Metallocene for manufacturing polypropylene

Abstract

The present disclosure relates to metallocene complexes of formula (I) wherein Mt is Zr or Hf; x is a sigma ligand; r < 1 >, each independently, equal to or different from each other, is a C1-C20 hydrocarbon group, optionally containing up to two heteroatoms of groups 14-16 of the periodic table, or forming together with the Si atom to which they are attached a C4-C8 ring; r1 and R2'are each independently, equal to or different from each other, a C1-C10-hydrocarbyl group, n are each independently an integer from 1 to 5, R3 and R4 are each independently H, a C1-C10-hydrocarbyl group, or an-OR31,-SR31 or-NR312 group, where R31 is a C1-C10-hydrocarbyl group, where at least one R3 of each phenyl group is not hydrogen and at least one R4 is not hydrogen, R51 'is a C1-C10-hydrocarbyl group, and R6' is C (R61) 3, where R61 is a linear or branched C1-C6-alkyl group.

Description

Technical Field

[0001] This disclosure relates to novel bisindenyl ligands, their complexes, and catalysts comprising these complexes. This disclosure also relates to the use of novel bisindenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers with high activity levels, high molecular weights, and consequently low MFRs, and desirable melting points. 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] WO2001048034 describes a C1-symmetric bis-indenyl complex with a 5-methoxy substituent and a 6-tert-butyl substituent, but the 2-substituent is linear. Such catalysts produce hPP with relatively low melting points (148-150 °C).

[0004] WO2018091684 describes a C2-symmetric racemic-Me2Si(2-Me-4-(3,5-Me2Ph)-ind)2ZrCl2 complex, which produces low T values ​​with a temperature of 150-151 °C. m hPP.

[0005] WO2005058916 describes a series of C1-symmetric bis-indene complexes that combine a 2-isopropyl-4-aryl-indene ligand and a 2-methyl-4-aryl-indacenyl ligand. While hPP's T m The temperature is relatively high, ranging from 152 to 160°C, but the catalyst activity remains low.

[0006] WO2019179959 describes a C1 symmetrical diindenyl complex comprising an indenyl moiety with 5-methoxy and 6-tert-butyl substituents and an indahernic acid moiety. In the presence of a borate co-catalyst, this catalyst provides a slightly higher Tp for hPP. m The temperature ranges from 154 to 156℃.

[0007] While these existing catalysts have their advantages, they lack selectivity, especially in the absence of borate co-catalysts, resulting in hPP with relatively low melting and crystallization temperatures due to the formation of insertion region defects in the PP chain.

[0008] The inventors sought new metallocenes and designed this ligand to provide high synthesis efficiency and high selectivity without compromising productivity, especially in the production of high melt temperature and high molecular weight polypropylene homopolymers (hPP). Summary of the Invention

[0009] One object of this disclosure is to provide new metallocene complexes and the resulting catalysts that overcome the aforementioned problems.

[0010] The objective of this disclosure is achieved by a metallocene complex of formula (I), a polymerization catalyst comprising the metallocene complex of formula (I), and optionally a method for polymerizing polypropylene with a comonomer, characterized as described in the independent claim. Preferred embodiments of this disclosure are disclosed in the dependent claims.

[0011] Surprisingly, it was found that specific modifications of C2-symmetric metallocenes, with the introduction of large aryl substituents at the 4- and 7-positions of the indene ligand and no substituents at the 5- and 6-positions, combined with specific substitutions of the indene ligand, provided the desired properties.

[0012] The inventors have identified a supported catalyst system consisting of a combination of a specific class of metallocene catalysts and an aluminum-containing co-catalyst. Compared to systems known in the art, this system exhibits improved polymerization behavior, higher catalyst productivity, and improved performance in the production of propylene polymers (especially homopolymers). This specific catalyst system offers greater flexibility and freedom in the design of propylene polymers compared to prior art catalyst systems.

[0013] This disclosure also provides a polymerization catalyst comprising, preferably, the following: (i) a metallocene complex of formula (I) as described herein; (ii) a cocatalyst comprising a group 13 element; and (iii) an optional support.

[0014] This disclosure provides a method for propylene polymerization, which includes polymerizing propylene in the presence of a polymerization catalyst described herein.

[0015] In one example, the method could be a method for preparing multiphase polypropylene copolymers. The method could include...

[0016] (I) Propylene is bulk polymerized in the presence of a polymerization catalyst as described herein to form a polypropylene homopolymer matrix.

[0017] (II) In the presence of the matrix and the polymerization catalyst, propylene and ethylene are polymerized in the gas phase to form a multiphase polypropylene copolymer comprising a homopolymer matrix and an ethylene-propylene rubber.

[0018] One advantage of this disclosure is that these metallocenes allow for the production of propylene polymers with high selectivity, particularly after MAO activation, to produce polymers with high TT. m Polypropylene homopolymer (hPP).

[0019] definition

[0020] The following definitions are used throughout this description:

[0021] The term "C1- 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 groups, such as C1-C8 alkyl groups. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, and benzyl.

[0022] It should be noted that straight-chain and branched hydrocarbon groups cannot contain cyclic units. Aliphatic hydrocarbon groups cannot contain aryl rings.

[0023] The term “heteroatoms of groups 14-16 of the periodic table” includes, for example, Si, N, O, or S.

[0024] As used herein, the term “C4-C8 ring” with the addition of -R'2Si- refers to a cyclic group containing 4 to 8 carbon atoms and one Si atom, including, for example, siliconediyl groups, such as siliconebutane, siliconepentane, or 9-siliconium.

[0025] When it comes to the definition of coordination compounds, the term "halogen" includes fluorine, chlorine, bromine, and iodine groups, especially chlorine or fluorine groups.

[0026] 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.

[0027] 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.

[0028] The numbering of these rings will be evident from the structure shown in this article.

[0029] In this application, catalyst activity is defined as the amount of polymer produced per gram of catalyst per hour. Catalyst metal activity is defined as the amount of polymer produced per gram of metal per hour. The term productivity is sometimes used to describe catalyst activity, although in this document it refers to the amount of polymer produced per unit weight of catalyst.

[0030] The term “molecular weight” as used in this article refers to weight-average molecular weight Mw, unless otherwise stated. Detailed Implementation

[0031] This invention relates to a series of novel ligands, metallocene catalyst complexes, and the resulting ideal propylene polymerization catalysts.

[0032] Metallocene catalyst complexes

[0033] The metallocene catalyst complexes of the present invention are asymmetric. Asymmetry refers only to the fact that the two ligands forming the metallocene are different, that is, each ligand carries a set of substituents with different chemical properties.

[0034] The metallocene complexes of the present invention are preferably the trans configuration of chiral racemic-bridged bis-indenyl C1-symmetric metallocenes. Although the complexes of the present invention are formally C1-symmetric, they ideally maintain pseudo-C2-symmetry because they maintain C2-symmetry near the metal center, although not around the ligands. In terms of their chemical properties, trans and cis enantiomer pairs are formed during the synthesis of the complexes (in the case of C1-symmetric complexes). For the purposes of the present invention, racemic-trans refers to the two indenyl ligands oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-cis refers to the two indenyl ligands oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the figure below.

[0035]

[0036] racemic trans racemic cis racemic

[0037] Formula (I) and any sub-formulas are intended to cover both cis and trans configurations. Preferred metallocene catalyst complexes are trans-configured.

[0038] 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 catalyst complexes are in the racemic trans isomer form.

[0039] For the purposes of this invention, the numbering scheme for indenyl ligands is as follows:

[0040]

[0041] Therefore, this invention relates to compounds of formula (I):

[0042]

[0043] in

[0044] Mt is Zr or Hf:

[0045] X is a σ-ligand;

[0046] R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached;

[0047] R 2 and R 2’ Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group;

[0048] n are each an independent integer from 1 to 5;

[0049] R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It is not hydrogen;

[0050] R 51’ It is C1-C 10 -hydrocarbon group; and

[0051] R 6’It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0052] Advantageously, one of the indenyl ligands is not substituted at positions 5 and 6.

[0053] For compounds of formula (I) as defined above, the following represent preferred embodiments, which may be selected individually or in combination:

[0054] In the complex of formula (I), Mt is preferably Zr or Hf, with Zr being more preferred.

[0055] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is an H, halogen, C1-C6 oxy, or R' group, wherein R' is a C1-C6 alkyl, phenyl, or benzyl group. More preferably, each X is independently the same or different from each other and is chlorine, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0056] Preferably, R 1 Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group, more preferably C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -Arylalkyl, C6-C 10 -Aryl or C7-C 10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, or even more preferably two Rs 1 All are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In one embodiment, each R... 1 Independently identical or different from each other, is arbitrarily determined by C1-C. 10 -Alkoxy-substituted C1-C10-alkyl. Preferably two R 1 The groups are identical. Most preferably, the two R groups are identical. 1 They are all methyl groups.

[0057] As mentioned above, R 2 and R 2’ Each being independently the same or different from the others is C1-C. 10 - Hydrocarbon group, such as straight-chain or branched C1-C 10 - Hydrocarbon group. Preferably, R 2 and R 2’ Each is independently identical or different from the others; they are C3-C of the α-branch. 10- Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6-C 10 Aryl, for example R 21 It is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is an α-branched C3-C6-alkyl or CH2-R. 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group.

[0058] Preferably, R 2 It is CH2-R 21 R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6- 10 Aryl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group, or even more preferably, R. 2 It is methyl or ethyl.

[0059] Preferably, R 2’ It is an α-branched C3-C 10 - Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6- 10 Aryl; more preferably, R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group, or even more preferably R. 2’ It is C(CH3)2, methyl, ethyl, or n-propyl;

[0060] Preferred R 2 It is methyl, R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group, more preferably, R 2 It is methyl and R 2’ It is CH2-R21 , where R 21 It is an H or a straight-chain or branched C1-C3-alkyl group. Most preferably, R 2 It is methyl, R 2’ It is methyl, ethyl, or propyl (e.g., isopropyl or n-propyl).

[0061] Ideally, each n is independently the same or different from each other, and is an integer from 1 to 3, such as 1, 2 or 3.

[0062] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3-, 4-, and / or 5-positions of the ring, with the 1-position connected to the indene ring.

[0063] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0064] Furthermore, each benzene ring may have the same substitution pattern, or the benzene ring may have different substitution patterns.

[0065] Therefore, when n is 1, it is preferable to have only R. 3 and / or R 4 The groups are located at the para position. If n is 2, then the two R groups are located at the para position. 3 and / or R 4 The groups are preferably located at the meta position.

[0066] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 10 aryl, more preferably H, straight-chain or branched C1-C4-alkyl, or -OR 31 , where R 31 It is a C1-4 hydrocarbon group, or even more preferably, each R 3 and R 4 Each is independently identical or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially hydrogen, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0067] As mentioned above, R 51’ It is C1-C 10 - Hydrocarbon group, for example, straight-chain or branched C1-C 10 - Hydrocarbon group. R is preferred. 51’It is a straight-chain or branched C1-C6-alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, C7-C 10 -Arylalkyl, C7-C 10 -alkylaryl or C6-C 10 -aryl, more preferably straight-chain or branched C1-C6 alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0068] Preferred R 6’ It is C(R) 61 )3, where R 61’ It is a straight-chain C1-C3 alkyl group; more preferably methyl. Therefore, advantageously, R 6’ It is tert-butyl.

[0069] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ia).

[0070] (Ia)

[0071] in

[0072] Mt is either Zr or Hf;

[0073] Each X is an independent σ ligand;

[0074] R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached;

[0075] R 2 and R 2’ Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group;

[0076] R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It is not hydrogen;

[0077] R 51’ It is C1-C 10 -hydrocarbon group; and

[0078] R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0079] Substituent R on the benzene ring 3 and R 4 They can be the same or different, and can be H or C1-C. 10 Hydrocarbon group.

[0080] Wherein at least one R of each phenyl 3 Not hydrogen and at least one R 4 It's not hydrogen.

[0081] For compounds of formula (Ia) as defined above, the following represent preferred embodiments, which may be selected individually or in combination:

[0082] In the complex of formula (Ia), Mt is preferably Zr or Hf, with Zr being more preferred.

[0083] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is an H, halogen, C1-C6 oxy, or R' group, wherein R' is a C1-C6 alkyl, phenyl, or benzyl group. More preferably, each X is independently the same or different from each other and is chlorine, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0084] Preferably, R 1 Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group, more preferably C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -Arylalkyl, C6-C 10 -Aryl or C7-C 10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, or even more preferably two Rs 1 All are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In one embodiment, each R... 1 Independently identical or different from each other, is arbitrarily determined by C1-C. 10 -alkoxy-substituted C1-C 10 -alkyl group. Preferably two R groups. 1 The groups are identical. Most preferably, the two R groups are identical. 1 They are all methyl groups.

[0085] As mentioned above, R 2 and R 2’ Each being independently the same or different from the others is C1-C. 10 - Hydrocarbon group, such as straight-chain or branched C1-C 10 - Hydrocarbon group. Preferably, R 2 and R 2’ Each is independently identical or different from the others; they are C3-C of the α-branch. 10 - Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6-C 10 Aryl, for example R 21 It is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is an α-branched C3-C6-alkyl or CH2-R. 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group.

[0086] Preferably, R 2 It is CH2-R 21 R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6- 10 Aryl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group, or even more preferably, R. 2 It is methyl or ethyl.

[0087] Preferably, R 2’ It is an α-branched C3-C 10 - Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6- 10 Aryl; more preferably, R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group, or even more preferably R. 2’It is C(CH3)2, methyl, ethyl, or n-propyl;

[0088] Preferred R 2 It is methyl, R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group, more preferably, R 2 It is methyl and R 2’ It is CH2-R 21 , where R 21 It is an H or a straight-chain or branched C1-C3-alkyl group. Most preferably, R 2 It is methyl, R 2’ It is methyl, ethyl, or propyl (e.g., isopropyl or n-propyl).

[0089] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 10 aryl, more preferably H, straight-chain or branched C1-C4-alkyl, or -OR 31 , where R 31 It is a C1-4 hydrocarbon group. Even more preferably, each R... 3 and R 4 Each is independent of the other, being the same or different, and is H, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially hydrogen, methyl or tert-butyl.

[0090] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3-, 4-, and / or 5-positions of the ring, with the 1-position connected to the indene ring.

[0091] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0092] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0093] Therefore, one or two R are preferred. 3 and / or R 4 The group is H. If the two R groups are H, then... 3 and / or 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. If an R 3 and / or R4 If the group is H, then the remaining R 3 and / or R 4 The group is preferably located at the meta position.

