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; r2 and R2'are each, independently, equal to or different from each other, CH2-R21 wherein R21 is H, a linear or branched C1-C6-alkyl group, a C3-C8-cycloalkyl group, or a C6-C9-aryl group, with the proviso that R2 and R2 'are not both methyl; r3 and R4 are each independently, equal to or different from each other, H, a linear or branched C1-C6-alkyl group, a C7-C20-arylalkyl group, a C7-C20-alkylaryl group, a C6-C20-aryl group or-OR31 wherein R31 is a C1-C10-hydrocarbyl group wherein at least one R3 is not H and at least one R4 is not H per phenyl group; r5 and R6, each independently equal to or different from each other, are C1-C10 hydrocarbyl groups, or may form together with the C atom to which they are attached a C5-C7 carbocyclic ring; r51'is a C1-C10-hydrocarbyl group, and R6 'is C (R61) 3, where R61 is a linear or branched C1-C6-alkyl group (I), in the formula (I), R51'is a C1-C10-hydrocarbyl group, and R6' is C (R61) 3.

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 in the production of polypropylene homopolymers or propylene copolymers, particularly copolymers with ethylene, especially multiphase polypropylene, which exhibit high activity levels, high molecular weights, and therefore low molecular weight filtration ratios (MFRs), and desirable melting points. These catalysts are particularly useful in the production of propylene-ethylene copolymers because they exhibit significant catalytic activity in such polymerizations. 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-based catalyst systems with different substitution modes, to produce polyethylene and polypropylene.

[0003] WO2019179959 describes a C1-symmetric bis-indenyl complex comprising an indenyl moiety with 5-methoxy and 6-tert-butyl substituents and an indacenyl moiety. In the presence of a borate co-catalyst, this catalyst provides a slightly higher Tm for hPP, ranging from 154 to 156 °C.

[0004] 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.

[0005] Therefore, the inventors are seeking new metallocene catalysts that can provide high selectivity without compromising productivity, particularly in the case of propylene homopolymerization or propylene-ethylene copolymerization. The desired catalysts should also exhibit improved performance in the production of high-melting-temperature and high-molecular-weight polypropylene homopolymers (hPP). The desired catalysts should also exhibit improved performance in the production of propylene-ethylene copolymers, for example, high activity for high-Mw copolymer products. The desired catalysts should also provide propylene-ethylene copolymers with high molecular weights. Furthermore, the desired catalysts should be able to produce T... m For hPP at least 157°C, it is particularly important that no borate-containing co-catalysts are required, due to regulatory issues associated with such compounds. Furthermore, the desired catalyst should be capable of producing multiphase copolymers in the gas phase at good productivity, achieving the desired loop / gas phase material separation, a higher matrix melting point, and a higher viscosity rubber phase. Summary of the Invention

[0006] One object of this disclosure is to provide new ligands, metallocene complexes, and catalysts therefrom to overcome the aforementioned problems.

[0007] The objectives of this disclosure are achieved by a polymerization method of polypropylene comprising a ligand of formula (II), a metallocene complex of formula (I), a polymerization catalyst comprising the metallocene complex of formula (I), and optionally a comonomer, as described in the independent claims. Preferred embodiments of this disclosure are disclosed in the dependent claims.

[0008] Surprisingly, it was found that specific modifications of C1 symmetric metallocenes, with the introduction of a larger alkyl substituent at one or both 2-positions of the ligand, preferably at the 2-position of the alkoxyindenyl ligand, combined with specific substitutions at other ligand positions, provided the desired properties. Attached Figure Description

[0009] In the following, the present disclosure will be described in more detail with reference to the accompanying drawings, in which...

[0010] Figure 1 The relationship between catalyst productivity in the gas phase and molecular weight of the soluble fraction (the amorphous phase generated in the gas phase) is shown.

[0011] Figure 2 The relationship between total catalyst productivity in the gas phase and molecular weight of the soluble fraction (the amorphous phase generated in the gas phase) is shown.

[0012] Figure 3 The relationship between the melting point of a multiphase copolymer and the molecular weight of the soluble portion (the amorphous phase generated in the gas phase) is shown.

[0013] definition

[0014] The following definitions are used throughout this description:

[0015] The term "C1-C" 20 "-hydrocarbon group" includes C1-C 20 -alkyl, C2-C 20 -Alkenyl, C2-C 20 -Alynyl group, C3-C 20 -Cycloalkyl, C3-C 20 -cycloalkenyl, C6-C 20 -Aryl, C7-C 20 -alkylaryl and C7-C 20 -Arylalkyl, or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C1-C1 is preferred. 20 -The hydrocarbon group is C1-C 20 -alkyl, C4-C 20 -Cycloalkyl, C5-C 20-cycloalkyl-alkyl, C7-C 20 -alkylaryl, C7-C 20 -Arylalkyl and C6-C 20 -Aryl, especially C1-C 10 -alkyl, C6-C 10 -Aryl and C7-C 12 -Arylalkyl, such as C1-C8 alkyl. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0016] The term "C1-C" 10 "-hydrocarbon group" includes C1-C 10 -alkyl, C2-C 10 -Alkenyl, C2-C 10 -Alynyl group, C3-C 10 -Cycloalkyl, C3-C 10 -cycloalkenyl, C6-C 10 -Aryl, C7-C 10 -alkylaryl and C7-C 10 -Arylalkyl, or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C1-C1 is preferred. 10 -The hydrocarbon group is C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -alkylaryl, C7-C 10 -Arylalkyl and C6-C 10 -Aryl, especially C1-C 10 -alkyl, C6-aryl and C7-C 10 -Arylalkyl, such as C1-C6-alkyl. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0017] It should be noted that straight-chain and branched hydrocarbon groups cannot contain cyclic units. Aliphatic hydrocarbon groups cannot contain aryl rings.

