group, wherein R' is a C1-C6-alkyl, phenyl or benzyl group. C1-C6 is preferred. 10 The hydrocarbon group does not contain Si, O, S, N or P atoms, OY' group or NY'2 group.

[0082] More preferably, each X is independently the same as or different from each other, and is H, Cl, F, C1-C6-alkoxy, or R' group, wherein R' is C1-C6-alkyl, phenyl, or benzyl. Even more preferably, each X is independently the same as or different from each other, and is Cl, benzyl, or methyl. Most preferably, each X is independently the same as or different from each other, and is Cl or methyl.

[0083] Typically, it is preferred that both X groups are identical. More preferably, both X groups are either Cl or methyl.

[0084] In some implementations, both X groups are Cl.

[0085] In some implementations, both X groups are methyl groups.

[0086] Advantageously, when neither of the two X groups is halogenated, the metallocene complex is halogen-free, and the resulting supported catalyst system is likely to be halogen-free.

[0087] Preferably, the supported catalyst system does not contain halogens, and more preferably, it does not contain fluorine and / or chlorine. Halogens are not intentionally added to the supported catalyst system. Halogens can be introduced into the supported catalyst system when the X group on the metallocene complex is a halogen. Fluorine can also be introduced into the supported catalyst system when a boron cocatalyst (e.g., trirityl tetrakispentafluoro-phenylborate) is used.

[0088] Preferably, R 1 Each is independently identical or different from the others, and is an H or C1-C8-alkyl group, wherein the C1-C8-alkyl group does not contain heteroatoms (e.g., at most two silicon, oxygen, sulfur, or nitrogen atoms). More preferably, each R 1 Independently identical or different from each other, they are H, C1-C8-alkyl, C4-C8-cycloalkyl, phenyl, or C7-C8-arylalkyl. Even more preferably, each R 1 Independently identical or different from each other, they are H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, or phenyl. Most preferably, one R 1 Selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl, another R 1 It is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl.

[0089] Typically, two Rs are preferred. 1 The groups are the same. More preferably, the two R groups are the same. 1 They are all methyl groups.

[0090] R 2 and R 2 Each is independently CH2-R 21 , where each R 21 It is independently H or a straight-chain or branched C1-C6 alkyl, C3-C8 cycloalkyl or C6-C 10 Aryl. Preferably, R 2 and R 2 'Each is independently the same as or different from the others, which is CH2-R' 21 , where each R 21 Independently, it is an H or a straight-chain or branched C1-C6-alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. More preferably, each R 21 Independently identical or different from each other, they are H, straight-chain C1-C3-alkyl, or branched C3-alkyl. Even more preferably, each R 21 They are either identical or different from each other independently, and are H or methyl.

[0091] R is also preferred 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2 'It is methyl or ethyl.' In some embodiments, R 2 and R 2 'Independently, it is methyl or ethyl.'

[0092] Typically, R is preferred. 2 and R 2 'They are the same. Therefore, R 2 and R 2 Each is CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group (e.g., R). 21 For R 2 and R 2 (The same), preferably H or a straight-chain C1-C3-alkyl group, more preferably H or a methyl group. Therefore, R 2 and R 2 'They can all be methyl or all be ethyl, but more preferably they can all be methyl.'

[0093] In some implementation schemes, R 2 and R 2 One of them is a methyl group, and the other has the formula CH2-R. 21 , where R 21 It is a C1-C6-alkyl group. In such an embodiment, R 2 and R 2 'non-methyl R 21 Preferably, it is a C1-C4-alkyl; more preferably, it is a straight-chain C1-C4-alkyl, and even more preferably, it is methyl or ethyl.

[0094] In some implementation schemes, R 2 It is methyl, R 2 'Having the formula CH2-R 21 , where R 21 It is a C1-C6-alkyl group. In such an embodiment, R 2 'of R 21 Preferably, it is a C1-C4-alkyl; more preferably, it is a straight-chain C1-C4-alkyl, and even more preferably, it is methyl or ethyl.

[0095] In a preferred embodiment, R 2 It is methyl or ethyl, R 2 'Is methyl or ethyl. In a more preferred embodiment, R 2 and R 2 Independently, it is methyl or ethyl. Most preferably, R 2 and R 2'They are all methyl or they are all ethyl.'

[0096] R 3 Same or different, R 4 Same or different, where each R 3 and each R 4 Independently selected from H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl, OY and NY2 groups (where each Y is independently C1-C) 10 - hydrocarbon group) and / or two adjacent R 3 Or two adjacent R 4 Together with the two carbon atoms of the benzene ring to which they are bonded, they form a 4 to 7 atomic ring.

[0097] Two adjacent R 3 Or two adjacent R 4 They can form a ring together with the two carbon atoms of the benzene ring they are bonded to. Preferably, two adjacent carbon atoms are present. 3 Or two adjacent R 4 It forms 5 to 6 atomic rings.

[0098] When two adjacent R 3 Or two adjacent R 4 When a 4- to 7-atom ring is formed, the ring is preferably a carbon ring. The ring is preferably a C4-C8 ring, more preferably a C5-C6 ring, and even more preferably a C6 ring.

[0099] Preferred for each R 3 and R 4 They are independently identical or different from each other, and are H, C1-C6-alkyl or C6-C 20 -aryl, more preferably H or C1-C4-alkyl. Even more preferably, each R 3 and each R 4 Each is independently the same as or different from the others, and is H, methyl, ethyl, isopropyl or tert-butyl, especially H, methyl or tert-butyl.

[0100] Preferably at least one R 3 Not H, and at least one R 4 Not H. More preferably any of the following: (a) at least two R 3 Not H, and at least one R 4 It is not H, or (b) at least one R. 3 Not H, and at least two Rs 4 Not H.

[0101] Furthermore, each benzene ring (e.g., with R) can be... 3and R 4 They have the same substitution pattern, or these benzene rings have different substitution patterns.

[0102] Preferably at least two R 3 Group and / or at least two R 4 The group is H. If the three R groups are H, then... 3 Group and / or three R 4 If the group is H, then the remaining R 3 and / or R 4 The group is preferably located in the meta position. If four R groups are present... 3 Group and / or four R 4 If the group is H, then the remaining R 3 and / or R 4 The groups are preferably located at the para position. The meta or para position refers to R... 3 Or R 4 The position of the group attached to the benzene ring.

[0103] Advantageously, at least two R 3 It is H, more preferably, at least three Rs. 3 It's H. The remaining R 3 It can be the same (e.g., the remaining R) 3 It is methyl), and can be, for example, 3',5'-dimethyl. Or, there is only one R. 3 It is not H, for example, it is 4'-tert-butyl.

[0104] Advantageously, at least two R 4 It is H, more preferably, at least three Rs. 4 It's H. The remaining R 4 It can be the same (e.g., the remaining R) 4 It is methyl or tert-butyl), and can be, for example, 3',5'-dimethyl or 3',5'-ditert-butyl.

[0105] Each R 5 R 6 and R 7 Independently selected from hydrogen and C1-C 20 -Hydrocarbon group. C1-C 20 -The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms or an OY group (where Y is C1-C). 10 - hydrocarbon group) and / or R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7 One of the C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4- to 7-atom ring, provided that (i) when R 7 When it is H, then R 5and R 6 Neither of them is H, and (ii) only if R 7 When it is not H, R 5 and R 6 Only then can it be hydrogen;

[0106] By R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7 One of the C1-C 20 The 4- to 7-atom ring formed by the hydrocarbon group and the two carbon atoms of the benzene ring may optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms. Preferably, the 4- to 7-atom ring is a 4- to 7-atom carbon ring.