[0094] Advantageously, one or two R on the phenyl group 3 Not H, but rather R on the two benzene rings. 3 Same as, for example, 3',5'-dimethyl or 4'-tert-butyl.

[0095] For the indenyl moiety, one or two R on the phenyl group are preferred. 4 Not H, two Rs are preferred. 4 It's not H, the optimal choice is these two Rs. 4 Similar to 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0096] As mentioned above, R 51’ It is C1-C 10 - Hydrocarbon group, for example, straight-chain or branched C1-C 10 - Hydrocarbon group. R is preferred. 51’ It is a straight-chain or branched C1-C6-alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, C7-C 10 -Arylalkyl, C7-C 10 -alkylaryl or C6-C 10 -aryl, more preferably straight-chain or branched C1-C6 alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0097] Preferred R 6’ It is C(R) 61 )3, where R 61’ It is a straight-chain C1-C3 alkyl group; more preferably methyl. Therefore, advantageously, R 6’ It is tert-butyl.

[0098] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ib).

[0099] (Ib)

[0100] in

[0101] Mt is either Zr or Hf;

[0102] Each X is an independent σ ligand;

[0103] R 1 Each being independently the same or different from the others is C1-C. 20Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached;

[0104] R 2’ It is C1-C 10 - Hydrocarbon group, preferably straight-chain or branched C1-C 10 -Hydrocarbon group;

[0105] R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It is not hydrogen;

[0106] R 51’ It is C1-C 10 -hydrocarbon group; and

[0107] R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0108] For compounds of formula (Ib) as defined above, the following represent preferred embodiments, which may be selected individually or in combination:

[0109] In the complex of formula (Ib), Mt is preferably Zr or Hf, with Zr being more preferred.

[0110] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is an H, halogen, C1-C6 oxy, or R' group, wherein R' is a C1-C6 alkyl, phenyl, or benzyl group. More preferably, each X is independently the same or different from each other and is chlorine, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0111] Preferably, R 1 Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group, more preferably C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -Arylalkyl, C6-C 10 -Aryl or C7-C10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, or even more preferably two Rs 1 All are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In one embodiment, each R... 1 Independently identical or different from each other, is arbitrarily determined by C1-C. 10 -alkoxy-substituted C1-C 10 -alkyl group. Preferably two R groups. 1 The groups are identical. Most preferably, the two R groups are identical. 1 They are all methyl groups.

[0112] Preferably, R 2’ It is an α-branched C3-C 10 - Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6-C 10 Aryl, for example R 21 It is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group; or even more preferably R. 2’ It is C(CH3)2, methyl, ethyl, or n-propyl;

[0113] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 10 aryl, more preferably H, straight-chain or branched C1-C4-alkyl, or -OR 31 , where R 31 It is a C1-4 hydrocarbon group. Even more preferably, each R... 3 and R 4 Each is independent of the other, being the same or different, and is H, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially hydrogen, methyl or tert-butyl.

[0114] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3-, 4-, and / or 5-positions of the ring, with the 1-position connected to the indene ring.

[0115] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0116] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0117] Therefore, one or two R are preferred. 3 and / or R 4 The group is H. If the two R groups are H, then... 3 and / or 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. If an R 3 and / or R 4 If the group is H, then the remaining R 3 and / or R 4 The group is preferably located at the meta position.

[0118] Advantageously, one or two R on the phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 Same as, for example, 3',5'-dimethyl or 4'-tert-butyl.

[0119] For the indenyl moiety, one or two R on the phenyl group are preferred. 4 Not H, two Rs are preferred. 4 It's not H, the optimal choice is these two Rs. 4 Similar to 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0120] As mentioned above, R 51’ It is C1-C 10 - Hydrocarbon group, for example, straight-chain or branched C1-C 10 - Hydrocarbon group. R is preferred. 51’ It is a straight-chain or branched C1-C6-alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, C7-C 10 -Arylalkyl, C7-C 10 -alkylaryl or C6-C 10 -aryl, more preferably straight-chain or branched C1-C6 alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0121] Preferred R 6’ It is C(R) 61 )3, where R 61’ It is a straight-chain C1-C3 alkyl group; more preferably methyl. Therefore, advantageously, R6’ It is tert-butyl.

[0122] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ic).

[0123] (Ic)

[0124] in

[0125] Mt is either Zr or Hf;

[0126] Each X is an independent σ ligand;

[0127] R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached;

[0128] R 2’ It is C1-C 10 - Hydrocarbon group, preferably straight-chain or branched C1-C 10 -Hydrocarbon group;

[0129] R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It's not hydrogen.

[0130] For compounds of formula (Ic) defined above, the following represent preferred embodiments, which may be selected individually or in combination:

[0131] In the complex of formula (Ic), Mt is preferably Zr or Hf, with Zr being more preferred.

[0132] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is an H, halogen, C1-C6 oxy, or R' group, wherein R' is a C1-C6 alkyl, phenyl, or benzyl group. More preferably, each X is independently the same or different from each other and is chlorine, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0133] Preferably, R 1 Each being independently the same or different from the others is C1-C.10 -Hydrocarbon group, more preferably C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -Arylalkyl, C6-C 10 -Aryl or C7-C 10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, or even more preferably two Rs 1 All are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In one embodiment, each R... 1 Independently identical or different from each other, is arbitrarily determined by C1-C. 10 -alkoxy-substituted C1-C 10 -alkyl group. Preferably two R groups. 1 The groups are identical. Most preferably, the two R groups are identical. 1 They are all methyl groups.

[0134] Preferably, R 2’ It is an α-branched C3-C 10 - Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6-C 10 Aryl, for example R 21 It is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group.

[0135] Preferably, R 2’ It is an α-branched C3-C 10 - Hydroxyl group or CH2-R 21 , where R 21 It is H, straight-chain or branched C1-C6-alkyl, C3-C8 cycloalkyl or C6- 10 Aryl; more preferably, R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-6-alkyl group, preferably R. 21 It is H or a straight-chain or branched C1-C3-alkyl group, or even more preferably R. 2’It is C(CH3)2, methyl, ethyl, or n-propyl;

[0136] Preferred R 2’ It is an α-branched C3-C6-alkyl or CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group, more preferably, R 2 It is methyl and R 2’ It is CH2-R 21 , where R 21 It is an H or a straight-chain or branched C1-C3-alkyl group. Most preferably, R 2’ It is methyl, ethyl, or propyl (e.g., n-propyl or isopropyl).

[0137] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 10 aryl, more preferably H, straight-chain or branched C1-C4-alkyl, or -OR 31 , where R 31 It is a C1-4 hydrocarbon group. Even more preferably, each R... 3 and R 4 Each is independent of the other, being the same or different, and is H, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially hydrogen, methyl or tert-butyl.

[0138] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0139] Advantageously, R on both rings 3 Same as, for example, 3',5'-dimethyl or 4'-tert-butyl.

[0140] For the indenyl moiety, the two R groups on the benzene ring are preferred. 4 Same as, such as 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0141] synthesis

[0142] The ligands required to form the complexes of this invention and the resulting catalysts can be synthesized by any method, and skilled organic chemists can devise a variety of synthetic schemes to produce the necessary ligand materials. For example, WO 2007 / 116034 discloses the necessary chemical schemes. Synthetic schemes can also typically be found in WO2002 / 02576, WO2011 / 135004, WO2012 / 084961, WO2012 / 001052, WO2011 / 076780, WO2015 / 158790, WO2018 / 122134, WO2019 / 179959, and WO2012 / 058740. The Examples section also provides ample guidance for those skilled in the art.

[0143] Polymerization catalyst

[0144] From another perspective, the present invention provides a polymerization catalyst comprising...

[0145] (i) Metallocene complexes of formula (I);

[0146] (ii) Catalysts containing Group 13 elements; and

[0147] (iii) Optional carrier.

[0148] Catalyst manufacturing

[0149] The metallocene complexes described above are used in combination with suitable cocatalysts as described below.

[0150] Metallocene catalysts can be used in supported or unsupported forms. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina, or zirconium oxide, or a mixed oxide (e.g., silica-alumina), particularly silica, alumina, or silica-alumina. Silica support is preferred. Those skilled in the art know the procedures required for supporting metallocene catalysts.

[0151] Particularly preferred is that the support is a porous material, allowing the complex to be loaded into the pores of the support, for example using methods similar to those described in WO94 / 14856 (Mobil), WO95 / 12622 (Borealis), and WO2006 / 097497. Particle size is not critical, but is preferably in the range of 5 to 200 μm, more preferably 20 to 80 μm. The use of such supports is conventional in the art. Particularly preferred procedures for producing such supported catalysts are those described in EP1828266, WO 2020 / 239598, and WO2020 / 239603.

[0152] Alternatively, no support may be used at all. Such catalysts can be prepared in solution (e.g., in an aromatic solvent such as toluene) by contacting a metallocene (as a solid or as a solution) with a co-catalyst (e.g., methylaluminoxane, borane, or borate pre-dissolved in an aromatic solvent), or by sequentially adding the dissolved catalyst components to a polymerization medium.

[0153] In one aspect, no external support is used, but the catalyst still exists in solid particulate form. Therefore, no external support material, such as an inert organic or inorganic support (e.g., silica as described above), is used, but the solid catalyst is prepared using an emulsion curing method. Such catalysts can be prepared as described, for example, in WO 2003 / 051934, WO 2014 / 060540, and WO 2019 / 179959.

[0154] The catalyst system of the present invention is preferably used in a supported form. The particulate support material used is an inorganic porous support, such as silica, alumina, or a mixed oxide (e.g., silica-alumina), especially silica.

[0155] Silica carrier is preferred.

[0156] The complex can be loaded into the pores of a particulate carrier, for example using methods similar to those described in WO94 / 14856, WO95 / 12622, WO2006 / 097497 and EP18282666.

[0157] The average particle size of the support (e.g., silica support) is typically 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.

[0158] The average pore size of inorganic porous 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 inorganic porous supports (e.g., silica supports) can range from 20 to 40 nm.

[0159] The surface area of ​​inorganic porous supports (such as silica supports) can typically range from 100 to 400 m². 2 Within the range of / g.

[0160] 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.

[0161] The use of these carriers is common practice in this field.

[0162] The catalyst may contain 5 to 500 µmol (e.g. 10 to 100 µmol) of metallocene transition metal / g support (e.g., silica) and 3 to 15 mmol Al / g support (e.g., silica).

[0163] The polymerization catalyst of the present invention can be produced by the method described in, for example, WO2020239603 or WO2020239598.

[0164] In one aspect of this disclosure, a method for manufacturing the polymerization catalyst of the present invention includes...

[0165] P1-a) A porous inorganic support is mixed with an aluminoxane co-catalyst in a hydrocarbon solvent to obtain an aluminoxane co-catalyst-treated support, which is then optionally heat-treated.

[0166] P-1b) Optionally, the metallocene complex is mixed with the aluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of the aluminoxane cocatalyst added in step a) is 75.0 to 97.0 wt% of the total amount of the aluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 3.0 to 25.0 wt% of the total amount of the aluminoxane cocatalyst.

[0167] P1-c) Add the boron-containing co-catalyst to the solution obtained in step a) or b) to obtain a solution of metallocene complex, boron-containing co-catalyst and aluminoxane co-catalyst, wherein the boron-containing co-catalyst is added in an amount such that the boron / M molar ratio of the feed is in the range of 0.1:1 to 10:1.

[0168] P1-d) Add the solution obtained in step c) to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0169] P1-e) The supported catalyst system thus obtained is dried.

[0170] In an alternative aspect of this disclosure, the method includes

[0171] P2-a) Treat a porous inorganic support with an aluminoxane co-catalyst in a hydrocarbon solvent, optionally followed by heat treatment of the aluminoxane-treated support;

[0172] P2-b) The metallocene complex is mixed with a boron-containing co-catalyst and optionally an aluminoxane co-catalyst in a hydrocarbon solvent;

[0173] P2-c) Load the solution from step b) onto the treated carrier from step a);

[0174] The amount of aluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt% of the total amount of aluminoxane cocatalyst, and the amount of aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of aluminoxane cocatalyst.

[0175] In step P2-b) of this method, the various components can be mixed in any order. The boron-containing cocatalyst can be mixed with a metallocene complex, followed by the addition of hydrocarbons and optionally aluminoxanes, or the metallocene complex can be mixed with optional aluminoxanes and hydrocarbons, followed by the addition of the boron-containing cocatalyst, etc. In some embodiments, all components can be mixed simultaneously. Only one impregnation step is used, i.e., the treated support of step a) is loaded with metallocenes in only one step.

[0176] In a preferred aspect of the invention, the method includes

[0177] P3-a) A porous inorganic support is mixed with an aluminoxane cocatalyst in a hydrocarbon solvent to obtain an aluminoxane cocatalyst-treated support, which is then optionally heat-treated, the hydrocarbon solvent is filtered off, and the support is optionally washed with an aromatic solvent. The filtration and washing steps are repeated to remove unreacted aluminum compounds. The final aluminoxane cocatalyst-treated support is then dried.

[0178] P3-b) Add the metallocene hydrocarbon flux solution to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0179] P3-c) The supported catalyst system thus obtained is dried.

[0180] If desired, the obtained 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%, such as up to 25 wt%.

[0181] The amounts of support, aluminoxane (preferably MAO), boron-containing cocatalyst, and metallocene depend on the desired ratios defined above (boron / M, Al / M, Al / SiO2, M / SiO2).

[0182] co-catalyst

[0183] To form an active catalytic material, a co-catalyst well known in the art is typically required. Co-catalysts comprising one or more Group 13 metal compounds (such as organoaluminum, organoboron, and / or borate compounds used for activating metallocene catalysts) are suitable for this invention. Preferably, only aluminum-containing co-catalysts (such as organoaluminum compounds used for activating metallocene catalysts) are used in this invention.

[0184] According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst is advantageously used in combination with the metallocene catalyst complexes defined above.

[0185] In one aspect of the invention, the cocatalyst system comprising an aluminoxane cocatalyst is advantageously used in conjunction with the metallocene catalyst complexes defined above. Therefore, preferably, other cocatalysts comprising one or more Group 13 metal compounds other than aluminum (such as organoboron and / or borate compounds for activating metallocene catalysts) are not suitable for this invention.

[0186] The appropriate amount of catalyst will be well known to those skilled in the art.

[0187] Preferably, the amount of co-catalyst is selected to achieve a molar ratio below the defined range.

[0188] The molar ratio of Al from aluminoxane to metal ions (Mt) (preferably zirconium) 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.