[0018] The term “heteroatoms of groups 14-16 of the periodic table” includes, for example, Si, N, O, or S.

[0019] As used in this article, the combination -R 1 The term "C4-C8-ring" in 2Si- refers to a cyclic group containing 4 to 8 carbon atoms and one Si atom, including, for example, silicone diesters, such as silicone butane, silicone pentane, or 9-silicon fluorene.

[0020] When it comes to complex definitions, the term "halogen" includes fluorine, chlorine, bromine, and iodine groups, especially chlorine or fluorine groups.

[0021] 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.

[0022] 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.

[0023] The numbering of these rings will be evident from the structure shown in this article.

[0024] In this application, catalyst activity is defined as the amount of polymer produced per hour per gram of catalyst. Catalyst metal activity is defined herein as the amount of polymer produced per hour per gram of metal. The term productivity is sometimes used to describe catalyst activity, although herein it refers to the amount of polymer produced per unit weight of catalyst.

[0025] The term “molecular weight” as used in this article refers to weight-average molecular weight Mw, unless otherwise stated.

[0026] The term “consistently composed of” as used herein refers to the presence of other components that do not substantially affect the essential characteristics of the compound or composition, such as trace amounts of impurities. Detailed Implementation

[0027] Metallocene catalyst complexes

[0028] 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.

[0029] 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.

[0030]

[0031] Formula (I) and any sub-formulas are intended to cover both cis and trans configurations. Preferred metallocene catalyst complexes are trans-configured.

[0032] 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.

[0033] The metallocene catalyst complexes of the present invention require a combination of three significant features of the ligand framework:

[0034] 1: Indene ligands with 4,8-diaryl substitution (preferably indane-based),

[0035] 2: A 5-alkyloxy group (preferably 5-alkoxyindene (preferably methoxyindene)) having a 6-tert-alkyl group (preferably tert-alkyl, most preferably tert-butyl) substituent, and

[0036] 3: At the 2-position of the ligand, preferably at the 2-position of the alkoxyindenyl ligand, there is at least one large alkyl substituent.

[0037] Therefore, the present invention relates to metallocene complexes of formula (I).

[0038]

[0039] in

[0040] Mt is either Zr or Hf;

[0041] X is a σ-ligand;

[0042] 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;

[0043] R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, provided that R is present. 2 and R 2’ Not all of them are methyl groups;

[0044] 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, C7-C20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - Hydrocarbon group, wherein each phenyl group has at least one R 3 Not H and at least one R 4 Not H;

[0045] R 5 and R 6 Each being independently the same or different from the others is C1-C. 10 Hydrocarbon groups, or they can form C5-C7 carbon rings together with the C atoms they are attached to;

[0046] R 51’ It is C1-C 10 -hydrocarbon group; and

[0047] R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0048] For the metallocene complex of formula (I) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0049] In the complex of formula (I), Mt is preferably Zr or Hf, with Zr being more preferred.

[0050] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, a halogen, a C1-C6-alkoxy group, or an 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 Cl, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0051] 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 1All 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.

[0052] Preferably, R 1 Each is independently the same or different from the others, and is a C1-C6 alkyl group, more preferably methyl.

[0053] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C3-C8 cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or cyclohexyl, provided that R is present. 2 and R 2’ Not all are methyl, R is preferred. 21 It is H, a straight-chain C1-C3-alkyl or a branched C3-alkyl, provided that R 2 and R 2 Not all are methyl groups. R is preferred. 2’ It is not methyl, but preferably CH2-R. 21 , where R 21 It is a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, more preferably R. 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl, R 2 It is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, preferably R. 21 It is H, a straight-chain C1-C6-alkyl group, or a branched C3-alkyl group. R is also preferred. 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2’ It is ethyl or n-propyl.

[0054] Advantageously, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21It is H or a straight-chain or branched C1-C6-alkyl group; preferably H or a straight-chain group, more preferably H or a straight-chain C1-C6-alkyl group, and even more preferably H or a straight-chain C1-C4-alkyl group; preferably H, methyl, or ethyl, provided that R 2 and R 2’ Not all of them are methyl.

[0055] In some implementation schemes, R 2 and R 2’ One of them is a methyl group, and the other has the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0056] In some implementation schemes, R 2 It is methyl, R 2’ Having the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0057] In some implementation schemes, R 2 and R 2’ None of them are methyl groups. For example, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

[0058] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31 , where R 31 It is a C1-C4 hydrocarbon group. 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 H, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0059] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0060] 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.