[0107] R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7 One of the C1-C 20 - Hydrocarbon groups can link together to form a ring. In other words, R 6 C1-C 20 - Hydrocarbon groups can be covalently bonded to R 5 and R 7 One of the C1-C 20 -Hydrocarbon group.

[0108] When R 6 With R 5 and R 7 When one of them and the two C atoms of the benzene ring they are bonded to form a 4 to 7-atom ring, R is preferred. 6 It is a C1-C3- hydrocarbon group, and R forms a 4- to 7-atom ring. 5 and R 7 One of them is the C1-C2- hydrocarbon group.

[0109] Preferred from R 6 hydrocarbon group and R 5 and R 7 One of the hydrocarbon groups, together with the two C atoms of the benzene ring, forms a 4 to 7-atom ring, which is a 5 or 6-atom ring, preferably a 5-atom ring.

[0110] (i) R 7 When it is H, then R 5 and R 6 Neither of them is H, and (ii) only if R 7 When it is not H, R 5 and R 6 Only then can it be hydrogen. In other words, R on the benzene ring 5 and R 7 At least one substituent at a position is not hydrogen.

[0111] When R7 If it is not H, then each R 5 and R 6 It can be hydrogen and C1-C independently. 20 -Hydrocarbon group, as defined herein.

[0112] Preferred for each R 5 R 6 and R 7 C atoms independently selected from hydrogen, straight-chain, or branched chains 1-6 Alkyl, C 7-20 Arylalkyl, C 7-20 alkylaryl and C 6-20 aryl, and / or R 6 It is a C1-C3-hydrocarbon group, R 5 and R 7 One of them is a C1-C2-hydrocarbon group, where R 6 C1-C3- hydrocarbon groups and R 5 and R 7 One of the C1-C2- hydrocarbon groups forms a 4- to 7-atom ring, preferably a 5- to 6-atom ring, together with the two C atoms of the benzene ring to which it is bonded, provided that (i) when R 7 When it is H, then R 5 and R 6 Neither of them is H, and (ii) only if R 7 When it is not H, R 5 and R 6 Only then can it be hydrogen.

[0113] In one instance, each R 5 and R 6 C atoms independently selected from hydrogen, straight-chain, or branched chains 1-6 Alkyl, C 7-20 Arylalkyl, C 7-20 alkylaryl and C 6-20 aryl, and / or R 6 It is a C1-C3-hydrocarbon group, R 5 It is a C1-C2- hydrocarbon group, where R 6 C1-C3- hydrocarbon groups and R 5 The C1-C2- hydrocarbon groups, together with the two C atoms of the benzene ring to which they are bonded, form a 4- to 7-atom ring, preferably a 5- to 6-atom ring, especially a 5-atom ring. 7 It is a straight-chain or branched C1-6 alkyl, C7- 20 Arylalkyl, C7- 20 alkylaryl or C6- 20 Aryl.

[0114] In this example, it is preferred that each R 5 and R 6 Independently selected from hydrogen and straight-chain or branched C1-6 Alkyl, and / or R 6 It is a C1-C3-hydrocarbon group, R 5 It is a C1-C2- hydrocarbon group, where R 6 C1-C3- hydrocarbon groups and R 5 The C1-C2- hydrocarbon groups, together with the two C atoms of the benzene ring to which they are bonded, form a 5- to 6-atom ring, preferably a 5-atom ring, R 7 It is C 7-20 alkylaryl or C 6-20 Aryl. More preferably, R 6 It is a C1-C3-hydrocarbon group, R 5 It is a C1-C2- hydrocarbon group, where R 6 C1-C3- hydrocarbon groups and R 5 The C1-C2- hydrocarbon groups, together with the two C atoms of the benzene ring they are bonded to, form a 5- to 6-atom ring, R 7 It is C 7-20 Alkyl aryl.

[0115] R 5 'and R 6 Each is independently C1-C 20 -Hydrocarbon group (where C1-C) 20 -The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms or an OY group (where Y is C1-C). 10 -hydrocarbon group), and optionally wherein R 5 'C1-C 20 - Hydrocarbon group and R 6 'C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring.

[0116] By R 5 'C1-C 20 - Hydrocarbon group and R 6 'C1-C 20 - The 4 to 7-atom ring formed by the hydrocarbon group and the two C atoms of the benzene ring may optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms.

[0117] R 5 'C1-C 20 - Hydrocarbon group and R 6 'C1-C 20 - Hydrocarbon groups can link together to form a ring. In other words, R 5 'C1-C 20 - Hydrocarbon group covalently bonded to R 6 'C1-C 20 -Hydrocarbon group.

[0118] When R 5 'and R6 When R forms a 4- to 7-atom ring together with the two C atoms of the benzene ring to which they are bonded, R is preferred. 5 'It is a C1-C3-hydrocarbon group, R 6 These are C1-C2-hydrocarbon groups that form a 4- to 7-atom ring. This 4- to 7-atom ring may optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms. Preferably, the 4- to 7-atom ring is a 4- to 7-atom carbon ring.

[0119] Preferred from R 5 ' of hydrocarbon group and R 6 The 4 to 7-atom ring formed by the hydrocarbon group and the two C atoms of the benzene ring is a 5 or 6-atom ring, more preferably a 5-atom ring.

[0120] Preferably, R 5 'and R 6 Each is independently C1-C 10 -Hydrocarbon group, where C1-C 10 -The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms or an OY group, wherein Y is C1-C. 10 -Hydrocarbon group. More preferably, R 5 'and R 6 Each C is either a straight chain or a branched chain. 1-6 Alkyl, straight-chain or branched C 1-6 Alkoxy, C 7-10 Arylalkyl, C 7-10 arylalkoxy, C 7-10 alkylaryl, C 7-10 Alkyl aryloxy, C 6-10 Aryl or C 6-10 Aryloxy.

[0121] In one instance, R 5 'and R 6 Each C is either a straight chain or a branched chain. 1-6 Alkyl, straight-chain or branched C 1-6 Alkoxy, phenyl-C 1-4 -alkyl, phenyl-C 1-4 Alkoxy, C 1-4 Alkylphenyl, C 1-4 Alkylphenoxy, phenyl, or phenoxy. Preferably, R 5 'and R 6 Each C is either a straight chain or a branched chain. 1-6 Alkyl, straight-chain or branched C 1-6 Alkyl or phenyl. More preferably, R 5 'Is it a straight chain or a branched chain C?' 1-6 Alkoxy, R 6 'Is it a straight chain or a branched chain C?' 1-6 alkyl.

[0122] From another perspective, the present invention utilizes the metallocene complex of formula (II):

[0123]

[0124] (II)

[0125] in:

[0126] Mt is either Zr or Hf;

[0127] X is a monoanion ligand;

[0128] R 1 Same or different, where each R 1 Independently selected from H and C1-C8-alkyl groups, wherein the C1-C8 alkyl group optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms;

[0129] R 2 and R 2 Each is independently CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6 alkyl, C3-C8 cycloalkyl, or C6-C 10 Aryl;

[0130] R 3 Same or different, and R 4 Same or different, where each R 3 and each R 4 Independently selected from H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl, OY and NY2 groups (where each Y is independently C1-C) 10 - hydrocarbon group) and / or two adjacent R 3 Or two adjacent R 4 Together with the two carbon atoms of the benzene ring they are bonded to, they form a 4- to 7-atom ring;

[0131] Each R 5 R 6 and R 7 Independently selected from hydrogen and C1-C 20 -Hydrocarbon group (where C1-C) 20 -The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms or an OY group (where Y is C1-C). 10 - hydrocarbon group), and / or R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7One of the C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4- to 7-atom ring, provided that (i) when R 7 When it is H, then R 5 and R 6 Neither of them is H, and (ii) only if R 7 When it is not H, R 5 and R 6 Only then can it be hydrogen;

[0132] R 5 "and R 6 Each is independently C1-C 10 -hydrocarbon group (where the C1-C 10 -The hydrocarbon group optionally contains at most one silicon, oxygen, sulfur, or nitrogen atom, or an OY group (where Y is C1-C). 10 -hydrocarbon group), and optionally wherein R 5 "C1-C 10 - Hydrocarbon group, R 5 "Bonded oxygen atoms and R" 6 'C1-C 10 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring.