[0189] The molar ratio of boron (B) to metallocene metal ions (Mt) (preferably zirconium) feed, B / Mt, can be in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, and especially 0.5:1 to 3:1 mol / mol. Even more preferably, the molar ratio of boron (B) to metallocene metal ions (Mt) (preferably zirconium) feed, B / Mt, is 0.5:1 to 2:1.

[0190] Aluminoxane co-catalyst

[0191] Aluminoxane co-catalysts can be one of formula (A):

[0192] (A)

[0193] Where n is typically between 6 and 20, and R has the following meanings.

[0194] 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).

[0195] The preferred aluminoxane is methylaluminoxane (MAO). 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.

[0196] Boron-containing cocatalyst

[0197] According to the present invention, a boron-containing cocatalyst can be used instead of an aluminum oxane cocatalyst, or an aluminum oxane cocatalyst can be used in combination with a boron-containing cocatalyst.

[0198] Those skilled in the art will understand that, when using a boron-based cocatalyst, the complex is typically pre-alkylated by reacting the complex with an alkylaluminum compound (e.g., TIBA). This procedure is well known, and any suitable alkylaluminum can be used, such as Al(C1-C6 alkyl)3. Preferred alkylaluminum compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum, and triisooctylaluminum.

[0199] Alternatively, when using a borate cocatalyst, the metallocene complex is in its alkylated form, i.e., dimethyl or dibenzyl metallocene complexes can be used, for example.

[0200] Meaningful boron-containing cocatalysts include those compounds of formula (B).

[0201] BY3 (B)

[0202] Where Y is the same or different, and is a hydrogen atom, C1- 10 - Haloalkyl or C6-C 20 - Halogenated aryl groups or fluorine, chlorine, bromine or iodine.

[0203] Preferred examples of Y are fluorine, trifluoromethyl, and unsaturated groups (e.g., halogenated aryl groups such as p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-bis(trifluoromethyl)phenyl).

[0204] Most preferably, Y is fluorine, trifluoromethyl, or an aromatic fluorinated group (e.g., p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-bis(trifluoromethyl)phenyl).

[0205] The preferred boron-containing cocatalyst of formula (B) is trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(pentafluorophenyl)borane and / or tris(3,4,5-trifluorophenyl)borane.

[0206] Tris(pentafluorophenyl)borane is particularly preferred.

[0207] However, borates, i.e., compounds containing borate anions, are preferred. These compounds have the formula (C):

[0208] Z4B –- W + (C)

[0209] Wherein Z is a substituted phenyl derivative, and the substituent is a halo-C1-C6-alkyl or halogen; W + It is a cationic counterion.

[0210] Preferably, the substituent of Z is fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0211] Borate anion Z4B – The preferred anion is a weakly coordinating anion, such as tetra(pentafluorophenyl)borate. A suitable cationic counterion W + It is a triarylcarbenium, such as triphenylcarbenium or a protonated amine or aniline derivative (e.g., methylammonium, aniline, dimethylammonium, diethylammonium, N-methylaniline, diphenylammonium, N,N-dimethylaniline, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylaniline or p-nitro-N,N-dimethylaniline).

[0212] Preferred ionic compounds that can be used according to the present invention include:

[0213] Tributylammonium tetra(pentafluorophenyl)borate

[0214] Tributylammonium tetra(trifluoromethylphenyl)borate

[0215] Tributylammonium tetra(4-fluorophenyl)borate,

[0216] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid

[0217] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid

[0218] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0219] N,N-di(propylammonium) tetra(pentafluorophenyl)borate,

[0220] di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate,

[0221] Triphenylcarbomon tetra(pentafluorophenyl)borate

[0222] Or ferrocene tetra(pentafluorophenyl)borate.

[0223] Preferred is triphenylcarbium tetra(pentafluorophenyl)borate,

[0224] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0225] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0226] The preferred option is triphenylcarbium tetra(pentafluorophenyl)borate.

[0227] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0228] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0229] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0230] polymerization

[0231] The catalyst according to the present invention is suitable for the production of propylene homopolymers, propylene-ethylene copolymers, or propylene C4-C. 10 α-olefin copolymers. Therefore, the method includes reacting propylene, propylene and ethylene, or propylene and C4-C... 10 α-olefins are polymerized. The ethylene content in such propylene-ethylene polymers can vary depending on the desired properties of the polymer. Typically, the ethylene content will range from 0.1 to 10 mol%. In particular, the catalyst of the present invention is used to produce propylene homopolymers or propylene copolymers with ethylene as a comonomer and propylene copolymers with butene as a comonomer.

[0232] Therefore, in a further aspect, this disclosure relates to a method for producing propylene homopolymers, propylene random copolymers, or multiphase propylene copolymers using a specific catalyst system as defined above.

[0233] 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.

[0234] This method may include an online prepolymerization step. This prepolymerization step is a routine step commonly used in polyolefin production equipment and can be carried out in a CSTR or loop reactor, after which the prepolymerized catalyst, along with one or more liquid monomers, is transferred from the reactor to the main loop reactor. Prepolymerization can be carried out at temperatures ranging from -10°C to 50°C, preferably from 10°C to 40°C.

[0235] In the case of propylene polymerization in a slurry reactor (e.g., a liquid loop reactor), the reaction temperature is typically in the range of 60 to 110°C (e.g., 60 to 90°C), the reactor pressure is typically in the range of 5 to 80 bar (e.g., 20 to 60 bar), and the residence time is typically in the range of 0.3 to 5 hours (e.g., 0.5 to 2 hours). Liquefied monomers are typically used as the reaction medium. A particular feature of the invention is that the polymerization is carried out at a temperature of at least 60°C.

[0236] For gas-phase reactors, the reaction temperature used is typically in the range of 60 to 115°C (e.g., 70 to 110°C), the reactor pressure is typically in the range of 10 to 30 bar-g (e.g., 15 to 25 bar-g), and the residence time is typically 0.5 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). In addition to the actual polymerization step and reactor, the method may include any additional polymerization steps, such as a prepolymerization step, and any other post-reactor treatment steps known in the art.

[0237] For solution polymerization, aliphatic or aromatic solvents can be used to dissolve the monomers and polymers, and the polymerization temperature is typically in the range of 80 to 200°C (e.g., 90 to 150°C).

[0238] 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.

[0239] The metallocene catalyst of this invention exhibits excellent catalytic activity and good comonomer response. This catalyst also provides high weight-average molecular weight (Mw) and polydispersity (Mw). w / M n Narrow polymer.

[0240] Furthermore, the random copolymerization behavior of the metallocene catalyst of the present invention shows a reduced tendency to transfer to the ethylene chain.

[0241] polymer

[0242] A feature of this invention is that the claimed catalyst is capable of forming propylene polymers with high molecular weights. These characteristics can be achieved at commercially meaningful polymerization temperatures (e.g., 60°C or higher, such as 60°C to 90°C). The polydispersity index (Mw / Mn) of the polymer depends on the polymerization conditions in each reactor and can be from 2.0 to 7.0. In a particular embodiment, the propylene polymer obtained using the catalyst of this invention has a narrow polydispersity index (Mw / Mn) of 2.0 to 4.0.

[0243] propylene homopolymer

[0244] Depending on the use and amount of hydrogen used as a Mw modifier, the Mw (weight average molecular weight) value of the propylene homopolymer prepared from the catalyst system containing the metallocene of the present invention can be in the range of 40 to 2000 kg / mol, preferably in the range of 50 to 1500 kg / mol. The catalyst of the present invention is capable of forming polypropylene homopolymers with high melting points. In a preferred embodiment, the propylene homopolymer formed by the method of the present invention has a melting point above 155°C, preferably above 157°C. propylene homopolymers with melting points up to 158°C or even up to 160°C can be formed.

[0245] propylene copolymer

[0246] The metallocene compounds prepared by this invention contain ethylene or C4-C 10 Propylene copolymers of α-olefin comonomers can be prepared with high productivity and low solubility.

[0247] 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.

[0248] The invention will now be described with reference to the following non-limiting examples.

[0249] experiment

[0250] Measurement methods

[0251] Determination of Al, B and Zr (ICP method)

[0252] In a glove box, an equal volume of catalyst (approximately 40 mg) was weighed into a glass weighing boat using an analytical balance. The sample was then exposed to air overnight while being placed in a second steel 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 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.

[0253] The instrument was calibrated for Al, B, Hf, Mg, Ti, and Zr 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 of Al, B, Hf, Mg, Ti, and Zr, respectively, in a 5% distilled aqueous solution of HNO3). However, not every calibration point was used for every wavelength. Each calibration solution contained 4 mg / L of LY and Rh standards. Al at 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. The calibration method for Al 167.079 nm is consistent with that for Al 394.401 nm, but 100 mg / L is excluded, and Zr 339.198 nm is calibrated using blank solution, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L standard solutions. Curve fitting and 1 / concentration weighting are used for the calibration curve.

[0254] Prior to analysis, the calibration solution was immediately validated and adjusted using a blank solution and 10 mg / L standard solutions of Al, B, Hf, Mg, Ti, and Zr (containing 4 mg / L LY and Rh) (instrument slope correction function). Quality control samples (QC: 1 mg / L Al, Au, Be, Hg & Se; 2 mg / L Hf & Zr, 2.5 mg / L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn & V; 4 mg / L Rh & Y; 5 mg / L Ca, K, Mg, Mn, Na & Ti; 10 mg / L Cu, Pb, and Zn; 25 mg / L Fe and 37.5 mg / L Ca in 5% HNO3 distilled aqueous solution) were tested to confirm the slope correction for Al, B, Hf, Mg, Ti, and Zr. QC samples were also tested at the end of the scheduled analysis.

[0255] Zr content was monitored using the Zr 339.198 nm {99} line. Aluminum content was monitored using the 167.079 nm {502} line when the Al concentration in the test section was below 2 wt%, and using the 394.401 nm {85} line when the Al concentration was above 2 wt%. Y 371.030 nm {91} was used as an internal standard for Zr 339.198 nm and Al 394.401 nm, and Y 224.306 nm {450} was used as an internal standard for Al 167.079 nm.

[0256] The content of B was monitored using the B 249 nm line. The reported values ​​of the original catalyst sample were inversely calculated using the original mass and dilution volume of the aliquots of the catalyst.

[0257] catalytic

[0258] Catalyst activity is calculated based on the following formula:

[0259]

[0260] GPC: Average molecular weight, molecular weight distribution, and polydispersity index (Mn, Mw, Mw / Mn)

[0261] The molecular weight distribution (MWD) and corresponding average molecular weight (M) of polymer samples were determined by gel permeation chromatography (GPC) at 160 °C. n M w M v and M z All samples were placed in a low M... w Integrate until the third-to-last calibration point of the calibration curve (PS = 1820 g / mol ~ 1340 g / mol PP equivalent).

[0262] A high-temperature GPC equipped with a suitable concentration detector (such as a PolymerChar (Valencia, Spain) IR5 or IR4), an online four-capillary bridge viscometer (PL-BV 400-HT), and dual light scattering detectors with 15° and 90° angles (PL-LS 15 / 90 light scattering detector) was used. Agilent 3x Olexis and 1x Olexis guard columns were used as the stationary phase, and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methylphenol) was used as the mobile phase at 160 °C and a constant flow rate of 1 mL / min. 200 μL of sample solution was injected for each analysis. All samples were prepared by dissolving 8.0–10.0 mg of polymer in 10 mL (at 160 °C) of stabilized TCB (same as the mobile phase) and continuously gently agitating at 160 °C for 2.5 h. The injected concentration of the polymer solution at 160 °C (c...) is... 160℃ ) Determine in the following manner.

[0263]

[0264] Where: w 25 (Polymer weight) and V 25 (Volume of TCB at 25℃).

[0265] Nineteen narrow MWD polystyrene (PS) standards were used, ranging from 0.5 kg / mol to 11500 kg / mol, and the column set was calibrated using universal calibration (according to ISO 16014-2:2019). The PS standards were dissolved at 160 °C for 15 min, or at room temperature, with a concentration of 0.2 mg / ml for molecular weights greater than or equal to 899 kg / mol and 1 mg / ml for molecular weights less than 899 kg / mol. The conversion of the polystyrene peak molecular weight to the polyethylene molecular weight was accomplished using the Mark Houwink equation and the following Mark Houwink constant:

[0266] K PS = 19 x 10 -5 ml / g, α PS = 0.655

[0267] K PP = 39 x 10 -5 ml / g, α PP = 0.725

[0268] Third-order polynomial fitting was used to fit the calibration data.

[0269] All samples were prepared to a concentration range of 0.5–1 mg / ml and dissolved by gentle shaking continuously at 160°C for 3 hours.

[0270] The average molecular weight (M) is determined using the following formula. n M w M v and M z Molecular weight distribution (MWD) and its width (derived from the polydispersity index PD=M) w / M n (where M) n It is the number average molecular weight, M w (This is a description of weight-average molecular weight).

[0271] (1)

[0272] (2)

[0273] (3)

[0274] (4)

[0275] DSC

[0276] 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.

[0277] melt flow rate

[0278] Melt flow rate (MFR) is determined according to ISO 1133 and expressed in g / 10 min. MFR is an indicator of polymer flowability and therefore also an indicator of processability. Higher melt flow rates generally correspond to lower molecular weight polymers. MFR is measured at 230°C and can be determined at different loads (e.g., 2.16 kg (MFR2) or 21.6 kg (MFR3)). 21 ))Measured under.

[0279] Metallocene synthesis

[0280] Comparison of the synthesis of metallocene CM1

[0281] The synthesis of this metallocene has been carried out as described in WO2019179959, MC-2.