[0061] Advantageously, for two phenyl groups, one or two R on each phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 It is the same as 3',5'-dimethyl or 4'-tert-butyl.

[0062] 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.

[0063] In one implementation, each phenyl group has two R groups. 3 Not H, and on each phenyl group, R 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and the two R's on the phenyl group are... 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

[0064] Preferred R 5 and R 6 Together form -(R 56 )m-, where each R 56 Independently, it is a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group, preferably methyl, and m is 3 to 5, preferably 3 to 4; more preferably, it is in the -(R 56 In m, each R 56 It is -CH2-, where m is 3 to 5, preferably 3 to 4, and most preferably 3.

[0065] Preferred R 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 C1-C6-alkyl, branched C3-C6-alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0066] 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.

[0067] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ia).

[0068] (Ia)

[0069] in

[0070] Mt is either Zr or Hf;

[0071] X is a σ-ligand;

[0072] n is 1 to 3, for example 1, 2 or 3, preferably 3;

[0073] 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;

[0074] R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, provided that R is present. 2 and R 2 Not all of them are methyl;

[0075] 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, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20-Aryl or -OR 31 , where R 31 It is C1-C 10 - Hydrocarbon group, wherein each phenyl group has at least one R 3 Not H and at least one R 4 Not H;

[0076] R 51’ It is C1-C 10 -hydrocarbon group; and

[0077] R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

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

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

[0080] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, a halogen, a C1-C6-alkoxy group, or an 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 Cl, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0081] 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.

[0082] Preferably, R 1 Each is independently the same or different from the others, and is a C1-C6 alkyl group, more preferably methyl.

[0083] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C3-C8 cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or cyclohexyl, provided that R is present. 2 and R 2’ Not all are methyl, R is preferred. 21 It is H, a straight-chain C1-C3-alkyl or a branched C3-alkyl, provided that R 2 and R 2 Not all are methyl groups. R is preferred. 2 'Not methyl, preferably CH2-R' 21 , where R 21 It is a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, more preferably R. 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl, R 2 It is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group. R is also preferred. 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2’ It is ethyl or n-propyl.

[0084] Advantageously, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group; preferably H or a straight-chain group, more preferably H or a straight-chain C1-C6-alkyl group, and even more preferably H or a straight-chain C1-C4-alkyl group; preferably H, methyl, or ethyl, provided that R 2 and R 2’ Not all of them are methyl.

[0085] In some implementation schemes, R 2 and R 2’ One of them is a methyl group, and the other has the formula CH2-R 21 , where R 21It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0086] In some implementation schemes, R 2 It is methyl, R 2’ Having the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0087] In some implementation schemes, R 2 and R 2’ None of them are methyl groups. For example, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

[0088] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31 , where R 31 It is a C1-C4 hydrocarbon group. 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 H, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0089] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0090] 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 4The 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.

[0091] Advantageously, for two phenyl groups, one or two R on each phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 It is the same as 3',5'-dimethyl or 4'-tert-butyl.

[0092] 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.

[0093] In one implementation, each phenyl group has two R groups. 3 Not H, and on each phenyl group, R 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and the two R's on the phenyl group are... 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

[0094] Preferred R 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 C1-C6-alkyl, branched C3-C6-alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0095] 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.

[0096] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ib).

[0097] (Ib)

[0098] in

[0099] Mt is either Zr or Hf;

[0100] X is a σ-ligand;

[0101] 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;

[0102] R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl group, provided that R 2 and R 2’ Not all of them are methyl groups;

[0103] 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, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - Hydrocarbon group, wherein each phenyl group has at least one R 3 Not H and at least one R 4 Not H.

[0104] For the metallocene complexes of formula (Ib) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0105] In the complex of formula (Ib), Mt is preferably Zr or Hf, with Zr being more preferred.

[0106] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, a halogen, a C1-C6-alkoxy group, or an 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 Cl, benzyl, or methyl. Preferably, the two X groups are the same. Most preferably, both X are Cl, methyl, or benzyl, especially Cl.

[0107] 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.

[0108] Preferably, R 1 Each is independently the same or different from the others, and is a C1-C6 alkyl group, more preferably methyl.

[0109] R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain C1-C3-alkyl or a branched C3-alkyl, such as methyl, ethyl, n-propyl, isopropyl, provided that R is present. 2 and R 2’ Not all are methyl; R is preferred. 2’ It is not methyl, but preferably CH2-R. 21 , where R 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl, R 2 It is CH2-R 21 , where R 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group. R is also preferred. 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2’ It is ethyl or n-propyl.

[0110] Advantageously, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group; preferably H or a straight-chain group, more preferably H or a straight-chain C1-C6-alkyl group, and even more preferably H or a straight-chain C1-C4-alkyl group; preferably H, methyl, or ethyl, provided that R 2 and R2’ Not all of them are methyl.

[0111] In some implementation schemes, R 2 and R 2’ One of them is a methyl group, and the other has the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0112] In some implementation schemes, R 2 It is methyl, R 2’ Having the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0113] In some implementation schemes, R 2 and R 2’ None of them are methyl groups. For example, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

[0114] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31 , where R 31 It is a C1-C4 hydrocarbon group. 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 H, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0115] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0116] 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.