[0133] In this paper, the descriptions of Mt, X, and R for metallocene complexes of formula (I) are as follows. 1 R 2 R 2 '、R 3 R 4 R 5 R 6 R 6 'and R 7 Each definition also applies to metallocene complexes of formula (II), unless the context otherwise requires. R 5 The definition of ' applies to R shown in equation (II) 5 "O group, as long as R" 5 The definition of 'allows the presence of oxygen atoms.

[0134] For the metallocene complex of formula (II) defined above, the following represent preferred embodiments, which can be selected individually or in combination.

[0135] By R 5 "C1-C 10 - Hydrocarbon group, R 5 "The bonded oxygen atom and R" 6 'C1-C 10 - The 4- to 7-atom ring formed by the hydrocarbon group and the two carbon atoms of the benzene ring may optionally contain another silicon, oxygen, sulfur, or nitrogen atom. In formula (I), the 4- to 7-atom ring has at least R5 The 'position' contains one oxygen atom.

[0136] R 5 "C1-C 10 - Hydrocarbon group and R 6 'C1-C 10 - Hydrocarbon groups can link together to form a ring. In other words, R 5 "C1-C 10 - Hydroxyl group covalently bonded to C1-C of R6' 10 -Hydrocarbon group.

[0137] When R 5 "、R 5 "The bonded oxygen atom and R" 6 When R forms a 4- to 7-atom ring together with the two C atoms of the benzene ring to which they are bonded, R is preferred. 5 "It is a C1-C2-hydrocarbon group, R" 6 These are C1-C2-hydrocarbon groups that form a 4- to 7-atom ring. This 4- to 7-atom ring may optionally contain further silicon, oxygen, sulfur, or nitrogen atoms. Preferably, the 4- to 7-atom ring contains a total of 1 or 2 oxygen atoms (e.g., R...). 6 'Is R 6 "O, where R" 6 "is with R" 5 The covalent bond or C1-alkyl group).

[0138] Preferred from R 5 "hydrocarbon group, R 5 "The bonded oxygen atom and R" 6 The hydrocarbon group and the two carbon atoms of the benzene ring together form a 4 to 7-atom ring, which is a 5 or 6-atom ring.

[0139] Preferably, R 5 "Is it a straight chain or a branched chain?" 1-6 Alkyl, C 7-10 Arylalkyl, C 7-10 alkylaryl or C 6-10 Aryl; and R 6 'Is it a straight chain or a branched chain C?' 1-6 Alkyl, straight-chain or branched C 1-6 Alkoxy, C 7-10 Arylalkyl, C 7-10 arylalkoxy, C 7-10 alkylaryl, C 7-10 Alkyl aryloxy, C 6-10 Aryl or C 6-10 Aryloxy group. R 6 It can be defined as in equation (I) above.

[0140] In one instance, R 5"Is it a straight chain or a branched chain?" 1-6 Alkyl, phenyl-C 1-4 -alkyl, C 1-4 Alkylphenyl or phenyl. Preferably, R 5 "Is it a straight chain or a branched chain?" 1-6 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, or hexyl, preferably methyl or ethyl, more preferably methyl.

[0141] From another perspective, the present invention utilizes the metallocene complex of formula (III):

[0142]

[0143] (III)

[0144] in:

[0145] Each Y is independently H or C1-C 10 -hydrocarbon group; and

[0146] n is 2, 3, or 4.

[0147] The descriptions of Mt, X, and R in the metallocene complexes of formulas (I) and (II) in this paper 3 R 4 R 5 "、R 6 'and R 7 Each definition also applies to metallocene complexes of formula (III), unless the context otherwise requires. 5 The definition of ' applies to R shown in equation (III) 5 "O group, as long as R" 5 The definition of 'allows the presence of oxygen atoms.

[0148] For the metallocene complex of formula (III) defined above, the following represent preferred embodiments, which can be selected individually or in combination.

[0149] Preferably, n is 3 or 4. In one instance, n is 3. In another instance, n is 4.

[0150] Preferably, each Y is independently an H or C1-C4-alkyl group. It is also preferred that the C1-C4-alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0151] More preferably, each Y is H.

[0152] Preferred metallocene complexes are selected from:

[0153] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0154] Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0155] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0156] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0157] Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0158] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0159] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0160] Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0161] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0162] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0163] Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; and

[0164] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium.

[0165] From another perspective, the present invention utilizes a metallocene complex of formula (IV):

[0166]

[0167] (IV)

[0168] in:

[0169] Each Y is independently H or C1-C 10 -hydrocarbon group; and

[0170] n is 2, 3, or 4.

[0171] In this paper, the descriptions of Mt, X, and R for metallocene complexes of formulas (I) to (III) are as follows. 3 R 4 R 5 "、R 6 Each definition of ', Y, and n also applies to metallocene complexes of equation (III), unless the context otherwise requires. 5 The definition of ' applies to R shown in equation (IV) 5 "O group, as long as R" 5 The definition of 'allows the presence of oxygen atoms.

[0172] For the metallocene complexes of formula (IV) defined above, the following represent preferred embodiments, which can be selected individually or in combination.

[0173] Preferred for each R 3 and each R 4 Independently selected from H and straight-chain or branched C1-C6-alkyl groups.

[0174] Preferred is any one of the following: (a) R with a bit position (e.g., 4' bits). 3 It is a straight-chain or branched C1-C6-alkyl group, with R in the meta position (e.g., at the 3' and 5' positions). 3 The group is H, or (b) meta-position (e.g., 3' and 5' positions) R. 3 The group is a straight-chain or branched C1-C6-alkyl group, with R at the para position (e.g., the 4' position). 3 It is H.

[0175] Preferred is any one of the following: (a) R with a bit position (e.g., 4' bits). 4 It is a straight-chain or branched C1-C6-alkyl group, with R in the meta position (e.g., at the 3' and 5' positions). 4 The group is H, or (b) meta-position (e.g., 3' and 5' positions) R. 4 The group is a straight-chain or branched C1-C6-alkyl group, with R at the para position (e.g., the 4' position). 4 It is H.

[0176] From another perspective, the present invention utilizes a metallocene complex of formula (V):

[0177]

[0178] (V).

[0179] In this paper, the metallocene complexes of formulas (I) to (IV) are described for Mt, X, and R. 3 and R 4 Each definition also applies to metallocene complexes of formula (V), unless the context otherwise requires.

[0180] Preferred metallocene complexes are selected from:

[0181] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0182] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0183] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0184] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0185] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0186] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0187] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0188] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0189] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0190] Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride;

[0191] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0192] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0193] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0194] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0195] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0196] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0197] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0198] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0199] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0200] Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium;

[0201] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0202] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0203] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0204] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0205] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0206] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0207] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0208] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0209] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0210] Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride;

[0211] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0212] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0213] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0214] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0215] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0216] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0217] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0218] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium;

[0219] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; and

[0220] Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium.