[0282] Comparison of the synthesis of metallocene CM2

[0283] 2,5,6-Trimethylindan-1-one

[0284]

[0285] 2-Bromo-2-methylpropionyl bromide (144.8 g, 77.9 ml, 0.63 mol) was added dropwise over 15 min to a suspension of AlCl3 (222.7 g, 1.67 mol, 2.65 equivalents) in 200 ml dichloromethane cooled to -30 °C. The reaction mixture was stirred at -30 °C for 0.5 h, then the temperature was raised to -20 °C, and a solution of o-xylene (66.9 g, 76.9 ml, 0.63 mol) in 200 ml dichloromethane was added dropwise over 30 min. The cooling bath was removed, the temperature was raised to room temperature, and the reaction mixture was stirred at this temperature for 5 h. The resulting mixture was poured onto 1 kg of ice, and 300 ml of 12 M HCl was added. The resulting mixture was extracted with 4 × 250 ml dichloromethane. The combined organic extracts were washed with an aqueous K₂CO₃ solution, dried with K₂CO₃, and then evaporated to dryness. The residue was purified by vacuum distillation to give 103.45 g (94.2%) of a mixture of straight-chain 2,5,6-trimethylindan-1-one and angular 2,4,5-trimethylindan-1-one in a ratio of approximately 2:1 (favoring the straight-chain isomer), as a yellow oil (bp 122-130℃ / 5 mm Hg). The resulting mixture was dissolved in 400 ml of n-hexane and then crystallized overnight at -30℃. The precipitate was crushed with a scraper, filtered (G3), and then allowed to stand until the temperature of the precipitate reached room temperature and the mother liquor dripping essentially stopped. The white, slightly oily substance remaining on the filter (approximately 56 g) was dissolved in 55 ml of n-hexane and then recrystallized at 0℃ to give 23.5 g (21%) of a white crystalline powder of 2,5,6-trimethylindan-1-one (free-flowing, non-sticky) and approximately 2-5% angular isomer impurities. 1 H NMR (CDCl3): δ 7.49 (s, 1H), 7.20 (s, 1H), 3.36-3.22 (m, 1H), 2.73-2.56 (m, 2H), 2.32 (s, 3H), 2.28 (s, 3H), 1.28 (d,J =7.2 Hz, 3H). 13C NMR (CDCl3): δ 209.56, 152.02, 145.22, 136.57, 134.83, 127.63, 124.63, 42.54, 34.91, 21.07, 20.09, 16.86.

[0286] 4,7-Dibromo-2,5,6-trimethylindan-1-one

[0287]

[0288] At -10 °C, a solution of 2,5,6-trimethylindan-1-one (33.8 g, 194 mol) in 35 mL of dichloromethane was added dropwise over 0.5 h to a suspension of AlCl3 (64 g, 480 mol, 2.47 equivalence) in 250 mL of dichloromethane. The reaction mixture was stirred at this temperature for 10 min, and then 0.35 g of iron powder was added. Next, 20.3 mL (63.0 g, 394.0 mmol, 2.03 equivalence) of bromine was added dropwise over 0.5 h. The resulting mixture was stirred overnight at room temperature and then poured into a 500 cm³ container. 3 The organic layer was separated from the aqueous layer in crushed ice. The aqueous layer was extracted with 2 × 250 ml dichloromethane. The combined organic extracts were washed with aqueous K₂CO₃ solution, dried over K₂CO₃, passed through a silica gel 60 short-shield (40–63 µm), and then evaporated to dryness. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 1000 mm, eluent: hexane / CH₂Cl₂ = 1:1). This procedure yielded 49.6 g (77.0%) pure 4,7-dibromo-2,5,6-trimethylindan-1-one.

[0289] 1 H NMR (CDCl3): δ 3.25 (dd,J = 17.6 Hz, J = 8.1 Hz, 1H), 2.79-2.68 (m,1H), 2.58 (dd, J = 17.6 Hz, J = 4.1 Hz, 1H), 2.55 (s, 3H), 2.51 (s, 3H), 1.32(d, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 205.74, 153.37, 144.43, 138.42, 133.10, 123.90, 120.96, 42.66, 35.88, 21.70, 19.99, 16.40.

[0290] 4,7-Bis(3,5-dimethylphenyl)-2,5,6-trimethylindan-1-one

[0291]

[0292] 43.99 g (132.49 mmol) of 4,7-dibromo-2,5,6-trimethylindan-1-one, 49.68 g (331.24 mmol, 2.5 equivalents) of 3,5-dimethylphenylboronic acid, and 2.0 g (3.91 mmol, 2.95 mol.%) of Pd(P t A mixture of Bu3)2, 84.4 g Na2CO3, 545 ml 2-methyltetrahydrofuran, and 380 ml water was refluxed for 6 h. Then, 500 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 300 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a brown solid. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane / CH2Cl2 = 1:1, then 1:3, vol.). 52.42 g (approximately 100%) of a white solid was obtained.

[0293] 1 H NMR (CDCl3): δ 7.03 (s, 1H), 7.01 (s, 1H), 6.86 (s, 1H), 6.84 (s,1H), 6.81 (s, 1H), 6.78 (s, 1H), 2.98 (dd,J = 17.2 Hz, J = 8.1 Hz, 1H), 2.58-2.48 (m, 1H), 2.38 (s, 6H), 2.37 (s, 3H), 2.35 (s, 3H), 2.38-2.29 (dd, 1H), 2.14 (s, 3H), 2.06 (s, 3H), 1.15 (d, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ208.13, 149.86, 141.74, 139.20, 139.16, 138.29, 137.99, 137.98, 137.03,136.96, 135.03, 130.91, 128.70, 128.60, 126.75, 126.72, 126.60, 42.47, 34.00, 21.52, 21.41, 21.38, 18.56, 16.96, 15.92.

[0294] 4,7-Bis(3,5-dimethylphenyl)-2,5,6-trimethyl-1H-indene

[0295]

[0296] NaBH4 (7.8 g, 206.2 mol, 1.51 equivalents) was added to a solution of 4,7-bis(3,5-dimethylphenyl)-2,5,6-trimethylindan-1-one (52.42 g, calculated 137.03 mmol) in 400 mL THF cooled to 5 °C. MeOH (200 mL) was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture thus obtained was evaporated to dryness, and 700 mL of dichloromethane and 700 mL of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 2 × 300 mL of dichloromethane. The combined organic extracts were passed through a silica gel 60 mat (40–63 µm; eluent: dichloromethane) (~30 mL) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a gray solid block. TsOH (0.5 g) was added to this solid in a 500 mL solution of toluene. The mixture was refluxed using a Dean-Stark separator for 10 min, then cooled to room temperature in a water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 500 mL of dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 250 mm, eluent: hexane / CH₂Cl₂ = 3:1, vol.). The combined eluent was evaporated to approximately 100 mL, and the white solid precipitated (G₃) was filtered off. The mother liquor was evaporated to dryness, and the residue was ground with a small amount of hexane and filtered off (G₃). The combined precipitates were dried under vacuum to give 47.29 g (97.4% yield of the two stages starting from 4,7-dibromo-2,5,6-trimethylindan-1-one) 4,7-bis(3,5-dimethylphenyl)-2,5,6-trimethyl-1H-indene.

[0297] 1 H NMR (CDCl3): δ 6.99 (s, 2H), 6.93 (s, 2H), 6.91 (s, 2H), 6.15 (m,1H), 3.06 (s, 2H), 2.37 (s, 12H), 2.14 (s, 3H), 2.10 (s, 3H), 1.98 (s, 3H). 13CNMR (CDCl3): δ 145.04, 141.77, 141.21, 140.71, 139.32, 137.58, 137.33,136.99, 133.36, 132.30, 129.82, 128.14, 128.01, 127.78, 126.97, 126.72, 43.17, 21.41, 17.67, 17.50, 16.66.

[0298] [4,7-bis(3,5-dimethylphenyl)-2,5,6-trimethyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane

[0299]

[0300] Will n A hexane solution of BuLi (2.5 M, 7.4 ml, 18.5 mmol) was added in a single dose to a suspension of 4,7-bis(3,5-dimethylphenyl)-2,5,6-trimethyl-1H-indene (6.75 g, 18.42 mmol) in a mixture of 100 ml diethyl ether and 25 ml THF cooled to -50 °C. The resulting mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C, followed by the addition of 150 mg CuCN. The resulting mixture was stirred at -25 °C for 0.5 h, and then a single dose of a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-methyl-5-methoxy-1H-indene-1-yl]chlorodimethylsilane (7.6 g, 18.4 mmol) in 150 ml diethyl ether was added. The mixture was stirred at room temperature for 5 h, then filtered through a silica gel 60 filter bed (40–63 µm) and washed with 2 × 50 ml of diethyl ether. The combined organic eluents were evaporated to dryness, and the residue was dried under vacuum at high temperature to give 13.87 g (approximately 100%, approximately 85% pure) of the title product (approximately a 1:1 mixture of stereoisomers) as a pale yellow glassy solid, which was ready for use without further purification.

[0301] trans-dimethylsilanediyl[2,5,6-trimethyl-4,7-bis(3,5-dimethylphenyl)-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

[0302]

[0303] At room temperature nA hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 mmol) was added in one step to [4,7-bis(3,5-dimethylphenyl)-2,5,6-trimethyl-1H-indene-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-indene-1-yl]dimethylsilane (7.43 g, approx. 10.0 mmol) in 50 ml n The mixture was stirred overnight at room temperature in a pale yellow solution of Bu₂O. The resulting turbid yellow solution was then cooled to 0°C in an ice bath, and ZrCl₄ (2.33 g, 10.0 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give a pale orange suspension. The mixture was evaporated to dryness (to an orange foamy state). Based on NMR spectral evidence, the resulting solid contained approximately 85 / 15 of a mixture of trans- and cis-zirconia dichlorocerocene. The solid was extracted with 70 mL of boiling n-hexane, the extract was evaporated to approximately 15 mL, and 15 mL of n-pentane was added. The orange crystalline solid precipitated overnight at room temperature was collected and dried under vacuum. This procedure yielded 3.2 g of trans-zirconia dichlorocerocerocene as a solvate with approximately 0.5 molecules of n-pentane; therefore, the adjusted net weight of the isolated trans isomer was 3.05 g.

[0304] C 53 H 60 Cl2OSiZr.(C5H 12 Calculated values: C, 71.42; H, 7.44. Measured values: C, 71.59; H, 7.74.

[0305] 1 H NMR (CDCl3): δ 7.60-6.95 (very br. s, 2H), 7.50 (s, 1H), 7.40 (s,1H), 7.09 (s, 1H), 7.01 (s, 1H), 6.96 (s, 2H), 6.92 (s, 1H), 6.77 (s, 1H),6.58 (s, 1H), 6.51 (s, 1H), 3.43 (s, 3H), 2.39 (s, 3H), 2.37 (s, 3H), 2.35(s, 9H), 2.32 (s, 3H), 2.26 (s, 3H), 2.25 (s, 3H), 2.11 (s, 3H), 2.04 (s, 3H), 1.34 (s, 9H), 1.10 (s, 3H), -0.19 (s, 3H).

[0306] 13C NMR (CDCl3): δ 159.80, 143.89, 141.54, 139.15, 138.52, 137.93,137.78, 137.09, 136.95, 136.05, 136.01, 135.18, 135.05, 134.89, 134.50,134.47, 131.11, 130.85, 129.91, 129.45, 129.14, 128.71, 128.65, 127.81,127.50, 127.22, 126.67, 125.17, 123.04, 121.17, 120.98, 82.76, 81.58, 62.78, 35.67, 30.39, 21.46, 21.41, 21.37, 21.24, 19.78, 18.86, 18.83, 18.79, 3.90, 0.88.

[0307] Synthesis of metallocene IM1 in this invention

[0308] Synthesis of 6-tert-butyl-5-methoxy-2-methylindan-1-one

[0309]

[0310] At 50°C, methacrylic acid (137.6 g, 1.6 mol) was added to a mixture of 220 g P4O 10 The mixture was prepared with Eaton's reagent obtained from 1120 ml of MeSO3H. 1-tert-butyl-2-methoxybenzene (131.2 g, 0.8 mol) was added dropwise to the mixture over approximately 1 h with vigorous stirring at 50–53 °C (water bath temperature). The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 1.5 L of cold water and 3 kg of ice. The crude product was extracted with 3 × 600 ml of dichloromethane. The combined organic extracts were washed with an aqueous K2CO3 solution, dried with K2CO3, and then evaporated to dryness. The residue was fractionally distilled to give 159.5 g of a pale yellow oil (bp 150–180 °C / 5 mm Hg.), which was crystallized at room temperature. The product was then dissolved in 300 ml of hot hexane. The crystals precipitated overnight from this solution at room temperature were collected, washed with 50 ml of cold hexane, and dried under vacuum. The procedure yielded 127.0 g of pure 6-tert-butyl-5-methoxy-2-methylindan-1-one. The mother liquor was evaporated to approximately 100 ml, resulting in the formation of a partially crystalline product. This procedure yielded an additional 10.5 g of the title product. Therefore, the total yield of the product was 137.5 g (74%).

[0311] 2-Methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one

[0312]

[0313] Bromine (45.0 g, 0.282 mol) was added over approximately 5 min with vigorous stirring to a mixture of 60.0 g (0.258 mol) of 6-tert-butyl-5-methoxy-2-methylindan-1-one, 130 g of NaOAc(H2O)3, 1.5 g of Et4NI, 220 ml of dichloromethane, and 450 ml of water cooled to 5 °C. The mixture was stirred at 5 °C for 1 h, and then a solution of 60.0 g of NaOAc(H2O)3 in 200 ml of water was added. Bromine (23.5 g, 0.147 mmol) was added to the resulting mixture at 5 °C. The resulting solution was stirred for 30 min and then washed with an aqueous solution of Na2SO3. The crude product was extracted with 3 × 300 ml of dichloromethane. The combined organic extracts were dried over K2CO3, passed through a silica gel 60 short layer (40–63 µm), and then evaporated to dryness. Vacuum drying of the residue yielded 79.9 g (99%) of the target product, which was ready for use without further purification.

[0314] 1 H NMR (CDCl3): δ 7.70 (s, 1H), 4.03 (s, 3H), 3.31 (dd, J = 17.4 Hz, J= 7.8 Hz, 1H), 2.72 (m, 1H), 2.62 (dd, J = 17.4 Hz, J = 3.8 Hz, 1H), 1.40 (s,9H), 1.32 (d, J = 7.6 Hz, 3H).

[0315] 13 C{ 1 H} NMR (CDCl3): δ 208.0, 162.8, 154.0, 145.5, 132.7, 121.5, 116.7, 61.7, 42.2, 36.1, 35.7, 30.6, 16.4.

[0316] 2-Methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-indan-1-one

[0317]

[0318] A mixture of 49.14 g (157.9 mmol) 2-methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one, 29.6 g (197.4 mmol, 1.25 equivalent) (3,5-dimethylphenyl)boric acid, 45.2 g (427 mmol) Na₂CO₃, 1.87 g (8.3 mmol, 5 mmol.%) Pd(OAc)₂, 4.36 g (16.6 mmol, 10 mol.%) PPh₃, 200 mL water, and 500 mL 1,2-dimethoxyethane was refluxed for 6.5 h. The DME was evaporated on a rotary evaporator, and 600 mL water and 700 mL dichloromethane were added to the residue. The organic layer was separated, and the aqueous layer was extracted again with 200 mL dichloromethane. The combined extracts were dried over K₂CO₃ and then evaporated to dryness to give a black oil. The crude product was purified by rapid chromatography on silica gel 60 (40-63 µm, hexane-dichloromethane = 1:1, vol., then 1:3, vol.) to give 48.43 g (91%) 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-indan-1-one as a brownish-brown oil.