[0117] Advantageously, for two phenyl groups, one or two R on each phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 It is the same as 3',5'-dimethyl or 4'-tert-butyl.

[0118] 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.

[0119] In one implementation, each phenyl group has two R groups. 3 Not H, and on each phenyl group, R 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and the two R's on the phenyl group are... 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

[0120] Preferred metallocene catalyst complexes are MC-IE1, MC-IE2, and MC-IE3, as described in the examples below.

[0121] intermediate

[0122] Although this invention relates primarily to catalysts, it should be understood that the complexes of this invention and the ligands used to form these complexes are also novel.

[0123] The novel ligands of this invention possess a combination of unique features of metallocene ligand frameworks:

[0124] 5-alkyloxy group having a 6-tert-alkyl group (preferably tert-alkyl (most preferably tert-butyl)) substituent (preferably 5-alkoxyindenyl (preferably methoxyindenyl)); and

[0125] There is a large hydrocarbon substituent at the 2-position of the ligand.

[0126] Therefore, the present invention also relates to indene of formula (II).

[0127] (II)

[0128] in

[0129] The dashed lines represent double bonds present between carbon 1 and 2 or carbon 2 and 3 in the indanyl ring;

[0130] R 2’ It is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group;

[0131] R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - hydrocarbon group, wherein at least one R 4 Not H;

[0132] R 51’ It is C1-C 10 -hydrocarbon group; and

[0133] R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0134] For indene in equation (II) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0135] Preferably, R 2’ It is CH2-R 21 , where R 21 It is a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, more preferably, R 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl. R is also preferred. 2’ It is ethyl or n-propyl.

[0136] Preferably, R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 -aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31, where R 31 It is a C1-C4 hydrocarbon group. Even more preferably, each R... 4 Each of them independently, identical to or different from the others, is H, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially H, methyl or tert-butyl.

[0137] Preferred one or two R 4 The group is H. If the two R groups are H, then... 4 If the group is H, then the remaining R 4 The group is preferably in the para position. If an R 4 If the group is H, then the remaining R 4 The group is preferably located at the meta position.

[0138] Two Rs are preferred 4 It's not H, the optimal choice is these two Rs. 4 Same as, for example, 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0139] Preferred R 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 C1-C6-alkyl, branched C3-C6-alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0140] 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.

[0141] Polymerization catalyst

[0142] From another perspective, the present invention provides a polymerization catalyst, which comprises, preferably essentially, the following:

[0143] (i) Metallocene complexes of formula (I);

[0144] (ii) a catalyst system comprising a catalyst containing a Group 13 element; and

[0145] (iii) Optional carrier.

[0146] co-catalyst

[0147] 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.

[0148] According to the present invention, a cocatalyst system comprising an aluminoxane cocatalyst and optionally a boron-containing cocatalyst is advantageously used in combination with the metallocene catalyst complexes defined above.

[0149] Preferably, only aluminum-containing cocatalysts (such as organoaluminum compounds used to activate metallocene catalysts) are used in this invention.

[0150] In a preferred aspect of the invention, the cocatalyst system comprising an aluminoxane cocatalyst is advantageously used in combination with the metallocene catalyst complexes defined above.

[0151] Therefore, the polymerization catalyst preferably does not contain other co-catalysts (such as organoboron and / or borate compounds) that contain one or more Group 13 metal compounds other than aluminum for activating the metallocene catalyst.

[0152] The appropriate amount of catalyst will be well known to those skilled in the art.

[0153] Preferably, the amount of co-catalyst is selected to achieve a molar ratio below the defined range.

[0154] 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.

[0155] When using a boron cocatalyst, the molar ratio of boron (B) to metallocene metal ions (Mt) (preferably zirconium), 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), B / Mt, is 0.5:1 to 2:1.

[0156] Aluminoxane co-catalyst

[0157] Aluminoxane co-catalysts can be one of formula (A):

[0158] (A)

[0159] Where n is typically between 6 and 20, and R has the following meanings.

[0160] 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).

[0161] 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.

[0162] Boron-containing cocatalyst

[0163] According to the present invention, the aluminoxane cocatalyst can be used in combination with the boron-containing cocatalyst.

[0164] 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.

[0165] 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.

[0166] Meaningful boron-containing cocatalysts include those compounds of formula (B).

[0167] BY3 (B)

[0168] Where Y is the same or different, and is hydrogen, C1-C 10 - Haloalkyl or C6-C 20 - Halogenated aryl groups or fluorine, chlorine, bromine or iodine.

[0169] 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).

[0170] 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).

[0171] 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.

[0172] Tris(pentafluorophenyl)borane is particularly preferred.

[0173] However, borates, i.e., compounds containing borate anions, are preferred. These compounds have the formula (C):

[0174] Z4B–-W + (C)

[0175] Wherein Z is a substituted phenyl derivative, and the substituent is a halo-C1-C6-alkyl or halogen; W + It is a cationic counterion.

[0176] Preferably, the substituent of Z is fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0177] 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).