[0221] The metallocene complexes disclosed herein can be prepared as described in WO2018 / 122134 or WO2019 / 179959.

[0222] Co-catalyst system (ii)

[0223] To form active catalytic species, a co-catalyst well known in the art is typically required. Co-catalysts comprising one or more organoaluminum compounds capable of activating metallocene catalysts are suitable for use in this invention.

[0224] According to the present invention, the cocatalyst system comprising an aluminoxane cocatalyst is advantageously used in combination with the metallocene complexes defined above.

[0225] The preferred cocatalyst system comprises an aluminoxane cocatalyst as the sole cocatalyst in the supported catalyst system. Therefore, the cocatalyst system can consist essentially of an aluminoxane cocatalyst, or be composed of only an aluminoxane cocatalyst. Thus, apart from the aluminoxane cocatalyst, no other cocatalysts containing one or more Group 13 metal compounds (such as organoboron and / or borate compounds (e.g., boron cocatalysts)) are used to activate the metallocene complexes in the supported catalyst system.

[0226] The advantage of using only aluminoxane cocatalysts is the absence of fluorine in the supported catalyst system. Therefore, any propylene polymer produced using a supported catalyst system will be free of fluorine and fluorinated derivatives.

[0227] The appropriate amount of co-catalyst is well known to those skilled in the art.

[0228] Preferably, the amount of co-catalyst is selected to achieve the molar ratio defined below.

[0229] The molar ratio of Al from the aluminoxane cocatalyst to the metal ion (Mt) (preferably zirconium) of the metallocene complex, Al / Mt, can be in the range of 10:1 to 2000:1 mol / mol, preferably 50:1 to 1000:1, and more preferably 100:1 to 600:1 mol / mol.

[0230] Aluminoxane co-catalyst

[0231] Aluminoxane co-catalysts can be one of formula (A):

[0232]

[0233] (A)

[0234] Where n is typically 6 to 20, and R has the following meanings.

[0235] Aluminoxanes are formed through the partial hydrolysis of organoaluminum compounds, such as those of the formula 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).

[0236] The preferred aluminum oxane cocatalyst is methylaluminoxane (MAO).

[0237] Since the aluminoxanes used as cocatalysts according to the present invention are prepared by means of their own process rather than as pure compounds, the molar concentrations of the aluminoxane solutions mentioned below are based on their aluminum content.

[0238] Porous inorganic carrier (iii)

[0239] The supported catalyst system of the present invention includes a porous inorganic support. The porous inorganic support is a particulate porous inorganic support material.

[0240] The preferred porous inorganic support is silica, alumina, or a mixed oxide, such as silica-alumina. More preferably, the porous inorganic support is silica.

[0241] The inorganic carrier is a porous material that allows 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, EP18282666 and US6,043,180.

[0242] The average particle size of porous inorganic supports (such as silica supports) can typically be 10 to 100 μm. However, it has been shown that if the average particle size of the support is 15 to 80 μm, preferably 18 to 50 μm, special advantages can be obtained.

[0243] The average pore size of porous inorganic supports (e.g., silica supports) can range from 10 to 100 nm, and the pore volume can range from 1 to 3 mL / g. The pore diameter of porous inorganic supports (e.g., silica supports) can range from 20 to 40 nm.

[0244] The surface area of ​​porous inorganic supports (such as silica supports) can typically range from 100 to 400 m². 2 Within the range of / g.

[0245] Examples of suitable support materials are, for example, ES757 manufactured and sold by PQ Corporation, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech Co. The support may optionally be calcined prior to its use in catalyst preparation to achieve optimal silanol group content.

[0246] The use of these carriers is common practice in this field.

[0247] The supported catalyst system may contain 5 to 500 pmol (e.g. 10 to 100 pmol) of transition metal per gram of support (e.g., silica) and 3 to 15 mmol of Al per gram of support (e.g., silica).

[0248] Methods for preparing supported catalyst systems

[0249] Methods for preparing supported catalyst systems include, preferably, essentially comprising, and more preferably, comprising:

[0250] A porous inorganic support is reacted with an aluminoxane co-catalyst in a first hydrocarbon solvent to obtain a support treated with the aluminoxane co-catalyst; and

[0251] A support treated with an aluminoxane cocatalyst is contacted with a composition to obtain a supported catalyst system, wherein the composition contains a metallocene complex of formula (I) in a second hydrocarbon solvent and does not contain an aluminoxane cocatalyst.

[0252] Step a)

[0253] In step a), the preferably treated porous inorganic support (iii) is reacted with the aluminoxane cocatalyst (ii). Preferably, the porous inorganic support (iii) is silica.

[0254] Preferably, the reaction between the porous inorganic support and the aluminoxane co-catalyst is carried out when the stoichiometric ratio of Al in the aluminoxane co-catalyst to the porous inorganic support is 3 to 12 mmol Al / g support.

[0255] The porous inorganic carrier (iii) is preferably calcined prior to step a) to remove moisture from its surface. The calcination temperature is typically in the range of 200 to 800°C, preferably in the range of 400 to 650°C.

[0256] The porous inorganic support (preferably a silica support) is then suspended in a suitable hydrocarbon solvent, referred to herein as the first hydrocarbon solvent. Suspension can be carried out at a temperature of 15°C to 25°C under an inert gas atmosphere (e.g., under nitrogen).

[0257] The preferred first hydrocarbon solvent is toluene.

[0258] The porous inorganic support and the first hydrocarbon solvent (e.g., silica and toluene) suspension are stirred for 5 to 60 minutes, more preferably 10 to 30 minutes. Then, an aluminoxane co-catalyst (preferably MAO (e.g., in the form of a 30 wt% toluene solution)) is added to the porous inorganic support and the first hydrocarbon solvent suspension, preferably at a stoichiometric ratio of 3 to 12 mmol Al / g support (e.g., silica).

[0259] According to the present invention, all of the aluminum oxane co-catalyst (ii) is added in step a). Therefore, 100.0 wt% of the total amount of aluminum oxane co-catalyst (ii) is added in step a).

[0260] Step a) of reacting the porous inorganic support with the aluminoxane co-catalyst in a first hydrocarbon solvent may include heating the porous inorganic support and the aluminoxane co-catalyst in the first hydrocarbon solvent to at least 50°C, preferably at least 60°C.

[0261] Preferably, after adding the aluminoxane cocatalyst, the mixture (e.g., a mixture of a porous inorganic support, a first hydrocarbon solvent, and the aluminoxane cocatalyst) is optionally heated, for example to a temperature in the range of 60°C to 120°C, preferably 70°C to 120°C, more preferably 80°C to 120°C, and even more preferably 80°C to 100°C. The porous inorganic support (iii) is preferably silica, and the first hydrocarbon solvent is preferably toluene.

[0262] The mixture can be stirred at a temperature of at least 50°C, preferably at least 60°C, or within the range defined above, for up to 12 hours, preferably 60 minutes to 5 hours, more preferably 90 minutes to 3 hours. Then stirring is stopped, the resulting slurry is allowed to settle, and the mother liquor is removed, for example by filtration or decantation.

[0263] Subsequently, the remaining support treated with the aluminoxane cocatalyst is washed once or more, for example once or twice, more preferably twice, with a first hydrocarbon washing solvent (preferably toluene) at a temperature ranging from 70°C to 115°C, preferably from 80°C to 110°C, more preferably from 90°C to 100°C, to obtain the support treated with the aluminoxane cocatalyst.

[0264] Preferably, the support treated with aluminoxane co-catalyst (preferably a silica support treated with aluminoxane co-catalyst) is then vacuum dried at a suitable temperature (e.g., at 40 to 100°C, preferably at 50 to 90°C, more preferably at 60 to 85°C).