[0319] C 23 H 28 Analytical values ​​for O2: C, 82.10; H, 8.39. Measured values: C, 82.39; H, 8.52.

[0320] 1 H NMR (CDCl3): δ 7.73 (s, 1H), 7.02 (s, 3H), 7.01 (s, 3H), 3.32 (s,3H), 3.13 (dd, J = 17.5 Hz, J = 7.8 Hz, 1H), 2.68-2.57 (m, 1H), 2.44 (dd, J =17.5 Hz, J = 3.9 Hz), 2.36 (s, 6H), 1.42 (s, 9H), 1.25 (d, J = 7.5 Hz, 3H). 13 C{ 1 H} NMR (CDCl3): δ 208.90, 163.50, 152.90, 143.32, 138.08, 136.26, 132.68,130.84, 129.08, 127.18, 121.30, 60.52, 42.17, 35.37, 34.34, 30.52, 21.38,16.40.

[0321] 2-Methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0322]

[0323] NaBH4 (8.2 g, 217 mmol) was added to a solution of 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-indan-1-one (48.43 g, 143.9 mmol) in 300 mL THF cooled to 5 °C. Then, 150 mL of methanol was added dropwise to the mixture over approximately 7 h at about 5 °C with vigorous stirring. The resulting mixture was evaporated to dryness, and the residue was partitioned between 500 mL dichloromethane and 500 mL 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 mL dichloromethane. The combined organic extracts were evaporated to dryness to give a pale yellow oil. 400 mg TsOH was added to a solution of this oil in 600 mL toluene, and the mixture was refluxed for 10 min using a Dean-Stark separator, then cooled to room temperature in a water bath. The solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 150 mL of dichloromethane. The combined organic extracts were dried with K₂CO₃ and then passed through a silica gel 60 short layer (40–63 µm). The silica gel layer was washed again with 100 mL of dichloromethane. The combined organic eluents were evaporated to dryness, and the resulting oil was dried under vacuum at high temperature. This procedure yielded 45.34 g (98%) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene, which was ready for use without further purification.

[0324] C 23 H 28 Analytical values ​​for O: C, 86.20; H, 8.81. Actual values: C, 86.29; H, 9.07.

[0325] 1 H NMR (CDCl3): δ 7.20 (s, 1H), 7.08 (br.s, 1H), 6.98 (br.s, 1H), 6.42(m, 1H), 3.25 (s, 3H), 3.11 (s, 2H), 2.36 (s, 6H), 2.06 (s, 3H), 1.43 (s,9H). 13 C{ 1H} NMR (CDCl3): δ 154.20, 145.22, 141.78, 140.82, 140.64, 138.30,137.64, 131.80, 128.44, 127.18, 126.85, 116.98, 60.65, 42.80, 35.12, 31.01,21.41, 16.65.

[0326] [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]chlorodimethylsilane

[0327]

[0328] Will n A hexane solution of BuLi (2.43 M, 14.6 ml, 35.5 mmol) was added in a single batch to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-methyl-1H-indene (11.3 g, 35.3 mmol) in 200 ml of diethyl ether, cooled to -50 °C. The resulting orange solution was stirred overnight at room temperature, and then the resulting orange solution containing a pale yellow precipitate was cooled to -78 °C (the precipitate almost completely disappeared), and dichlorodimethylsilane (22.8 g, 177 mmol, 5 equivalents) was added in a single batch. The resulting solution was warmed to room temperature and stirred overnight at room temperature. The resulting mixture was filtered through a glass frit (G4) funnel. The precipitate was washed again with 2 × 10 ml of diethyl ether. The combined filtrates were evaporated to dryness to give the title substance as a pale orange oil, which was ready for use without further purification.

[0329] 1,4-Dibromo-2-(bromomethyl)benzene

[0330]

[0331] Bromine (15.5 ml, 47.9 g, 0.30 mmol) was added dropwise to 2,5-dibromotoluene (74.9 g, 0.30 mol) over 3 h at 200 °C with vigorous stirring. The resulting mixture was cooled to room temperature. Fractional distillation yielded a colorless liquid, bp 132 °C–135 °C / 3 mm Hg. The yield was 84.3 g (85%, approximately 82% purity).

[0332] 1H NMR (CDCl3): δ 7.59 (s, 1H), 7.43 (d, J = 8.5 Hz, 1H), 7.29 (d, J =8.5 Hz, 1H), 4.52 (s, 2H). 13 C NMR (CDCl3): δ 138.94, 134.64, 133.95, 133.04, 130.31, 121.44, 32.11.

[0333] 4,7-Dibromo-2-methylindan-1-one

[0334]

[0335] Dissolve 6.10 g (0.27 mol) of metallic sodium in 200 mL of anhydrous ethanol. Add 45.5 g (0.26 mol) of diethyl methylmalonate to the resulting solution. Stir the mixture for 15 min, then add 84.3 g (0.26 mol) of 1,4-dibromo-2-(bromomethyl)benzene at a rate maintained by slight reflux of the reaction mixture. Reflux the mixture for 4 h, then cool to room temperature. Add a solution of 52.1 g of KOH in 140 mL of water. Reflux the mixture for 6 h to saponify the formed ester. Distill off the ethanol. Add 200 mL of water to the residue, then add 12 M HCl to pH 1. Filter off the precipitated substituted methylmalonate, wash with 2 × 100 mL of cold water, and air dry. Crude 3-(2,5-dibromophenyl)-2-methylpropionic acid was obtained by decarboxylating substituted methylmalonic acid by heating at 180 °C for 0.5 h in a round-bottom flask. The crude 3-(2,5-dibromophenyl)-2-methylpropionic acid thus obtained can be used without further purification. A mixture of this acid, 7 ml (114.6 g, 0.96 mol) SOCl2, and 100 ml dichloromethane was stirred overnight at room temperature. Excess thionyl chloride and dichloromethane were distilled off. The residue was dried under vacuum and then dissolved in 95 ml dichloromethane. The resulting solution was added dropwise to a suspension of 47.0 g (0.35 mol) AlCl3 in 470 ml dichloromethane over 1 h at 0 °C. The resulting mixture was refluxed for 3 h, cooled to ambient temperature, and then poured into a 1000 cm³ container. 3On ice. Separate the organic layer. Extract the aqueous layer with 3 × 200 ml dichloromethane. Dry the combined organic extracts with K₂CO₃ and evaporate to dryness. Purify crude 4,7-dibromo-2-methylindan-1-one by column chromatography on silica gel 60 (40–63 µm, d 50 mm, l 1250 mm, eluent: hexane / CH₂Cl₂ = 1:1, vol.). Yield: 54.1 g (70%).

[0336] 1 H NMR (CDCl3): δ 7.52 (d, J= 8.4 Hz, 1H), 7.37 (d, J= 8.4 Hz, 1H), 3.27 (dd, J= 17.7 Hz, J= 8.0 Hz, 1H), 3.73 (m, 1H), 2.58 (dd, J= 17.7 Hz, J=4.2 Hz, 1H), 1.31 (d, J= 7.3 Hz, 3H). 13 C NMR (CDCI3): δ 205.5, 155.4, 137.6, 135.3, 133.9, 121.0, 118.6, 42.6, 35.3, 16.1.

[0337] 4,7-Dibromo-2-methyl-1H-indene

[0338]

[0339] NaBH4 (9.40 g, 0.248 mmol) was added to a solution of 4,7-dibromo-2-methyl-1-indanone (54.1 g, 0.178 mol) in 200 mL THF cooled to 5 °C. Then, 8 mL of methanol was added dropwise to the mixture over approximately 3 h at 5 °C. The resulting mixture was stirred overnight at ambient temperature. The mixture was evaporated to dryness, and the residue was partitioned between 500 mL dichloromethane and 500 mL 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 mL dichloromethane. The combined organic extracts were evaporated to dryness. 500 mL toluene and 5.0 g TsOH were added to the residue. The toluene solution was refluxed using a Dean-Stark separator until water was completely removed. After cooling to room temperature, the reaction mixture was washed with 200 mL 10% NaHCO3. The organic layer was separated, and the aqueous layer was extracted again with 2 × 50 mL toluene. The combined organic extracts were dried with K₂CO₃ and evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 550 mm, eluent: hexane / CH₂Cl₂ = 10:1, vol.). The yield was 47.2 g (92%).

[0340] 1 H NMR (CDCl3): δ 7.18 (d, J= 8.4 Hz, 1H), 7.03 (d, J= 8.4 Hz, 1H), 6.55 (s, 1H), 3.29 (s, 2H), 2.14 (s, 3H). 13 C NMR (CDCI3): δ 148.17, 146.88, 144.28, 131.09, 127.88, 126.85, 116.93, 112.61, 45.38, 16.73.

[0341] 4,7-Bis(3,5-dimethylphenyl)-2-methyl-1H-indene

[0342]

[0343] 46.79 g (162.48 mmol) of 4,7-dibromo-2-methyl-1H-indene, 56.0 g (370 mmol) of (3,5-dimethylphenyl)boric acid, 93.1 g (906 mmol) of Na2CO3, and 1.3 g (2.54 mmol) of Pd(P tA mixture of Bu3)2, 420 ml water, and 600 ml 2-methyltetrahydrofuran was refluxed for 5 h. The organic layer was separated and evaporated to dryness. Crude 4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-indene was purified by column chromatography on silica gel 60 (40–63 µm, d 50 mm, l 1000 mm, eluent: hexane / CH2Cl2 = 5:1, vol.). The eluent was evaporated to dryness, and the residue was refluxed with 300 ml hot n-hexane. The white crystals precipitated at -5 °C were collected and dried under vacuum. This procedure yielded 52.5 g (95%) of the title product.

[0344] 1 H NMR (CDCl3): δ 7.31 (d, J= 7.8 Hz, 1H), 7.17-7.15 (m, 5H), 7.00 (s,2H), 6.72-6.70 (m, 1H), 3.43 (s, 2H), 2.39-2.38 (m, 12H), 2.13 (s, 3H). 13 C NMR(CDCI3): δ 146.50, 143.78, 141.23, 141.19, 140.94, 137.82, 136.43, 133.20,128.65, 128.40, 127.41, 126.74, 126.34, 126.32, 124.64, 43.06, 21.42, 16.82.

[0345] [4,7-Bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane

[0346]

[0347] Will nA hexane solution of BuLi (2.5 M, 8.35 ml, 20.8 mmol) was added in a single addition to a solution of 4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-indene (7.05 g, 20.8 mmol) cooled to -50 °C in a mixture of 100 ml diethyl ether and 25 ml THF. The resulting mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C and 150 mg CuCN was added. The resulting mixture was stirred at -25 °C for 0.5 h, and then a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-5-oxomethyl-2-methyl-1H-indene-1-yl]chlorodimethylsilane (8.6 g, 20.8 mmol) in a mixture of 125 ml diethyl ether and 35 ml THF was added in a single addition. The resulting mixture was stirred overnight at room temperature, then filtered through a silica gel 60 filter (40–63 μm) and washed with 2 × 50 mL of diethyl ether. The combined organic eluents were evaporated to dryness. The crude product was purified by column chromatography on silica gel 60 (40–63 µm, d 50 mm, l 600 mm, eluent: hexane / CH₂Cl₂ = 10:1, then 2:1, vol.). This procedure yielded 12.9 g (18.0 mmol, approximately 86.7%, purity approximately 95%) of the title product (a mixture of approximately 55:45 stereoisomers) as a pale yellow glassy solid, ready for use without further purification.

[0348] trans-dimethylsilanediyl[2-methyl-4,7-bis(3,5-dimethylphenyl)-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

[0349]

[0350] At room temperature, nA hexane solution of BuLi (2.5 M, 13.1 mL, 32.72 mmol) was added in a single batch to a solution of [4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane (11.7 g, 16.35 mmol) in 100 mL of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting red solution was then cooled to 0 °C in an ice bath, followed by the addition of ZrCl4 (3.81 g, 16.35 mmol). The reaction mixture was stirred at room temperature for 24 h to give a yellow suspension. The suspension was evaporated to dryness. The solid residue was extracted with 150 mL of boiling toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of trans- and cis-zirconium dichloroethylene in a ratio of approximately 83:17.

[0351] The mother liquor was evaporated to approximately 80 ml. The orange solid precipitated from this solution at room temperature was collected and dried under vacuum. This procedure yielded 8.20 g of trans-zirconia containing approximately 0.8 mol toluene, thus the adjusted net weight of the isolated trans isomer was 7.56 g. The mother liquor was evaporated to approximately 25 ml, and 25 ml of hexane was added. The orange solid precipitated from this solution at room temperature was collected and dried under vacuum. This procedure yielded 2.30 g of trans-zirconia and trace amounts of polymer byproduct impurities, thus the adjusted net weight of the isolated trans isomer was 2.12 g. Therefore, the total yield of trans-zirconia isolated in this synthesis was 9.68 g (67.7%).

[0352] C 51 H 56 Analytical values ​​of Cl2OSiZr*0.8(C7H8): C, 71.64; H, 6.62. Actual values: C, 71.75; H, 6.84.

[0353] 1 H NMR (CDCl3): δ 7.44 (s, 1H), 7.39 (d, J =7.2 Hz, 1H), 7.37 (s, 2H), 7.30-7.10 (m, 5H), 6.99 (d, J =6.3 Hz, 2H), 6.96-6.91 (m, 2H), 6.61 (s, 1H), 3.44 (s, 3H), 2.39-2.32 (m, 21H), 1.96 (s, 3H), 1.38 (s, 9H), 1.19 (s, 3H), -0.04 (s, 3H).

[0354] 13 C NMR (CDCl3): δ 160.01, 144.55, 143.27, 139.37, 139.08, 138.42,137.96, 136.74, 135.78, 134.21, 134.12, 130.77, 130.41, 130.34, 129.34,129.31, 128.82, 128.28, 127.38 (br. s.), 127.00, 126.72, 126.07, 125.10,123.66, 123.56, 122.49, 121.01, 82.88, 82.41, 62.64, 35.72, 30.41, 21.44, 21.35, 21.22, 19.72, 18.43, 3.35, 2.76.