[0178] Preferred ionic compounds that can be used according to the present invention include:

[0179] Tributylammonium tetra(pentafluorophenyl)borate

[0180] Tributylammonium tetra(trifluoromethylphenyl)borate

[0181] Tributylammonium tetra(4-fluorophenyl)borate,

[0182] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid

[0183] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid

[0184] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0185] N,N-di(propylammonium) tetra(pentafluorophenyl)borate,

[0186] di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate,

[0187] Triphenylcarbomon tetra(pentafluorophenyl)borate

[0188] Or ferrocene tetra(pentafluorophenyl)borate.

[0189] Preferred is triphenylcarbium tetra(pentafluorophenyl)borate,

[0190] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0191] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0192] The preferred option is triphenylcarbium tetra(pentafluorophenyl)borate.

[0193] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0194] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0195] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0196] Catalyst manufacturing

[0197] 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.

[0198] 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, WO95 / 12622, 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 WO2020 / 239598 and WO2020 / 239603.

[0199] In another embodiment, 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. Such a catalyst can be prepared as described, for example, in WO2003 / 051934, WO2014 / 060540, and WO2019 / 179959.

[0200] The particulate carrier material used is an inorganic porous carrier, such as silica, alumina, or mixed oxides (e.g., silica-alumina), especially silica.

[0201] Silica carrier is preferred.

[0202] 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.

[0203] 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.

[0204] 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 size of inorganic porous supports (e.g., silica supports) can range from 20 to 40 nm.

[0205] 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.

[0206] 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.

[0207] The use of these carriers is common practice in this field.

[0208] 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).

[0209] The polymerization catalyst of the present invention can be produced by methods such as those described in WO2020 / 239603 or WO2020 / 239598.

[0210] Polymerization catalysts containing such metallocenes can be produced by a method comprising the following steps:

[0211] P1-a) The porous inorganic support is mixed with the first part of the aluminoxane cocatalyst in a hydrocarbon solvent to obtain a support treated with the aluminoxane cocatalyst, and optionally the aluminoxane-treated support is then heat-treated.

[0212] P1-b) The metallocene complex is dissolved in a hydrocarbon solvent (preferably an aromatic solvent, more preferably toluene), optionally with the addition of a second portion of aluminoxane cocatalyst, optionally with the addition of a boron-containing cocatalyst, wherein the amount of the first portion 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 the second portion of aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of aluminoxane cocatalyst, wherein the amounts of the added and boron-containing cocatalyst (if present) are such that the molar ratio of boron to M in the feed is in the range of 0.1:1 to 10:1;

[0213] P1-c) Add the solution obtained in step b) to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0214] P1-d) The supported catalyst system thus obtained is dried.

[0215] In steps P1-b) of this method, the various components can be mixed in any order. An optional boron-containing cocatalyst can be mixed with a metallocene complex dissolved in a hydrocarbon solvent, followed by the addition of an optional aluminoxane, or a metallocene complex dissolved in a hydrocarbon solvent can be mixed with an optional aluminoxane and hydrocarbon, followed by the addition of a 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 metallocene in only one step.

[0216] In a preferred aspect of the invention, the method includes:

[0217] P2-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, 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 co-catalyst-treated support is then dried.

[0218] P2-b) The metallocene is dissolved in a hydrocarbon solvent, optionally with the addition of a methylaluminoxane cocatalyst, wherein the amount of the methylaluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt% of the total amount of the methylaluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of the methylaluminoxane cocatalyst, to obtain a metallocene solution optionally containing an aluminoxane cocatalyst;

[0219] P2-c) Add the metallocene solution to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0220] P2-d) The supported catalyst system thus obtained is dried.

[0221] 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%.

[0222] The amounts of support, aluminoxane (preferably MAO), boron-containing cocatalyst, and metallocene depend on the desired ratios defined herein (boron / M, Al / M, Al / SiO2, M / SiO2).

[0223] polymerization

[0224] The catalyst according to the present invention is suitable for the production of propylene homopolymers, propylene-ethylene copolymers or propylene C4- 10 Alpha-olefin copolymers, particularly multiphase polypropylene and propylene-ethylene copolymers. Therefore, 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. 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.

[0225] Therefore, the present invention relates to a method for polymerizing propylene, polymerizing propylene and ethylene, or polymerizing propylene and C4- ethylene in the presence of a polymerization catalyst as described herein. 10 Methods for α-olefins.

[0226] In a preferred aspect, the present invention relates to a method for preparing a multiphase polypropylene copolymer (hPP), comprising:

[0227] (I) Propylene is bulk polymerized in the presence of a polymerization catalyst as defined herein to form a polypropylene homopolymer matrix;

[0228] (II) In the presence of the polypropylene homopolymer matrix and the polymerization catalyst and in the gas phase, propylene and ethylene are polymerized to form a multiphase polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber.

[0229] In another aspect, the present invention relates to a method for preparing a multiphase polypropylene copolymer, comprising:

[0230] (I) Propylene is subjected to bulk polymerization in the presence of a polymerization catalyst as defined herein to form a polypropylene homopolymer;

[0231] (II) In the presence of the homopolymer and the polymerization catalyst and in the gas phase, propylene is polymerized to form a polypropylene homopolymer matrix;

[0232] (III) In the presence of the polypropylene homopolymer matrix and the polymerization catalyst and in the gas phase, propylene and ethylene are polymerized to form a multiphase polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber (EPR).