[0265] Step b)

[0266] In step b), the support treated with the aluminoxane cocatalyst is contacted with a solution containing a metallocene complex as defined herein and a second hydrocarbon solvent. This solution does not contain the aluminoxane cocatalyst.

[0267] In one instance, the solution may consist essentially of a metallocene complex and a second hydrocarbon solvent, or a metallocene complex and a second hydrocarbon solvent.

[0268] Preferably, the second hydrocarbon solvent is the same as the first hydrocarbon solvent.

[0269] The second hydrocarbon solvent is selected from toluene, xylene, hexane, isohexane, and heptane. Preferably, the second hydrocarbon solvent is toluene.

[0270] In the solution in b), preferably, at least 1 wt%, more preferably at least 5 wt%, of the metallocene complex is soluble in the second hydrocarbon solvent at a temperature of 20°C to 80°C.

[0271] Step b) may include mixing the metallocene complex with a second hydrocarbon solvent. The mixture may be stirred until the metallocene complex is completely dissolved. In other words, step b) includes mixing the metallocene complex with a second hydrocarbon solvent to produce a solution of the metallocene complex (e.g., a solution of the second hydrocarbon solvent). Stirring may be carried out at a temperature of 10°C to 50°C, preferably 15°C to 25°C.

[0272] The concentration of the metallocene complex in the second hydrocarbon solvent is preferably 0.5 to 20 wt%.

[0273] Step b) further includes adding a solution of the metallocene complex to a support treated with an aluminoxane cocatalyst (e.g., the one obtained in step a). This is to obtain a supported catalyst system.

[0274] In an optional final step, the supported catalyst system can be washed with a suitable hydrocarbon solvent (e.g., toluene or heptane) and then dried, preferably at a suitable temperature (e.g., at 0 to 100°C, preferably at 20 to 90°C, more preferably at 30 to 60°C), preferably under vacuum, to obtain a free-flowing powder.

[0275] If desired, the supported catalyst system can be provided in the form of a slurry with the required solids content. The solid catalyst content in the slurry can be, for example, up to 30 wt%, or, for example, up to 25 wt%.

[0276] The amounts of porous inorganic support (iii), aluminoxane cocatalyst (ii) (preferably MAO) and metallocene complex (i) depend on the desired ratios defined above (e.g., Al / Mt, Al / SiO2, Mt / SiO2).

[0277] polymerization

[0278] This disclosure provides a method for preparing polypropylene homopolymers or polypropylene copolymers of one or more C2 to 8 α-olefin comonomers. For polypropylene homopolymers, the method includes polymerizing propylene in the presence of the supported catalyst system of the present invention. For polypropylene copolymers of one or more C2 to 8 α-olefin comonomers, the method includes polymerizing propylene and one or more C2 to 8 α-olefin comonomers in the presence of a supported catalyst system. This method is preferably used for preparing polypropylene homopolymers.

[0279] The catalyst system prepared according to the present invention is particularly suitable for forming propylene homopolymers or copolymers, especially copolymers with ethylene, which have high activity levels, high molecular weights, and therefore low MFRs, and polymers with ideal melting temperatures, preferably with improved melting temperatures of propylene homopolymers.

[0280] The polymerization in the method of the present invention can be carried out in one or more (e.g., 1, 2 or 3) polymerization reactors using conventional polymerization techniques (e.g., gas-phase polymerization, solution-phase polymerization, slurry polymerization or bulk polymerization, or combinations thereof), such as a combination of a slurry reactor and at least one gas-phase reactor.

[0281] The method may also include a prepolymerization step. This prepolymerization step is a routine step commonly used in polymer synthesis and is different from the offline prepolymerization step for catalysts prepared using emulsion / curing techniques discussed in the prior art.

[0282] Typically, the amount of catalyst used will depend 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 the polymer.

[0283] The catalyst systems prepared according to the present invention exhibit particularly excellent catalytic activity and / or productivity. As used herein, the term "catalytic activity" refers to the amount of polymer produced per gram of catalyst per hour. The metallocene activity of the catalyst herein is defined as the amount of polymer produced per gram of metal or per millimole of metal. The term "catalytic productivity" is sometimes also used to indicate catalytic activity, although herein it refers to the amount of polymer produced per unit weight of catalyst.

[0284] The catalyst system prepared according to the present invention can also provide polymers with high weight-average molecular weight (Mw).

[0285] For both bulk copolymerization and gas-phase copolymerization, the reaction temperatures used are typically in the range of 60 to 115°C (e.g., 70 to 90°C). For gas-phase reactions, the reactor pressure is typically in the range of 10 to 25 bar, while bulk polymerization is carried out at higher pressures. Residence times are typically 0.25 to 8 hours (e.g., 0.5 to 4 hours). The gas used will be the monomer, which may optionally be a mixture with a non-reactive gas (e.g., nitrogen or propane). A particular feature of the invention is that polymerization is carried out at a temperature of at least 60°C.

[0286] polymer

[0287] The supported catalyst system prepared according to the present invention can form polymers with high molecular weight. These characteristics can be achieved at industrially relevant polymerization temperatures (e.g., 60°C or higher).

[0288] A preferred feature of the present invention is that the supported catalyst system of the present invention is used to polymerize propylene at a temperature of at least 60°C, preferably at least 70°C, for example at least 80°C.

[0289] In one example, the propylene polymer obtained using the supported catalyst system of the present invention has a polydispersity index (Mw / Mn) of 2.0 or greater (e.g., 2.2 to 4.5).

[0290] Preferred propylene polymers (e.g., polypropylene homopolymers or polypropylene copolymers of one or more C2-8 α-olefin comonomers) are free of halogens and / or fluorine derivatives. The halogen is chlorine, bromine, or fluorine, preferably chlorine or fluorine. The presence or absence of halogens and / or fluorine derivatives in the propylene polymer will depend on the supported catalyst system used to prepare the polymer, i.e., whether the halogen atom is bonded to a metallocene transition metal and / or whether a fluorinated boron cocatalyst is used.

[0291] Polypropylene homopolymer

[0292] The Mw (weight-average molecular weight) value of the polypropylene homopolymer prepared by the catalyst system according to the present invention can be in the range of 50 to 2000 kg / mol, preferably in the range of 100 to 1500 kg / mol, more preferably in the range of 150 to 1000 kg / mol, and even more preferably in the range of 200 to 800 kg / mol, depending on the use and amount of hydrogen as the Mw modifier. The catalyst of the present invention is capable of forming polypropylene homopolymers with high melting points. In a preferred embodiment, the melting point of the propylene homopolymer formed by the method of the present invention is above 149.0°C, preferably above 149.5°C, and particularly above 150.0°C.

[0293] The polymers prepared by the catalyst of this invention can be used in a variety of end products, such as pipes, films (cast, blown or BOPP films, such as BOPP for capacitor films), fibers, molded products (such as injection molded, blow molded, rotational molded products), extruded coatings, etc.

[0294] propylene copolymer

[0295] The propylene copolymers having one or more C2 to 8 α-olefin comonomers prepared according to the present invention can be prepared with high productivity.

[0296] The polymers prepared by the catalyst in this specification can be used in a variety of end products, such as pipes, films (cast, blown or BOPP films, such as BOPP for capacitor films), fibers, molded products (such as injection molded, blow molded, rotational molded products), extruded coatings, etc.

[0297] Example

[0298] The invention will now be described with reference to the following non-limiting embodiments.