[0355] Synthesis of metallocene IM2 in this invention

[0356] Ethylmalonic acid

[0357]

[0358] 196.4 g (3.5 mol) of potassium hydroxide was heated at 1000 cm⁻¹ 3 The aqueous solution was added to a solution of 188.2 g (1.0 mol) diethyl malonate in 500 mL of methanol. The resulting mixture was refluxed for 5 h, and then the ethanol and methanol were distilled off. 1000 cm³ of water was then added, and the resulting mixture was acidified to pH 1.0 with 12 M HCl. Ethyl malonate was extracted with 5 × 300 mL of diethyl ether. The combined extracts were evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 120.2 g (91.0%) ethyl malonate as a white solid.

[0359] 1 H NMR (DMSO-d6): δ 4.28 (br.s, 2H), 3.12 (d, J = 7.4 Hz, 1H), 1.71 (quin, J = 7.40 Hz, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 171.12, 53.36, 22.01, 11.95.

[0360] 2-Ethylacrylic acid

[0361]

[0362] Diethylamine (108.2 ml, 76.82 g, 1.05 mol) was added dropwise to a solution of ethylmalonic acid (118.8 g, 899.2 mmol) in 1300 ml of ethyl acetate at 5 °C. Paraform (38.4 g, 1.28 mol) was added to the resulting suspension. The mixture was refluxed for 5 h, then cooled to 5 °C, and then 600 ml of diethyl ether and 1700 cm⁻¹ of ethyl acetate were added. 3 2M HCl. After mixing, separate the organic layer and extract the aqueous layer with 2 × 700 ml diethyl ether. Dry the combined organic extracts with Na₂SO₄ and then carefully evaporate to dryness. Purify the residue by vacuum distillation to give 2-ethylacrylic acid, bp 75-77℃ / 6 mm Hg. 79.8 g (88.6%) of colorless liquid was obtained.

[0363] 1 H NMR (CDCl3): δ 12.55 (br.s, 1H), 6.28 (m, 1H), 5.64 (m, 1H), 2.32(qm, J = 7.5 Hz, 2H), 1.08 (t, J = 7.5 Hz, 3H).

[0364] 6-tert-butyl-5-methoxy-2-ethylindan-1-one

[0365]

[0366] At 50°C, 47.6 g of 2-ethylacrylic acid (475.5 mmol, 1.27 equivalents) was added to a mixture of 103.5 g of P4O. 10 The mixture was added dropwise to Eaton's reagent obtained from 520 ml MeSO3H over approximately 1 h at 50–53 °C (hot water bath). The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 1.0 L cold water and 1 kg ice. The crude product was extracted with 3 × 400 ml dichloromethane. The combined organic extracts were washed with an aqueous K2CO3 solution, dried over K2CO3, filtered through a silica gel 60 short pad (40–63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 81.18 g (87.7%, approximately 90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one as a pale yellow oil (bp 150–170 °C / 5 mm Hg).

[0367] 1H NMR (CDCl3): δ 7.65 (s, 1H), 6.85 (s, 1H), 3.90 (s, 3H), 3.20 (dd,J= 17.2 Hz, J = 7.7 Hz, 1H), 2.71 (dd,J = 17.2 Hz, J = 3.6 Hz, 1H), 2.59-2.51(m, 1H), 1.99-1.87 (m, 1H), 1.54-1.41 (m, 1H), 1.35 (s, 9H), 0.97 (t, J = 7.4Hz, 3H). 13 C NMR (CDCl3): δ 207.59, 164.52, 154.75, 138.65, 129.31, 121.87,107.72, 55.15, 48.86, 35.00, 31.93, 29.54, 24.61, 11.56.

[0368] 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one

[0369]

[0370] At 5 °C, bromine (18.5 ml, 57.4 g, 359.1 mmol) was added dropwise over 5 min to 6-tert-butyl-2-ethyl-5-methoxyindan-1-one (81.18 g, 329.5 mmol), 100.4 g sodium acetate, and 3.0 g sodium acetate. n A mixture of Bu4NI, 280 ml dichloromethane, and 570 ml water was added. The mixture was stirred at 5 °C for 2 h, then a solution of 46.3 g sodium acetate in 260 ml water was added, followed by 9.7 ml (30.1 g, 188.3 mmol) bromine. The resulting mixture was stirred at this temperature for another 1 h, then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 3 × 250 ml dichloromethane. The combined organic extracts were dried over K2CO3, evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 105.3 g (98.1%, approximately 90% purity) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one as a pale yellow oil, which was ready for use without further purification.

[0371] 1H NMR (CDCl3): δ 7.69 (s, 1H), 4.03 (s, 3H), 3.21 (dd,J = 17.6 Hz, J= 7.8 Hz, 1H), 2.70 (dd, J = 17.6 Hz, J = 3.7 Hz, 1H), 2.66-2.58 (m, 1H), 2.03-1.91 (m, 1H), 1.60-1.47 (m, 1H), 1.40 (s, 9H), 1.03 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 207.14, 162.57, 154.07, 145.20, 133.07, 121.13, 116.50, 61.45, 48.79, 35.46, 33.36, 30.45, 24.34, 11.43.

[0372] 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0373]

[0374] 64.08 g (197.0 mmol) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 37.32 g (248.8 mmol, 1.26 equivalents) of 3,5-dimethylphenylboronic acid, and 1.02 g (2.0 mmol, 1 mol.%) of Pd (P t A mixture of Bu3)2, 63.4 g Na2CO3, 325 ml 2-methyltetrahydrofuran, and 290 ml water was refluxed for 6 h. Then 500 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 200 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a pale yellow oil. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane-dichloromethane = 1:1, then 1:5, vol.). 62.95 g (91.2%, approximately 95% purity) of a pale yellow oil was obtained.

[0375] 1H NMR (CDCl3): δ 7.73 (s, 1H), 7.03 (s, 1H), 7.02 (s, 2H), 3.32 (s,3H), 3.06 (dd,J = 18.3 Hz, J = 8.6 Hz, 1H), 2.57-2.47 (m, 2H), 2.39 (s, 6H), 2.00-1.87 (m, 1H), 1.54-1.40 (m, 1H), 1.42 (s, 9H), 0.95 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 208.30, 163.42, 153.15, 143.21, 138.06, 136.27, 132.68,131.42, 129.07, 127.17, 121.11, 60.47, 49.00, 35.33, 31.69, 30.49, 24.48,21.36, 11.67.

[0376] 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0377]

[0378] NaBH4 (10.2 g, 269.6 mmol, 1.5 equivalents) was added to a solution of 62.95 g (179.6 mmol) of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 300 ml of THF cooled to 5 °C. 150 ml of MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 700 ml of dichloromethane and 700 ml of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 ml of dichloromethane. The combined organic extracts were passed through a silica gel 60 filter (40–63 µm; eluent: dichloromethane) (~30 ml) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a gray oil. The oily substance was dissolved in 300 ml of toluene, and TsOH (0.3 g) was added to it. The mixture was refluxed using a Dean-Stark separatory for 10 min, and then cooled to room temperature using a water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 150 ml of dichloromethane. The combined organic extracts were dried over K₂CO₃ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, hexane-dichloromethane = 10:1), followed by vacuum distillation, to give 53.14 g (88.5%) of 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene as a pale yellow oil (bp 175–195 °C / 2 mm Hg).

[0379] 1 H NMR (CDCl3): δ 7.22 (s, 1H), 7.09 (s, 2H), 6.99 (s, 1H), 6.45 (t,J= 1.4 Hz, 1H), 3.25 (s, 3H), 3.13 (s, 2H), 2.41 (q, J = 7.4 Hz, 2H), 2.37 (s,6H), 1.44 (s, 9H), 1.14 (d, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 154.25,151.76, 141.51, 140.88, 140.43, 138.31, 137.66, 131.91, 128.46, 127.20,124.97, 117.17, 60.66, 41.00, 35.13, 31.01, 24.25, 21.43, 13.47.

[0380] [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane

[0381]

[0382] Will n A hexane solution of BuLi (2.5 M, 10.9 mL, 27.25 mmol) was added in a single dose to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene (9.05 g, 27.06 mmol) cooled to -50 °C in 200 mL of diethyl ether. The mixture was stirred overnight at room temperature, and the resulting orange-yellow solution was then cooled to -50 °C, to which dichlorodimethylsilane (16.3 mL, 17.44 g, 135.1 mmol, 5.0 equivalents) was added in a single dose. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3), and the filter cake was washed with 2 × 50 mL of toluene. The combined filtrates were evaporated to dryness to give the title compound as a pale yellow viscous oil, which was ready for use without further purification.

[0383] 1 H NMR (CDCl3): δ 7.39 (s, 1H), 7.09 (s, 2H), 6.99 (s, 1H), 6.45 (s,1H), 3.65 (s, 1H), 3.24 (s, 3H), 2.67-2.46 (m, 2H), 2.38 (s, 6H), 1.43 (s,9H), 1.15 (t,J = 7.5 Hz, 3H), 0.43 (s, 3H), 0.15 (s, 3H). 13 C NMR (CDCl3): δ155.83, 152.58, 143.55, 137.96, 137.58, 137.55, 136.53, 128.33, 127.90,127.74, 124.52, 121.00, 60.46, 48.34, 35.16, 31.17, 24.71, 21.44, 13.76,1.21, -0.66.

[0384] [4,7-Bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]dimethylsilane

[0385]

[0386] Will n A hexane solution of BuLi (2.5 M, 8.3 ml, 20.75 mmol) was added in a single addition to a solution of 4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-indene (7.03 g, 20.77 mmol) cooled to -50 °C in a mixture of 100 ml diethyl ether and 70 ml THF. The resulting mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C and 150 mg CuCN was added. The resulting mixture was stirred at -20 °C for 0.5 h, and then a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]chlorodimethylsilane (8.87 g, 20.77 mmol) in 150 ml diethyl ether was added in a single addition. The resulting mixture was stirred overnight at room temperature, filtered through a silica gel 60 filter (40-63 m), and washed with 2 × 50 ml diethyl ether. The combined organic eluents were evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, 600 ml, eluent: hexane: dichloromethane = 5:1, vol.). The combined organic eluents were evaporated to dryness, and the residue was dried under vacuum at high temperature to give 13.8 g (18.92 mmol, yield approximately 91.1%, purity approximately 98%) of the title product (a mixture of approximately 40:60 stereoisomers) as a pale yellow glassy solid.

[0387] trans-dimethylsilanediyl[2-methyl-4,7-bis(3,5-dimethylphenyl)-inden-1-yl][2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl]zirconium dichloride

[0388]

[0389] At room temperature, nA hexane solution of BuLi (2.5 M, 14.04 mL, 35.1 mmol) was added in a single batch to a solution of [4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-indene-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]dimethylsilane (12.8 g, 17.55 mmol) in 100 mL of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting red solution was then cooled to 0 °C in an ice bath, and ZrCl4 (4.1 g, 17.6 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give a yellow suspension. The suspension was evaporated to dryness. The solid formed was extracted with 150 mL of hot toluene. The mother liquor was evaporated to about 25 mL. The orange solid precipitated from the solution at room temperature was collected and dried under vacuum. The procedure yielded 12.3 g of trans-zirconium dichloroethylene (a solvate formed with about 0.5 molecules of toluene) (78%).

[0390] Synthesis of metallocene IM3 in this invention

[0391] Isopropylmalonic acid

[0392]

[0393] Add 125 g of potassium hydroxide to a solution of 110.0 g (544 mmol) diethyl isopropyl malonate in 500 ml of methanol at a concentration of 1000 cm⁻¹. 3 The solution was prepared in water. The resulting mixture was refluxed for 5 h, and then ethanol and methanol were distilled off. Then, 1000 cm⁻¹ was added. 3 The resulting mixture was acidified to pH 1.0 with 12 M HCl. Isopropylmalonic acid was extracted with 4 × 500 ml diethyl ether. The combined extracts were evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 76.4 g (96.1%) isopropylmalonic acid as a white solid.

[0394] 1 H NMR (CDCl3): δ 9.72 (br.s, 2H), 3.24 (d, J = 8.3 Hz, 1H), 2.48-2.34(m, 1H), 1.07 (d, J = 6.8 Hz, 6H).

[0395] 2-Isopropylacrylic acid

[0396]

[0397] At 5 °C, 62.4 ml (44.3 g, 0.606 mol) of diethylamine was added dropwise to a solution of 76.4 g (523 mmol) of isopropylmalonic acid in 750 ml of ethyl acetate. Paraformaldehyde (22.1 g, 0.736 mol) was added to the resulting suspension. The resulting mixture was refluxed for 5 h, then cooled to 5 °C, and 350 ml of diethyl ether and 1000 cm⁻¹ were added. 3 2M HCl. After mixing, the organic layer was separated, and the aqueous layer was extracted again with 2 × 500 ml diethyl ether. The combined organic extracts were dried over Na₂SO₄ and then evaporated to dryness. The residue was purified by vacuum distillation to give 2-isopropylacrylic acid, bp 65℃ / 4 mm Hg. 57.0 g (95.5%) of colorless liquid was obtained.

[0398] 1 H NMR (CDCl3): δ 12.45 (br.s, 1H), 6.30 (s, 1H), 5.65 (t, 1H), 2.81(septd,J = 6.9 Hz, J = 0.9 Hz, 1H), 1.11 (d, J = 6.9 Hz, 6H). 13 C NMR (CDCl3): δ 173.30, 146.47, 124.31, 28.94, 21.76.

[0399] 6-tert-butyl-5-methoxy-2-isopropylindan-1-one

[0400]

[0401] At 50°C, 114.1 g (1.0 mol) of 2-isopropylacrylic acid was added to a mixture of 220 g P4O 10 The mixture was added dropwise to Eaton's reagent obtained from 1120 ml MeSO3H over approximately 1 h with vigorous stirring at 50–53 °C (water bath temperature). The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 1.5 L cold water and 3 kg ice. The crude product was extracted with 3 × 600 ml dichloromethane. The combined organic extracts were washed with an aqueous K2CO3 solution, dried over K2CO3, filtered through a silica gel 60 short pad (40–63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 193.8 g (93.0%, approximately 95% purity) of 6-tert-butyl-5-methoxy-2-isopropylindan-1-one as a pale yellow oil (bp 150–190 °C / 4 mm Hg).

[0402] 1 H NMR (CDCl3): δ 7.66 (s, 1H), 6.89 (s, 1H), 3.93 (s, 3H), 3.04 (dd,J= 17.4 Hz, J = 8.0 Hz, 1H), 2.84 (dd,J = 17.4 Hz, J = 3.8 Hz, 1H), 2.67-2.60(m, 1H), 2.48-2.34 (m, 1H), 1.37 (s, 9H), 1.05 (d, J = 6.9 Hz, 3H), 0.77 (d,J = 6.9 Hz, 3H). 13 C NMR (CDCl3): δ 207.45, 164.44, 155.10, 138.54, 130.07,121.69, 107.64, 55.14, 53.20, 35.00, 29.54, 28.87, 27.65, 20.96, 17.00.