[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 standard procedure commonly used in polyolefin production equipment and can be carried out in a continuous stirred tank reactor (CSTR) or a 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 propylene polymerization in a slurry 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-g (e.g., 20 to 60 bar-g), 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 this 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 polypropylene with a very high melting point. These characteristics can be achieved at commercially meaningful polymerization temperatures, such as 60°C or higher, for example, 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 one particular embodiment, the propylene polymer obtained using the catalyst of this invention has a narrow polydispersity index (Mw / Mn), from 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 range from 40 to 2000 kg / mol, preferably from 50 to 1500 kg / mol. The catalyst of the present invention is capable of forming polypropylene homopolymers with very high melting points. In a preferred embodiment, the propylene homopolymer formed by the method of the present invention has a melting point above 157°C, preferably above 158°C. propylene homopolymers with melting points up to 160°C or even up to 162°C can be formed.

[0245] propylene copolymer

[0246] Metallocene compounds containing ethylene or C4-C prepared by the present invention 10 Propylene copolymers of α-olefin comonomers can be prepared with high productivity and low solubility.

[0247] The polymers prepared by the catalysts described 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 (such as spunbond and meltblown fibers), molded products (such as injection molded, blow molded, rotational molded products), extrusion 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 glass volumetric flask. A standard solution containing 1000 mg / L LY and Rh (0.4 mL) was added. The flask was then filled with distilled water and shaken thoroughly. The solution was filtered through a 0.45 µm nylon syringe filter and analyzed using a Thermo iCAP 6300 ICP-OES and iTEVA software.

[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 both LY and Rh standard solutions. 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 a 10 mg / L standard solution 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] Catalyst activity

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

[0259]

[0260] Catalyst productivity is calculated based on the following formula:

[0261]

[0262] Polymer powder bulk density

[0263] Instrument: Electronic balance: measuring range 0.1 g-11000 g

[0264] Glass graduated cylinder: Volume = Maximum 250 ml

[0265] Plastic medicine spoon: Volume = 125 ml

[0266] Plastic funnel: D=105 mm

[0267] Procedure: Pour the unstable polymer powder into a glass graduated cylinder to a volume of 250 ml using a plastic spatula and a plastic funnel.

[0268] Calculation: Polymer mass (g) / Measurement volume (ml)

[0269] XS

[0270] The xylene soluble fraction (XS) defined and described in this invention is determined according to ISO 16152 as follows: 2.5 ± 0.1 g of polymer is dissolved in 250 ml of o-xylene under reflux and continuous stirring in a nitrogen atmosphere. After 30 minutes, the solution is cooled, first at ambient temperature for 15 minutes, and then maintained at a controlled temperature of 25 ± 0.5 °C for 30 minutes. The solution is then filtered through filter paper. To determine the xylene soluble content, an equal fraction of the filtrate (100 ml) is taken. This fraction is evaporated in a nitrogen stream, and the residue is vacuum dried at 100 °C until constant weight is achieved.

[0271] The soluble fraction (weight percentage) of xylene can then be determined as follows:

[0272] XS% = (100 xm 1 xv 0 ) / (m 0 xv 1 ),

[0273] Where m 0 Indicates the initial polymer amount (grams), m 1 Defined as the weight (grams) of the residue, v 0 Defined as initial volume (ml), v 1 Defined as the volume (milliliters) of the sample being analyzed.

[0274] To obtain the amorphous copolymer component for further characterization using GPC and NMR, the remaining xylene-soluble filtrate was precipitated with acetone. The precipitated polymer was filtered and dried to constant weight in a vacuum oven at 100°C.

[0275] GPC: Average molecular weight Molecular weight distribution and polydispersity index (Mn, Mw, Mw / Mn)

[0276] The molecular weight distribution (MWD) of the polymer samples was determined by gel permeation chromatography (GPC) at 160 °C, and the corresponding values ​​were calculated. Average molecule quantity M 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).

[0277] 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-LS15 / 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), followed by continuous gentle shaking 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.

[0278]

[0279] Where: w 25 (Polymer weight) and V 25(Volume of TCB at 25℃).

[0280] 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 polypropylene molecular weight was accomplished using the Mark Houwink equation and the following Mark Houwink constant:

[0281] K PS = 19 x 10 -5 ml / g, α PS = 0.655

[0282] K PP = 39 x 10 -5 ml / g, α PP = 0.725

[0283] Third-order polynomial fitting was used to fit the calibration data.

[0284] 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.

[0285] Use the following formula to determine Average molecular weight (M 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).

[0286] (1)

[0287] (2)

[0288] (3)

[0289] (4)

[0290] DSC

[0291] 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.

[0292] Melt flow rate

[0293] 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 processing performance. The higher the melt flow rate, the lower the molecular weight of the polymer. MFR is measured at 230°C and can be measured at different loads (e.g., 2.16 kg (MFR2) or 21.6 kg (MFR21)).