[0299] Measurement methods

[0300] Determination of Al (ICP method)

[0301] In a glove box, an equal volume (approximately 40 mg) of the catalyst 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 with 5 mL of concentrated nitric acid (65%). The sample was then microwave-assisted digested at 150 °C for 35 min using a MARS 6 laboratory microwave apparatus. The digested sample was allowed to cool for at least 4 h and then transferred to a 100 mL glass volumetric flask. A standard solution containing 1000 mg / L LY and Rh (0.4 mL) was added. The flask was then filled with distilled water and shaken thoroughly. The solution was filtered through a 0.45 µm nylon syringe filter and analyzed using a Thermo iCAP 6300 ICP-OES and iTEVA software.

[0302] The instrument's Al was calibrated using a blank solution (5% HNO3 solution) and six standard solutions (containing 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L Al in 5% distilled HNO3 aqueous solution, respectively). Each calibration solution contained 4 mg / L of LY and Rh standards. However, not every calibration point was used for every wavelength: Al 394.401 nm was calibrated using the following calibration points: blank solution, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L. Al 167.079 nm was calibrated in the same manner as Al 394.401 nm, excluding the 100 mg / L standard solution. Curve fitting and 1 / concentration weighting were used for the calibration curve.

[0303] Prior to analysis, the calibration solution was immediately validated and adjusted (instrument slope correction function) using a blank solution and a 10 mg / L Al standard solution (containing 4 mg / L LY and Rh). Quality control samples were run to confirm the slope calibration results.

[0304] When the Al concentration in the test section is below 2 wt%, the aluminum content is monitored using the 167.079 nm {502} line; when the Al concentration is above 2 wt%, the aluminum content is monitored using the 394.401 nm {85} line. Y 371.030 nm {91} is used as an internal standard for Al 394.401 nm, and Y 224.306 nm {450} is used as an internal standard for Al 167.079 nm.

[0305] Metallocene complexes

[0306] Synthesis of MC-1

[0307] The synthesis of racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride was carried out as described in the chapter entitled "Synthesis of MC-2" in WO2019 / 179959.

[0308] Synthesis of MC-1M

[0309] MC-1M is racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium.

[0310] A solution of MeMgBr in ether (2.0 M, 6.0 mL, 12.0 mmol) was added to a suspension of MC-1 (i.e., racemic-trans-dimethylsilanediyl[2-methyl-4,8-di(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride) in a mixture of 20 mL toluene and 30 mL ether. The resulting mixture was stirred overnight at room temperature, refluxed for 30 min, and then evaporated to approximately 15 mL. The resulting suspension was filtered through a glass frit funnel (G4), and the filtrate was evaporated to almost dryness. The residue was dissolved in 20 mL of n-hexane and filtered (G4). The yellow powder precipitated overnight from the solution at -30°C was collected and dried under vacuum. This procedure yielded 3.3 g (approximately 88%) of MC-3M containing an equivalent of n-hexane molecules.

[0311] Solubility of metallocene complexes

[0312] The solubility of MC-1 and MC-1M metallocene complexes in toluene was determined (at room temperature). Table 1 shows the results of the solubility tests.

[0313] Table 1: Solubility Test Results

[0314]

[0315] In order to prepare a supported catalyst system, at least 1 wt% of the metallocene complex must be soluble in a second hydrocarbon solvent (e.g., toluene) at the temperature used in step b) of the method.

[0316] Catalyst preparation

[0317] All catalysts were prepared using a toluene solution of MAO from Lanxess.

[0318] Synthesis of catalyst SiO2 / MAO / MC-1, compared with catalyst 1 (CE1)

[0319] First, 5 kg of SiO2 support (Sunspera AGC DM-L-303-C1) was added to the reactor, followed by 21.8 kg of toluene. The SiO2 / toluene mixture was stirred at 23 °C for 15 min. A 30 wt% MAO toluene solution was slowly added to the reactor (60-70 min), maintaining the reactor temperature at approximately 23 °C (Al⁻¹ = 9.4 mol / kg SiO2). After adding MAO, the reactor temperature was rapidly increased to 90 °C, and the mixture was stirred at this temperature for 120 min. The hot toluene was then siphoned off, and the support filter cake was washed twice with hot toluene (21.8 kg, 95 °C), followed by vacuum drying at 80 °C for 6 h.

[0320] In a separate reactor, a metallocene complex solution was prepared by adding 5.7 kg of toluene (part of which was reserved for rinsing the metallocene cylinder) to the reactor at 25 °C, followed by the addition of 0.71 kg of MAO (30 wt% toluene solution, 0.7 mol / kg SiO2). The mixture was stirred for 20 min, and then 0.1509 kg of the metallocene complex MC-1 (30 mmol / kg SiO2) and 1.7 kg of “rinsing toluene” were added to the reactor. The complex solution was stirred at 25 °C for 60 min.

[0321] The above complex solution was added to a reactor with a SiO2 / MAO support over 50 min, and then stirred at 25 °C for 30 min. Stirring was then stopped, and the catalyst was allowed to stabilize at 25 °C for 30 min. The catalyst was then vacuum dried at 60 °C for 9 h.

[0322] Synthesis of SiO2 / MAO (SM1)

[0323] First, 10 kg of SiO2 support (PQ silica, PD-19057, ES757) was added to the reactor, followed by 43.5 kg of toluene. The SiO2 / toluene mixture was stirred at 22 °C for 25 min. Then, 18 kg of a toluene solution of 30 wt% MAO was slowly added to the reactor (130–140 min), maintaining the reactor temperature at approximately 22 °C (Al₁ = 9.3 mol / kg SiO2). After adding MAO, the reactor temperature was rapidly increased to 90 °C, and the mixture was stirred at this temperature for 120 min. The hot toluene was then siphoned off, and the support filter cake was washed twice with hot toluene (43.5 kg, 90 °C), followed by vacuum drying at 80 °C for 9 h.

[0324] SiO2 / MAO (SM1) (Al = 14.5 wt%, toluene = 0.27 wt%) was used in the synthesis of catalysts IE1 and IE2.

[0325] Synthesis of SiO2 / MAO (SM2)

[0326] The silica used was AGC Sunspera DM-L-303-C1. This is silica calcined, for example, at 600°C. For example, commercially available silica AGC Sunspera DM-L-303 calcined, for example, at 600°C for 24 hours can be used. The steel reactor equipped with a mechanical stirrer and filter was purged with nitrogen. First, 10 kg of SiO2 support was added to the reactor from the feed tank, followed by careful pressurization and depressurization with nitrogen. Then, toluene (43.5 kg) was added. The SiO2 / toluene slurry was stirred at 22°C for 25 min. Then, 18 kg of a toluene solution of 30 wt% MAO (Axion CA 1330) was slowly (140 min) added through a 12 mm line at the top of the reactor, maintaining the temperature at approximately 22°C. After the addition of MAO, the reactor temperature was rapidly raised to 90°C, and the mixture was stirred at this temperature for 120 min. The hot toluene was then filtered off, and the solid filter cake was washed twice with hot toluene while stirring (43.5 kg, 90°C, 30 min, 40 rpm). The hot toluene was filtered off each time. Finally, the solid filter cake was vacuum dried at 80°C for 9 h while stirring slowly (5 rpm).

[0327] The composition of the SiO2 / MAO samples was analyzed using MW-AD-ICP-OES (microwave-assisted acid digestion, inductively coupled plasma optical emission spectrometry). The solvent (toluene) content of the prepared SiO2 / MAO and catalyst samples was examined using HS-GC-MS (headspace gas chromatograph with mass spectrometer).

[0328] Synthesis of the catalyst SiO2 / MAO / MC-1, catalyst 1 (IE1) of this invention.