[0403] 4-Bromo-6-tert-butyl-2-isopropyl-5-methoxyindan-1-one

[0404]

[0405] At 5°C, over 5 minutes, 20.8 ml (64.9 g, 405.9 mmol) of bromine was added dropwise to 97.0 g (0.372 mol) of 6-tert-butyl-2-isopropyl-5-methoxyindan-1-one, 113.2 g of sodium acetate, and 3.0 g of other compounds under vigorous stirring. n A mixture of Bu4NI, 310 ml dichloromethane, and 645 ml water was added. The mixture was stirred at 5 °C for 2 h, then a solution of 52.2 g sodium acetate in 290 ml water was added, followed by 10.8 ml (33.7 g, 210.8 mmol) bromine. The resulting mixture was stirred at this temperature for another 1 h, then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 3 × 250 ml dichloromethane. The combined organic extracts were dried over K2CO3, evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 124.84 g (98.9%, approximately 95% purity) of a pale yellow oil, ready for use without further purification.

[0406] 1H NMR (CDCl3): δ 7.68 (s, 1H), 4.04 (s, 3H), 3.04 (dd,J = 17.9 Hz, J= 8.1 Hz, 1H), 2.80 (dd, J = 17.9 Hz, J = 3.9 Hz, 1H), 2.71-2.64 (m, 1H), 2.49-2.35 (m, 1H), 1.40 (s, 9H), 1.08 (d, J = 6.9 Hz, 3H), 0.80 (d, J = 6.8Hz, 3H). 13 C NMR (CDCl3): δ 207.21, 162.59, 154.47, 145.24, 133.82, 121.03,116.56, 61.54, 53.32, 35.56, 30.54, 29.41, 28.94, 20.78, 17.17.

[0407] 6-tert-butyl-2-isopropyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0408]

[0409] 124.84 g (368.0 mmol) of 4-bromo-6-tert-butyl-2-isopropyl-5-methoxyindan-1-one, 69.7 g (464.7 mmol, 1.26 equivalents) of 3,5-Me2C6H3B(OH)2, and 1.9 g (3.72 mmol, 1 mol.%) of Pd (P t A mixture of Bu3)2, 118.3 g Na2CO3, 600 ml 2-methyltetrahydrofuran, and 540 ml water was refluxed for 6 h. Then, 500 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 300 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a pale yellow solid. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane-dichloromethane = 1:1, then 1:5, vol.). 121.55 g (90.6%, approximately 95% purity) of pale yellow crystalline material was obtained.

[0410] 1H NMR (CDCl3): δ 7.71 (s, 1H), 7.04 (s, 1H), 7.03 (s, 2H), 3.31 (s,3H), 2.87 (dd,J = 18.5 Hz, J = 8.8 Hz, 1H), 2.65-2.54 (dd and m, 2H), 2.43-2.34 (s and m, 7H), 1.42 (s, 9H), 0.99 (d, J = 6.9 Hz, 3H), 0.77 (d, J = 6.8Hz, 3H). 13 C NMR (CDCl3): δ 208.19, 163.34, 153.44, 143.11, 138.08, 136.33,132.64, 132.12, 129.08, 127.20, 120.93, 77.00, 60.46, 53.37, 35.33, 30.50,28.88, 27.38, 21.39, 20.90, 17.25.

[0411] 5-tert-butyl-2-isopropyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0412]

[0413] 18.9 g (0.5 mol, 1.5 equivalent) of NaBH4 was added to a solution of 121.55 g (333.45 mmol) of 6-tert-butyl-2-isopropyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 600 ml of THF cooled to 5 °C. 300 ml of MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 1000 ml of dichloromethane and 1000 ml of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 ml of dichloromethane. The combined organic extracts were passed through a silica gel 60 filter (40–63 mm; eluent: dichloromethane) (~30 ml) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a gray solid block. 1.0 g of TsOH was added to this block in a 1000 mL solution of toluene. The mixture was refluxed using a Dean-Stark separator for 10 min, then cooled to room temperature in a water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 300 mL of dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, hexane-dichloromethane = 5:1), followed by recrystallization from n-hexane (heat → -30 °C). This procedure yielded 96.93 g (83.4%) of pure 5-tert-butyl-7-(3,5-dimethylphenyl)-2-isopropyl-6-methoxy-1H-indene.

[0414] 1 H NMR (CDCl3): δ 7.24 (s, 1H), 7.09 (s, 2H), 6.99 (s, 1H), 6.46 (m,1H), 3.24 (s, 3H), 3.15 (m, 2H), 2.68 (sept,J = 6.8 Hz, 1H), 2.37 (s, 6H), 1.43 (s, 9H), 1.14 (d, J = 6.8 Hz, 6H). 13 C NMR (CDCl3): δ 156.43, 154.33,141.34, 140.95, 140.23, 138.29, 137.69, 131.99, 128.49, 127.22, 123.86,117.32, 60.67, 39.15, 35.13, 31.00, 30.04, 22.64, 21.44.

[0415] [6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane

[0416]

[0417] Will n A hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 mmol) was added in a single batch to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-isopropyl-6-methoxy-1H-indene (6.97 g, 20.0 mmol) cooled to -50 °C in 200 ml of diethyl ether. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C. Dichlorodimethylsilane (12.1 ml, 12.95 g, 100.3 mmol, 5.02 equivalents) was added in a single batch, followed by 5 ml of THF. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3). The filter cake was washed with 2 × 50 ml of toluene. The combined filtrates were evaporated to dryness to obtain [6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane, a pale yellow viscous oil that can be used without further purification.

[0418] 1 H NMR (CDCl3): δ 7.40 (s, 1H), 7.10 (br.s, 2H), 7.00 (m, 1H), 6.44(s, 1H), 3.76 (s, 1H), 3.23 (s, 3H), 2.89 (sept.d,J = 6.8 Hz, J = 1.3 Hz,1H), 2.39 (s, 6H), 1.43 (s, 9H), 1.20 (d, J = 6.7 Hz, 3H), 1.12 (d, J = 6.9Hz, 3H), 0.43 (s, 3H), 0.12 (s, 3H). 13 C NMR (CDCl3): δ 157.53, 155.85,143.40, 137.91, 137.60, 136.43, 128.33, 127.92, 127.89, 122.52, 121.06,60.45, 47.72, 35.16, 31.16, 29.45, 24.43, 21.45, 21.17, 1.35, -0.77.

[0419] [4,7-Bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl]-[6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]dimethylsilane

[0420]

[0421] Will n A hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 mmol) was added in a single addition to a solution of 4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-indene (6.77 g, 20.0 mmol) cooled to -50 °C in a mixture of 100 ml diethyl ether and 65 ml THF. The resulting mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C and 150 mg CuCN was added. The resulting mixture was stirred at -15 °C for 0.5 h, and then a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-indene-1-yl]chlorodimethylsilane (8.7 g, 19.72 mmol) in 150 ml diethyl ether was added in a single addition. The resulting mixture was stirred overnight at room temperature, filtered through a silica gel 60 filter (40–63 m), and washed with 2 × 50 ml diethyl ether. The combined organic eluents were evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, 600 ml, eluent: hexane: dichloromethane = 5:1, vol.). The combined organic eluents were evaporated to dryness, and the residue was dried under vacuum at high temperature to give 13.9 g (18.7 mmol, yield approximately 93.5%, purity approximately 95%) of the title product (a mixture of approximately 35:65 stereoisomers) as a pale yellow glassy solid.

[0422] trans-dimethylsilanediyl[2-methyl-4,7-bis(3,5-dimethylphenyl)-inden-1-yl][2-isopropyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

[0423]

[0424] At room temperature, nA hexane solution of BuLi (2.5 M, 3.64 mL, 34.1 mmol) was added in a single batch to a solution of [4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]dimethylsilane (12.67 g, 17.05 mmol) in 100 mL of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting red solution was then cooled to 0 °C in an ice bath, and ZrCl4 (4.0 g, 17.1 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give a yellow suspension. The suspension was evaporated to dryness. The solid formed was extracted with 150 mL of hot toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of approximately 80:20 trans and cis dichlorozirconia. The mother liquor was evaporated to approximately 35 mL. The orange solid precipitated from the solution at room temperature was collected and dried under vacuum. This procedure yielded 8.8 g of trans-zirconium chloride (as a solvate with about 0.8 molecules of toluene) (57%). The mother liquor was evaporated to about 5 ml, and 30 ml of hexane was added. The orange solid precipitated from the solution at room temperature was collected and dried under vacuum. This procedure yielded 3.3 g of trans-zirconium chloride and some polymers.

[0425] Synthesis of metallocene IM4 in this invention

[0426] n-propylmalonic acid

[0427]

[0428] 99.7 g (1.78 mol) of potassium hydroxide was heated at 500 cm⁻¹ 3 The aqueous solution was added to a solution of 101.1 g (0.5 mol) diethyl n-propylmalonate in 100 mL of methanol. The resulting mixture was refluxed for 5 h, and then the ethanol and methanol were distilled off. Then 500 cm⁻¹ of the aqueous solution was added. 3 The resulting mixture was acidified to pH 1.0 with 12 M HCl. Propylmalonic acid was extracted with 4 × 400 ml diethyl ether. The combined extracts were evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 76.4 g (approximately 100%) of n-propylmalonic acid, which was ready for use without further purification.

[0429] 2-n-Propylacrylic acid

[0430]

[0431] Diethylamine (42.4 g, 0.58 mol) was added dropwise to a solution of approximately 0.5 mol of n-propylmalonic acid in 650 mL of ethyl acetate at 5 °C. 21.3 g (0.71 mol) of paraformaldehyde was added to the resulting suspension. The mixture was refluxed for 5 h, then cooled to 5 °C, and 350 mL of diethyl ether and 1000 cm⁻¹ of ethyl acetate were added. 3 2M HCl. After mixing, separate the organic layer, and extract the aqueous layer again with 2 × 500 ml diethyl ether. Dry the combined organic extracts with Na₂SO₄, and then evaporate to dryness. Purify the residue by vacuum distillation to give 2-n-propylacrylic acid, bp 67-70℃ / 4 mm Hg. 46.1 g (80%) of colorless liquid is obtained.

[0432] 1 H NMR (CDCl3): δ 12.54 (br.s, 1H), 6.30 (m, 1H), 5.65 (m, 1H), 2.29(t,J = 7.3 Hz, 2H), 1.52 (sext, J = 7.4 Hz, 2H), 0.94 (t, J = 7.4 Hz, 3H). 13 CNMR (CDCl3): δ 173.24, 140.02, 127.04, 33.44, 21.48, 13.58.

[0433] 6-tert-butyl-5-methoxy-2-n-propylindan-1-one

[0434]

[0435] At 50°C, 46.1 g (0.4 mol) of 2-n-propylacrylic acid was added to a mixture of 55 g P4O 10 The mixture was added dropwise to Eaton's reagent obtained from 280 ml MeSO3H at 50–53 °C (water bath temperature) over approximately 1 h with vigorous stirring. The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 0.5 L cold water and 1 kg ice. The crude product was extracted with 3 × 300 ml dichloromethane. The combined organic extracts were washed with an aqueous K2CO3 solution, dried over K2CO3, filtered through a silica gel 60 short pad (40–63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 62.6 g (75%) 6-tert-butyl-5-methoxy-2-n-propylindan-1-one as a pale yellow oil (bp 155–170 °C / 4 mm Hg).

[0436] 1 H NMR (CDCl3): δ 7.67 (s, 1H), 6.87 (s, 1H), 3.93 (s, 3H), 3.23 (dd,J= 17.1 Hz, J = 7.6 Hz, 1H), 2.71 (dd,J = 17.1 Hz, J = 3.5 Hz, 1H), 2.66-2.60(m, 1H), 1.94-1.88 (m, 1H), 1.51-1.39 (m, 3H), 1.37 (s, 9H), 0.95 (t, J = 7.4Hz, 3H). 13 C NMR (CDCl3): δ 207.76, 164.51, 154.70, 138.64, 129.18, 121.89,107.70, 55.15, 47.41, 34.99, 33.83, 32.47, 29.53, 20.63, 14.05.

[0437] 4-Bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one

[0438]

[0439] At 5°C, over 15 min, under vigorous stirring, 31.3 g (0.120 mol) of 6-tert-butyl-2-n-propyl-5-methoxyindan-1-one, 39.45 g of sodium acetate, and 1.0 g of... n 6.2 ml (19.2 g, 120 mmol) of bromine was added dropwise to a mixture of Bu4NI, 100 ml dichloromethane, and 200 ml water. The mixture was stirred at 5 °C for 1 h, followed by the addition of a solution of 20 g sodium acetate in 100 ml water, and then 3.1 ml (60 mmol) of bromine. The resulting mixture was stirred at the same temperature for another 1 h, and then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 3 × 100 ml dichloromethane. The combined organic extracts were dried over K2CO3, filtered through a silica gel 60 filter (40–63 µm), and evaporated to dryness. The residue was crystallized from about 50 ml of n-pentane at -15 °C to give 33.2 g of the title product (81.6%).

[0440] 1H NMR (CDCl3): δ 7.69 (s, 1H), 4.03 (s, 3H), 3.22 (dd,J = 18.3 Hz, J= 8.4 Hz, 1H), 2.72-2.65 (m, 2H), 1.97-1.88 (m, 1H), 1.54-1.43 (m, 3H), 1.40(s, 9H), 0.97 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ 207.70, 162.75, 154.24,145.43, 133.15, 121.38, 116.66, 61.64, 47.52, 35.66, 34.04, 33.64, 30.62,20.59, 14.03.

[0441] 6-tert-butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0442]

[0443] 16.6 g (48.9 mmol) of 4-bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one, 9.45 g (63.0 mmol, 1.28 equivalents) of 3,5-Me2C6H3B(OH)2, and 0.26 g (0.5 mmol, 1 mol.%) of Pd (P t A mixture of Bu3)2, 15.8 g Na2CO3, 80 ml 2-methyltetrahydrofuran, and 75 ml water was refluxed for 6 h. Then, 100 ml water was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 50 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, eluent: dichloromethane-hexane = 2:1, vol.). The combined eluents were evaporated to dryness, and the residue was washed with 30 ml n-pentane and dried under vacuum. This procedure yielded 15.7 g (88.0%) of the title product.