[0294] Comonomer content determined by FTIR

[0295] Quantitative infrared (IR) spectroscopy was used to estimate the C2 content of the copolymer by calibrating the primary method (NMR spectroscopy).

[0296] By using a set of quantitative 13 Internal, non-commercial calibration standards with known C2 content were used to facilitate calibration for C2 solution-state nuclear magnetic resonance (NMR) spectroscopy determination. The calibration procedure was performed in accordance with the standard method detailed in the literature [Spectroscopy of Polymers, 2nd edition, JL Koenig, Elsevier Science, 1999]. The calibration set consisted of eight calibration standards with C2 content ranging from 0.0 to 3.5 wt%.

[0297] Quantitative FTIR spectra were recorded in solid-state mode using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 300 μm thick, 25 × 25 mm square films prepared by compression molding at 180–210 °C and 70 bar. Standard transmission FTIR spectroscopy was used, with the spectral range of 5000–400 cm⁻¹. -1 Aperture size of 6 mm and spectral resolution of 2 cm -1 16 background scans, 16 spectral scans, interferogram zero-padding factor of 32, and Norton Beer strong apodization were used.

[0298] By analyzing 732.5 cm -1 CH2 vibration deformation (peak height) (A) Q Quantitative analysis was performed by integration, and the vibrational deformation corresponded to isolated ethylene bonds in the PEP comonomer sequence (integration method: K-OPUS, limit: 759 to 702 cm). -1 The quantitative bands were normalized to CH binding bands (A). R At a height of 4323 cm⁻¹, it corresponds to the CH structural element (integration method K, limit 4480, 3950 cm). -1 Then, a linear calibration curve is used based on the normalized absorbance (A0=A). Q / A R The C2 content, expressed as a weight percentage, is predicted. The calibration curve has been pre-constructed using least-squares regression of normalized absorbance and comonomer content measured by the primary technique (NMR spectroscopy). A typical linear calibration curve has the following form:

[0299] Equation 1

[0300] In this paper, C1 is the slope of the calibration curve, where 0.96 > C1 > 1, and the intercept is -0.02 > C0 > 0.06. The usual determination confidence level (COD) or R0 is used. 2 Assess calibration quality. COD is approximately 0.998.

[0301] NMR

[0302] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the isotactic regularity and regional defect content of polypropylene homopolymers. A Bruker Avance III 400 NMR spectrometer was used to measure the isotropic regularity and regional defect content of polypropylene homopolymers at 400.15 MHz and 100.62 MHz, respectively. 1 H and 13 C performed the operation and recorded the quantitative data in the solution state. 13 C{ 1 ¹H NMR spectroscopy. All spectra were performed at 125 °C. 13Recordings were taken using a C-optimized 10 mm selective excitation probe, with nitrogen used for all pneumatic setups. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). This setup was chosen primarily for the high resolution required to quantify stereoregularity distributions (Busico, V., Cipullo, R., Prog.Polym.Sci.26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed, using a NOE and a two-stage WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J.Mag.Reson.187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R.,Pellecchia, R., Severn, J., Talarico, G., Macromol.Rapid Commun.2007, 28,11289). A 3 s recirculation delay was used, yielding a total of 6144 (6k) transients per spectrum. For quantitative analysis... 13 C{ 1 The ¹H NMR spectra were processed and integrated, and the relevant quantitative properties were determined by integration using a proprietary computer program. All chemical shifts were internally referenced to the methyl signal at 21.85 ppm for the isotactic pentamematic group mmmm.

[0303] Quantitative analysis of stereoregularity distribution was performed by integrating the methyl regions from 23.6 to 19.7 ppm and correcting for any sites unrelated to meaningful stereo sequences (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Quintet isotactic regularity was determined by direct integration of the methyl regions and reported as the mole fraction or percentage of the isotactic pentatonic unit mmmm relative to all spatial pentatonic units, i.e., [mmmm] = mmmm / the sum of all spatial pentatonic units. The corresponding integral values ​​were corrected to remove the effects of sites not directly associated with spatial pentatonic units.

[0304] Characteristic signals corresponding to regional irregular propylene insertions were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem.Rev. 2000, 100, 1253). The presence of two methyl signals at 17.7 and 17.2 ppm indicated the presence of secondary propylene insertions in the form of 2,1-erythromeric regional defects, and was confirmed by the presence of other characteristic signals. The amount of 2,1-erythromeric regional defects was quantified using the average integral (e) of the e6 and e8 sites observed at 17.7 and 17.2 ppm, respectively, i.e., e = 0.5*(e6+e8). Characteristic signals corresponding to other types of regional irregularities were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem.Rev. 2000, 100, 1253). The amount of primary inserted propylene (p) is quantified based on the integral of all signals in the methyl region (CH3) from 23.6 to 19.7 ppm, taking into account other substances unrelated to the primary insertion and primary insertion signals excluded from the region, such that p = CH3 + 2*e. The relative content of a particular type of regional defect is reported as the mole fraction or percentage of said regional defect relative to all observed forms of propylene insertion, i.e., the sum of propylene units of all primary (1,2), secondary (2,1), and tertiary (3,1) insertions, for example [21e] = e / (p + e + t + i). The total amount of secondary inserted propylene in the form of 2,1-erythro or 2,1-threo regional defects is quantified as the sum of all said regional irregular units, i.e.,

[21] = [21e] + [21t].