[0329] In a nitrogen-filled glove box, 2.1 ml of dry toluene was added to an equal volume of the metallocene complex MC-1 (97.1% purity, 43.1 mg, 45.7 µmol). The mixture was stirred at room temperature for 30 minutes. Next, 2.0 g of MAO-treated silica SM1 (Al = 14.5 wt%) was placed in a glass vial. The toluene solution of the metallocene complex was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting mixture was shaken to homogenize and allowed to stand for 1 hour. The resulting solid was dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a red, free-flowing powder.

[0330] Synthesis of the catalyst SiO2 / MAO / MC-1M, catalyst 2 (IE2) of this invention.

[0331] In a nitrogen-filled glove box, 2.1 ml of dry toluene was added to an equal volume of the metallocene complex MC-1M (1 mol equivalent to toluene for zirconium, 40.1 mg, 41.3 µmol). The mixture was stirred at room temperature for 30 minutes. Next, 2.0 g of MAO-treated silica SM1 (Al = 14.5 wt%) was placed in a glass vial. The toluene solution of the metallocene complex was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting mixture was shaken to homogenize and allowed to stand for 1 hour. The resulting solid was dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a red, free-flowing powder.

[0332] The synthesis of SiO2 / MAO-MC-1, using catalyst 3 (IE3) of this invention.

[0333] In a nitrogen-filled glove box, 2.5 mL of dry toluene was added to 32.3 mg of metallocene racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (metallocene complex MC-1) placed in a diaphragm flask. The mixture was stirred at room temperature for 30 minutes. Next, 2.0 g of SiO2 / MAO SM2 was placed in a diaphragm flask. The toluene solution of the metallocene was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting powder was allowed to stand for 1 hour, then transferred to a Schlenk flask and dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a salmon-red free-flowing powder.

[0334] The composition of the catalyst is shown in Table 2.

[0335] Table 2: Catalysts tested and their metallocene (MC) content

[0336]

[0337] a =Measured by ICP method.

[0338] Polymer Analysis

[0339] MFR

[0340] MFR was measured according to DIN ISO 1133 on a Schmelz-Index-Prüfgerät MI-4 (Göttfert Werkstoff-PrüfmaschinenGmbH) at 230°C and under a load of 2.16 kg (MFR2), and is expressed in g / 10 min.

[0341] Polymer powder bulk density

[0342] Instrument: Electronic balance: measuring range 0.1g-11000g

[0343] Glass graduated cylinder: Volume = Maximum 250 ml

[0344] Plastic medicine spoon: Volume = 125 ml

[0345] Plastic funnel: D=105 mm

[0346] Procedure: Pour the unstable polymer powder into a glass graduated cylinder to a volume of 250 ml using a plastic spatula and a plastic funnel.

[0347] Calculation: Polymer mass (g) / Measurement volume (ml)

[0348] DSC

[0349] DSC curves and data were generated on a DSC Q200 TA instrument by placing 5–7 mg samples cut from polymer MFR strands into a sealed DSC aluminum disk, heating the samples from -10°C to 225°C at a rate of 10°C / min, holding at 225°C for 10 min, cooling from 225°C to -30°C, holding at -30°C for 5 min, and then heating from -30°C to 225°C at a rate of 10°C / min. The reported T... m The value is the value of the endothermic heat flux peak determined by the second heating scan according to BTM00121.

[0350] GPC

[0351] As described in BTM 00192, the MWD and corresponding values ​​of polymer samples were determined at 160°C using gel permeation chromatography (GPC). Average molecular weight and All samples were at low M w Integrate at the end until the third-to-last calibration point of the calibration curve (PS = 1820 g / mol ~ 1340 g / mol PP equivalent), instead of the last point of the calibration curve as described in the BTM00192 method.

[0352] polymerization

[0353] monomers and gases

[0354] Ethylene was purified using a column packed with molecular sieve 3A EPG 1 / 16, PolyMax 301 T-4427B, and Selexsorb COS. Hydrogen (6.0g by mass) was supplied by Air Liquide and was ready for use upon receipt. Propylene (2.3g by mass) was purified using a column packed with PolyMax301 T-4427B (60°C; Cu / CuO), MS13X-APG 1 / 16, and Selexsorb COS.

[0355] propylene homopolymerization process

[0356] Add 4.45 kg of propylene to a 20.9 dm³ stainless steel reactor equipped with a ribbon agitator, containing 0.2 bar-g of propylene. Add triethylaluminum (0.8 ml of 0.62 mol / L n-heptane solution) using a 250 g propylene feed stream, followed by 0.5 NL H₂ over one minute via a mass flow controller. Stabilize the reactor temperature at 25 °C (HB-Therm) and stir the solution at 250 rpm for at least 20 min. Then, inject the catalyst as described below.

[0357] Load the required amount of solid catalyst into a 5 ml stainless steel vial, and add a second 5 ml vial containing 4 ml of n-heptane to the top of the glove box. Then pressurize the top vial with 5 bars of nitrogen. Install this dual-feed system on the port of the autoclave lid. Open the valve between the two vials, contact the solid catalyst with n-heptane under N2 pressure for 2 s, and then flush the reactor with 250 g of propylene. Maintain the stirring speed at 250 rpm and prepolymerize at 25°C for 10 minutes. Then raise the polymerization temperature to 85°C. At 62°C, add a second portion of H2 over 2 minutes. Keep the reactor temperature constant throughout the polymerization process. When the temperature is 2°C lower than the set polymerization temperature, begin measuring the polymerization time. When 40 min of polymerization time has elapsed, stop the reaction by injecting 5 ml of ethanol, cooling the reactor, and simultaneously flash-evaporating the volatile components. After purging the reactor three times with N2 and performing one vacuum / N2 cycle, open the reactor, remove the polymer powder, and dry it overnight in a fume hood. Add 0.5 wt% Irganox B225 (dissolved in acetone) to 100 g of polymer, then dry overnight in a fume hood and then dry for another hour in a vacuum drying oven at 60°C.

[0358] Bulk propylene polymerization experiments were conducted at 85°C using two different H2 concentrations and the three catalysts described above. The results are as follows: Figures 1 to 3 As shown in the results, the following points can be observed.

[0359] 1. At both H2 levels, catalyst 2 (IE2) of the present invention, containing the metallocene complex MC-1M, exhibits higher activity than catalyst 1 (IE1) of the present invention, containing the metallocene complex MC-1. Both IE1 and IE2 show higher catalyst productivity compared to comparative catalyst 1 (CE1).

[0360] 2. Compared to the control catalyst (CE1), the two catalysts (IE1 and IE2) without the second addition of MAO showed faster initiation. This indicates that the second addition of MAO has no positive effect on the activation of MC-1 and MC-1M, and therefore can be omitted from the method of catalyst synthesis.

[0361] 3. The catalytic behavior of the two catalysts (IE1 and IE2) without a second addition of MAO was almost identical. Furthermore, the melting points of polypropylene were almost identical, confirming that MC-1 and MC-1M were comparable in catalysis.

[0362] Compared to the control catalyst, the catalyst without a second MAO addition showed faster activation and better productivity. The catalyst productivity after 40 minutes was as follows: Figure 4 As shown.

[0363] Two-step (bulk + gas phase) homopolymerization experiments of propylene were also conducted.

[0364] Both bulk and gas-phase propylene polymerization steps

[0365] Perform step 1 as described above.

[0366] Proceed to step 2 as follows. After the main body step is completed, reduce the agitator speed to 50 rpm and reduce the pressure to 20 bar-g by discharging propylene. Set the agitator speed to 180 rpm and the reactor temperature to 80°C. Then, feed 1 NL of hydrogen into the reactor through the mass flow controller and increase the reactor pressure to 21 bar-g by feeding propylene.