[0444] 1H NMR (CDCl3): δ 7.73 (s, 1H), 7.03 (s, 1H), 7.02 (s, 2H), 3.31 (s,3H), 3.06 (dd,J = 17.3 Hz, J = 7.6 Hz, 1H), 2.58 (m, 1H), 2.49 (dd, J = 17.3Hz, J = 3.8 Hz, 1H), 2.39 (s, 6H), 1.94-1.84 (m, 1H), 1.42 (s, 9H), 1.40-1.34(m, 3H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ 208.45, 163.41, 153.09,143.21, 138.06, 136.28, 132.67, 131.33, 129.07, 127.17, 121.14, 60.48, 47.51,35.33, 33.67, 32.20, 30.50, 21.37, 20.62, 14.02.

[0445] 5-tert-butyl-2-n-propyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0446]

[0447] 2.44 g (64.6 mmol) NaBH4 was added to a solution of 15.7 g (43 mmol) 6-tert-butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 180 ml THF cooled to 5 °C. 70 ml MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 200 ml dichloromethane and 200 ml water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 2 × 50 ml dichloromethane. The combined organic extracts were evaporated to dryness. 300 mg TsOH was added to the residue in a solution of 300 ml toluene. The mixture was refluxed using a Dean-Stark separator for 10 min and then cooled to room temperature using a water bath. The solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 2 × 50 ml dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, eluent: dichloromethane-hexane = 1:1, vol.), and dried under vacuum to give 14.0 g (93.4%) of pure product, a mixture of two isomers of indene.

[0448] 1 H NMR (CDCl3): δ 7.34 (s), 7.23 (s), 7.10 (s), 7.09 (s), 6.98 (s), 6.45 (m), 6.34 (s), 3.30 (s), 3.25 (s), 3.12 (s), 2.38-2.34 (m), 1.55 (sext,J = 7.4 Hz), 1.44 (s), 0.91 (t,J = 7.3 Hz). 13C NMR (CDCl3): δ 156.08,154.24, 151.14, 149.97, 144.16, 141.56, 140.85, 140.44, 138.30, 137.87,137.72, 137.65, 137.53, 137.43, 131.87, 128.46, 128.28, 127.84, 127.20,126.05, 125.40, 120.81, 117.13, 60.65, 60.44, 41.13, 41.04, 35.12, 35.04,33.52, 33.29, 31.11, 31.00, 22.44, 22.29, 21.42, 14.01, 13.94.

[0449] [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl]chlorodimethylsilane

[0450]

[0451] Will n A hexane solution of BuLi (2.5 M, 6.3 mL, 16.0 mmol) was added in a single dose to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-propyl-1H-indene (5.5 g, 15.78 mmol) cooled to -50 °C in a mixture of 120 mL diethyl ether and 10 mL THF. The mixture was stirred overnight at room temperature, and the resulting yellow solution was then cooled to -50 °C, and dichlorodimethylsilane (9.5 mL, 10.07 g, 78.0 mmol, 5.0 equivalents) was added in a single dose. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3), and the filter cake was washed with 2 × 50 mL toluene. The combined filtrates were evaporated to dryness to give the title product, which was ready for use without further purification.

[0452] 1 H NMR (CDCl3): δ 7.39 (s, 1H), 7.09 (br. s, 2H), 6.99 (s, 1H), 6.45(s, 1H), 3.64 (s, 1H), 3.25 (s, 3H), 2.54-2.49 (m, 2H), 2.38 (s, 6H), 1.68-1.48 (m, 2H), 1.43 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H), 0.42 (s, 3H), 0.15 (s,3H).13 C NMR (CDCl3): δ 155.79, 150.92, 143.54, 137.95, 137.56, 137.49, 136.54,128.31, 127.89, 127.65, 125.43, 120.99, 60.46, 48.22, 35.16, 33.72, 31.16,22.75, 21.44, 14.06, 1.19, -0.64.

[0453] [4,7-Bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl]dimethylsilane

[0454]

[0455] Will n A hexane solution of BuLi (2.5 M, 3.0 ml, 7.5 mmol) was added in a single batch to a solution of 2.53 g (7.47 mmol) of 4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-indene in a mixture of 40 ml diethyl ether and 20 ml THF cooled to -50 °C. The resulting mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C and 75 mg CuCN was added. The resulting mixture was stirred at -20 °C for 0.5 h, and then a single batch of 3.3 g (7.48 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-indene-1-yl]chlorodimethylsilane in 50 ml THF was added. The resulting mixture was stirred overnight at room temperature, filtered through a silica gel 60 filter (40-63 m), and washed with 2 × 50 ml diethyl ether. The combined organic eluents were evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, 600 ml, eluent: hexane-dichloromethane = 5:1, vol.). This procedure yielded 3.3 g (60%, approximately 98% purity) of the title product (a mixture of two stereoisomers in approximately 2:3 ratio) as a pale yellow glassy solid.

[0456] trans-dimethylsilanediyl[2-methyl-4,7-bis(3,5-dimethylphenyl)-inden-1-yl][2-propyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

[0457]

[0458] At room temperature,n A hexane solution of BuLi (2.5 M, 3.54 ml, 8.75 mmol) was added in a single batch to a solution of 3.3 g (4.4 mmol) of [4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-propyl-5-methoxy-1H-inden-1-yl]dimethylsilane in 40 ml of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting red solution was then cooled to 0 °C in an ice bath, and ZrCl4 (1.03 g, 4.45 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give a yellow suspension. The suspension was evaporated to dryness. The resulting solid was extracted with 50 ml of hot toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of approximately 80:20 trans and cis-zirconium dichloroethylene. The mother liquor was evaporated to approximately 10 ml. The orange solid precipitated from the solution at room temperature was collected and dried under vacuum. This procedure yielded 2.4 g of trans-zirconia, which was further recrystallized from a mixture of 10 ml toluene and 20 ml hexane to give 2.00 g of yellow trans-zirconia powder containing 0.4 mol of toluene per mol of the complex. Therefore, the adjusted net weight of the isolated complex was 1.92 g (48%).

[0459] C 53 H 60 Analytical values ​​of Cl2OSiZr*0.4(C7H8): C, 71.29; H, 6.78. Measured values: C, 71.43; H, 6.97.

[0460] 1 H NMR (CDCl3): δ 7.46 (s, 1H), 7.39 (d, J = 7.3 Hz, 1H), 7.36 (s,2H), 7.25 (very br. s, 2H), 7.22 (s, 1H), 7.15 (s, 2H), 7.01 (s, 1H), 6.98(s, 1H), 6.96 (s, 1H), 6.93 (d, J = 7.3 Hz, 1H), 6.61 (s, 1H), 3.42 (s, 3H), 2.46-2.33 (m, 22H), 2.11-2.03 (m, 1H), 1.38 (s, 9H), 1.27-1.15 (m, 5H), 0.80 (t, J = 7.3 Hz, 3H), -0.03 (s, 3H). 13C NMR (CDCl3): δ 160.05, 144.67, 143.25,139.82, 139.40, 138.90, 138.48, 137.97, 137.82, 137.77, 136.71, 135.90,134.18, 130.79, 130.48, 129.75, 129.39, 129.34, 128.79, 128.35, 127.46 (br.s), 127.16, 126.73, 126.06, 125.40, 123.95, 123.66, 121.29, 121.09, 82.60, 81.75, 62.63, 35.74, 34.11, 30.43, 27.19, 21.45, 21.36, 21.24, 19.83, 13.85, 3.58, 3.35.

[0461] Catalyst synthesis, the chemicals used

[0462] All catalysts were prepared using Sunspera AGC DM-L-303 silica calcined at 600°C. MAOAxion CA1330 was ready to use upon receipt and should be stored at -20°C for no more than 6 months.

[0463] Catalyst preparation

[0464] These catalysts were prepared using a two-step method. The first step was the preparation of SiO2 / MAO (activated support), followed by a second step in which a toluene solution of the metallocene complex was impregnated onto the dried support from the first step. Only when the solubility of the metallocene in toluene was insufficient (metallocene C), a second equal amount of MAO was added to the metallocene / toluene slurry to promote complete dissolution of the metallocene.

[0465] Preparation of SiO2 / MAO Activated Support

[0466] A steel reactor equipped with a mechanical stirrer and filter screen 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 added (140 min) 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 out, 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 out each time. Finally, the solid filter cake was vacuum dried at 80°C for 9 h while slowly stirring (5 rpm).

[0467] Synthesis of SiO2 / MAO / CM1 (comparative catalyst 1, CC1)

[0468] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to an equal volume of metallocene CM1 (32.3 mg). The mixture was stirred at room temperature for 30 minutes. Next, 2,000 g of silica / MAO support was placed in a glass vial. 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 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.

[0469] Synthesis of SiO2 / MAO / CM2 (comparative catalyst 2, CC2)

[0470] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 28.1 mg of metallocene CM2. The mixture was stirred at room temperature for 30 minutes to obtain a clear yellow solution. Next, 2,000 g of SiO2 / MAO 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.

[0471] Synthesis of SiO2 / MAO / IM1 (catalyst 1, IC1 of this invention)

[0472] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 26.3 mg of metallocene IMI. The mixture was stirred at room temperature for 30 minutes to obtain a clear yellow solution. Next, 2,000 g of SiO2 / MAO 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.

[0473] Synthesis of SiO2 / MAO / IM2 (catalyst 2, IC2 of this invention)

[0474] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 27.0 mg of metallocene IM2 in a diaphragm flask. Next, 2.004 g of SiO2 / MAO was placed in the 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.

[0475] Synthesis of SiO2 / MAO / IM3 (catalyst 3, IC3 of this invention)

[0476] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 27.3 mg of metallocene IM3 in a diaphragm flask. Next, 2,000 g of SiO2 / MAO was placed in the 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 light yellow, free-flowing powder.

[0477] Synthesis of SiO2 / MAO / IM4 (catalyst 4 of this invention, IC4)

[0478] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 27.0 mg of metallocene IM4 in a diaphragm flask. Next, 2.001 g of SiO2 / MAO was placed in the 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 reddish-brown free-flowing powder.

[0479] The metallocene content in each catalyst was calculated using mass balance. These values ​​are listed in Table 1:

[0480] Table 1: Catalysts tested and their metallocene content

[0481]

[0482] Aggregate Examples

[0483] Propylene homopolymerization process (bulk, 20-L reactor)

[0484] Add 3.95 kg of propylene to a stainless steel reactor equipped with a ribbon agitator, containing 0.2 bar-g of propylene, with a total volume of 20.9 dm³. 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.

[0485] Load the required amount of solid catalyst into a 5 ml stainless steel vial. Install this feed system onto the port on the autoclave lid. Then purge the catalyst into the reactor with 350 g of propylene. Maintain the stirring speed at 250 rpm and prepolymerize at 25°C or 30°C for 10 minutes. Then raise the polymerization temperature to 75°C. Add a second equal amount of H2 over 1 minute at 60°C.

[0486] Maintain a constant reactor temperature throughout the polymerization process. Begin measuring the polymerization time when the temperature drops 2°C below the set polymerization temperature. Stop the reaction by injecting 5 ml of ethanol, cooling the reactor, and simultaneously flash-evaporating the volatile components once the set polymerization time has elapsed. 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, followed by an additional 1 hour of drying in a vacuum drying oven at 60°C.

[0487] Results Analysis

[0488] 1. Metallocene Synthesis

[0489] Comparing the synthesis efficiencies of the four metallocenes IM1-IM4 with those of the two metallocenes CM1 and CM2 (Table 2), it can be seen that the synthesis efficiencies of IM1, IM2 and IM3 are much higher than those of CM1 and CM2 (the separation yield of the target trans isomer is higher).

[0490] Table 2: Synthesis Results

[0491]

[0492] 2. Propylene polymerization results

[0493] Comparing the performance of four catalysts IC1-IC4 based on the metallocene IM1-IM4 of this invention with two catalysts CC1 and CC2 based on the comparative metallocene CM1 and CM2 in liquid propylene polymerization, it can be seen that the polypropylene homopolymers produced by all catalysts of this invention have higher melting points than the polypropylene homopolymers produced by the comparative catalysts (Table 3).

[0494] Table 3: Results of Liquid Propylene Polymerization

[0495]

[0496] Therefore, complete removal of the indolecyclopentane ring in CM1 provides a more efficient metallocene synthesis, while removing only one carbon atom of the ring (as in CM2) degrades the synthesis efficiency and catalyst performance.

Claims

1. Metallocene complexes of formula (I) in Mt is Zr or Hf: X is a σ-ligand; R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2 and R 2’ Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group; n are each an independent integer from 1 to 5; R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It is not hydrogen; R 51’ It is C1-C 10 -hydrocarbon group; and R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

2. The metallocene complex of formula (I) according to claim 1, having formula (Ia) (I-a) in Mt is either Zr or Hf; Each X is an independent σ ligand; R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2 and R 2’ Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group; R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It is not hydrogen; R51' is C1-C 10 -hydrocarbon group; and R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

3. The metallocene complex of formula (I) according to claim 1 or 2, having formula (Ib) (I-b) in Mt is either Zr or Hf; Each X is an independent σ ligand; R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2’ It is C1-C 10 -Hydrocarbon group; R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It is not hydrogen; R 51’ It is C1-C 10 -hydrocarbon group; and R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

4. The metallocene complex of formula (I) according to any one of claims 1 to 3, having formula (Ic) (I-c) in Mt is either Zr or Hf; Each X is an independent σ ligand; R 1 Each being independently the same or different from the others is C1-C. 20 Hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2’ It is C1-C 10 -Hydrocarbon group; R 3 and R 4 Each is independently H, C1-C 10 hydrocarbon group, or -OR 31 -SR 31 or -NR 31 2 groups, wherein R 31 It is C1-C 10 Hydrocarbon group, wherein each phenyl group contains at least one R 3 Not hydrogen and at least one R 4 It's not hydrogen.

5. The metallocene complex according to any one of claims 1 to 4, wherein... One or two R on each phenyl group 3 It is not H, and R is on both phenyl groups. 3 They are the same, and The two R's on the phenyl group 4 It's not H, and these two Rs 4 They are the same.

6. A polymerization catalyst, comprising, preferably, the following: (i) The metallocene complex of formula (I) according to any one of claims 1 to 5; (ii) Catalysts containing elements of Group 13; as well as (iii) Optional carrier.

7. The polymerization catalyst according to claim 6, wherein the co-catalyst (ii) is an aluminoxane co-catalyst, preferably without any other co-catalyst.

8. The catalyst according to claim 6 or 7, wherein it is supported on silica.

9. A method for polymerizing propylene, comprising polymerizing propylene in the presence of a catalyst according to any one of claims 6 to 8.

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