[0367] The temperature was maintained constant using a thermostat, and the pressure was maintained constant by feeding propylene via a mass flow controller until the set time for this step was completed. The reactor was then cooled (to approximately 30°C) to flash-evaporate volatile components. After purging the reactor three times with N2 and performing one vacuum / N2 cycle, the product was removed and dried overnight in a fume hood. 100 g of the polymer was added to 0.5 wt% Irganox B225 (acetone solution), dried overnight in a fume hood, and then dried in a vacuum drying oven at 60°C for 2 hours.

[0368] Storage lifespan

[0369] The storage life of the catalysts was evaluated by storing them in dry powder and slurry form under an inert atmosphere in the dark and at room temperature, and then testing them in a two-step homopolymerization experiment of propylene after increasing the storage time.

[0370] Catalysts prepared using MAO added twice (such as catalyst CE1 above) have storage life issues and typically lose significant activity after only a few months of storage at room temperature. For example, a batch of dry catalyst CE1 was tested more than a year after its preparation. During this period, its productivity decreased by approximately 50%.

[0371] Catalyst IE3 was tested. This catalyst was tested over a 25-month period in both dry and slurry forms. It was found to be very stable, as indicated by its productivity, gas phase split, melting point, and bulk density. Figures 5 to 7 middle.

Claims

1. A method for preparing a supported catalyst system, wherein the supported catalyst system comprises: (i) Metallocene complexes of formula (I); (ii) A cocatalyst system containing aluminoxane cocatalyst; as well as (iii) Porous inorganic carriers; The method includes: a) React the porous inorganic support with the aluminoxane cocatalyst in a first hydrocarbon solvent to obtain a support treated with the aluminoxane cocatalyst. b) Contact the support treated with the aluminoxane cocatalyst with a solution to obtain the supported catalyst system, wherein the solution contains the metallocene complex of formula (I) and a second hydrocarbon solvent, and the solution does not contain the aluminoxane cocatalyst. The metallocene complex of formula (I) is (I) in: Mt is either Zr or Hf; X is a monoanion ligand; R 1 Same or different, where each R 1 Independently selected from H and C1-C8-alkyl groups, wherein the C1-C8 alkyl group optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms; R 2 and R 2 Each is independently CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6 alkyl, C3-C8 cycloalkyl, or C6-C 10 Aryl; R 3 Same or different, and R 4 Same or different, where each R 3 and each R 4 Independently selected from H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl, OY and NY2 groups, wherein each Y is independently C1-C 10 - hydrocarbon group, and / or two adjacent R 3 Or two adjacent R 4 Together with the two carbon atoms of the benzene ring they are bonded to, they form a 4- to 7-atom ring; Each R 5 R 6 and R 7 Independently selected from hydrogen and C1-C 20 - hydrocarbon group, wherein the C1-C 20 - The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms, or an OY group, wherein Y is C1-C. 10 - hydrocarbon group, and / or R 6 C1-C 20 - Hydrocarbon group and R 5 and R 7 One of the C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4- to 7-atom ring, provided that (i) when R 7 When it is H, then R 5 and R 6 Neither of them is H, and (ii) only if R 7 When it is not H, R 5 and R 6 Only then can it be hydrogen; R 5 'and R 6 Each is independently C1-C 20 - hydrocarbon group, wherein the C1-C 20 - The hydrocarbon group optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms, or an OY group, wherein Y is C1-C. 10 -hydrocarbon group, and optionally R 5 'C1-C 20 - Hydrocarbon group and R 6 'C1-C 20 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring.

2. The method according to claim 1, wherein the porous inorganic support is a silica support.

3. The method according to claim 1 or 2, wherein the aluminum oxane cocatalyst in a) is a methylaluminoxane (MAO) cocatalyst.

4. The method according to any one of claims 1 to 3, wherein the first hydrocarbon solvent is toluene.

5. The method according to any one of claims 1 to 4, wherein the second hydrocarbon solvent is selected from toluene, xylene, pentane, hexane, isohexane and heptane, preferably toluene.

6. The method according to any one of claims 1 to 5, wherein the step of reacting the porous inorganic support with the aluminoxane co-catalyst in a first hydrocarbon solvent comprises heating the porous inorganic support and the aluminoxane co-catalyst in the first hydrocarbon solvent to a temperature of at least 50°C, preferably at least 60°C.

7. The method according to any one of claims 1 to 6, wherein the metallocene complex has formula (II): (II) in: R 5 "and R 6 Each is independently C1-C 10 -Hydrocarbon group, where C1-C 10 -The hydrocarbon group optionally contains at most one silicon, oxygen, sulfur, or nitrogen atom or an OY group, wherein Y is C1-C 10 -hydrocarbon group, and optionally R 5 "C1-C 10 - Hydrocarbon group, R 5 "Bonded oxygen atoms and R" 6 'C1-C 10 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring.

8. The method according to any one of claims 1 to 7, wherein the metallocene complex has formula (III): (III) in: R 5 "and R 6 Each is independently C1-C 10 -Hydrocarbon group, where C1-C 10 -The hydrocarbon group optionally contains at most one silicon, oxygen, sulfur, or nitrogen atom or an OY group, wherein Y is C1-C 10 -hydrocarbon group, and optionally R 5 "C1-C 10 - Hydrocarbon group, R 5 "Bonded oxygen atoms and R" 6 'C1-C 10 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring; Each Y is independently H or C1-C 10 -hydrocarbon group; and n is 2, 3, or 4.

9. The method according to any one of claims 1 to 8, wherein the metallocene complex has formula (IV): (IV) in: R 5 "and R 6 Each is independently C1-C 10 -Hydrocarbon group, where C1-C 10 -The hydrocarbon group optionally contains at most one silicon, oxygen, sulfur, or nitrogen atom or an OY group, wherein Y is C1-C 10 -hydrocarbon group, and optionally R 5 "C1-C 10 - Hydrocarbon group, R 5 "Bonded oxygen atoms and R" 6 'C1-C 10 -The hydrocarbon group, together with the two carbon atoms of the benzene ring to which it is bonded, forms a 4 to 7-atom ring; Each Y is independently H or C1-C 10 -hydrocarbon group; and n is 2, 3, or 4.

10. The method according to any one of claims 1 to 9, wherein the metallocene complex has formula (V): (V)。 11. The method according to any one of claims 1 to 10, wherein the metallocene complex is selected from: Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylzirconium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]hafnium dichloride; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium; and Racemic-trans-dimethylsilanediyl[2-ethyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]dimethylhafnium.

12. The method according to any one of claims 1 to 11, wherein each X is independently C1-C 10 The hydrocarbon group, preferably each X is independently a C1-C6-alkyl group, more preferably both X are methyl groups.

13. A supported catalyst system obtained by or obtainable by any one of claims 1 to 12, preferably the supported catalyst system according to claim 13, wherein the supported catalyst system does not contain halogens, and preferably does not contain fluorine and / or chlorine.

14. A method for preparing a polypropylene homopolymer or a polypropylene copolymer of one or more C2 to 8 α-olefin comonomers, wherein the method comprises polymerizing propylene and optionally one or more C2 to 8 α-olefin comonomers in the presence of a supported catalyst system according to claim 13.

15. A polypropylene homopolymer or a polypropylene copolymer of one or more C2 to 8 α-olefin comonomers obtained by the method according to claim 14, wherein the polypropylene homopolymer or polypropylene copolymer is halogen-free.

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