[0305] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the ethylene content and isotactic regularity of copolymers.

[0306] Using a Bruker Avance III 400 NMR spectrometer, the NMR spectrometer was used to perform NMR measurements at 400.15 MHz and 100.62 MHz. 1 H and 13 C performed the operation and recorded the quantitative data in the solution state. 13 C{ 1 ¹H NMR spectroscopy. All spectra were performed at 125 °C. 13 Recorded using a C-optimized 10 mm extended temperature probe, all pneumatic devices used nitrogen. As described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475, approximately 200 mg of material was dissolved with chromium acetylacetone (Cr(acac)3) in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) to obtain a 65 mM relaxant solution in the solvent.

[0307] To ensure solution homogeneity, after initial sample preparation in the heating module, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This apparatus was chosen primarily for its high resolution and quantitative analytical performance required for accurate ethylene content quantification. Standard single-pulse excitation was used in the absence of a NOE, with an optimized pulse tip angle, a 1 s recirculation delay, and a two-stage WALTZ16 decoupling scheme, as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. A total of 6144 (6k) transients were obtained for each spectrum.

[0308] Quantitative 13 C{ 1The ¹H NMR spectra were processed, integrated, and the quantitative properties were determined from the integration. The chemical shifts of the solvent were used, with all chemical shifts indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. This method allows for comparative reference even in the absence of this structural unit.

[0309] In cases where characteristic signals corresponding to 2,1 erythromorphic region defects are observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, HN, Macromolecules 1984, 17, 1950, and WJ. Wang and S. Zhu, Macromolecules 2000, 33, 1157), it is necessary to correct for the effect of region defects on measurement performance. No characteristic signals corresponding to other types of region defects were observed.

[0310] Observing the characteristic signal corresponding to the introduction of ethylene (as described in Cheng, HN, Macromolecules 1984, 17, 1950), the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer:

[0311] fE = (E / (P + E))

[0312] Using the method described in WJ. Wang and S. Zhu, Macromolecules 2000, 33, 1157, by... 13 C{ 1 Integrating multiple signals across the entire spectral region of the H spectrum to quantify the comonomer fraction. This method was chosen because of its robust nature and ability to account for regional defects when necessary. The integration region was slightly adjusted to increase applicability across the entire range of comonomer contents encountered.

[0313] The molar percentage introduced by the comonomer is calculated from the mole fraction:

[0314] E [mol%] = 100 * fE

[0315] The weight percentage of comonomers introduced is calculated as a mole fraction:

[0316] E [wt%] = 100 * ( fE * 28.06 ) / ( (fE * 28.06) + ((1-fE) * 42.08) )

[0317] The isotactic regularity of the copolymer was determined according to known methods, such as those described in Macromolecules 2005, Vol. 38, pp. 3054-3059.

[0318] Crystallinity meter Law (Crystex)

[0319] The crystalline and soluble fractions (CF) of multiphase acrylic resin, along with the comonomer content and intrinsic viscosity of each fraction, were analyzed using a crystallinity analyzer. The crystalline and amorphous fractions were separated by a temperature cycle involving dissolution at 160°C, crystallization at 40°C, and redissolution at 160°C in 1,2,4-trichlorobenzene (1,2,4-TCB). Quantification of SF and CF, as well as determination of ethylene content (C2), were performed using an infrared detector (IR4), while an online dual-capillary viscometer was used to measure intrinsic viscosity (iV).

[0320] The IR4 detector is a multi-wavelength detector that detects IR absorbance at two different wavelength bands (CH3 and CH2) to determine the concentration and ethylene content in ethylene-propylene copolymers. The IR4 detector uses a series of known ethylene contents ranging from 2 wt.% to 69 wt.%. 13 EP copolymer calibration (measured by C-NMR).

[0321] The amounts of the soluble fraction (SF) and the crystalline fraction (CF) were determined by XS calibration in relation to the amount of xylene-soluble (XS) and the corresponding xylene-insoluble (XI) fraction, according to the standard gravimetric method of ISO 16152 (2005). XS calibration was performed by testing various EP copolymers with XS contents ranging from 2 to 31 wt%.

[0322] The intrinsic viscosity (iV) of the parent EP copolymer and its soluble and crystalline portions was determined using an online dual capillary viscometer and correlated with the corresponding iV determined in decahydronaphthalene according to ISO 1628-3 (2010).

[0323] Calibration was performed using a variety of commercial EP / PP copolymers with iV = 2-4 dL / g.

[0324] Weigh out the PP composition sample to be analyzed at a concentration of 10 mg / ml to 20 mg / ml. After filling the vial with 1,2,4-TCB containing 250 mg / L 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, dissolve the sample at 160°C until completely dissolved, typically for 60 min, while continuously stirring at 800 rpm.

[0325] A certain volume of sample solution is injected into a column packed with an inert support, where crystallization of the sample and separation of the soluble and crystalline fractions occur. This process is repeated twice. During the first injection, the entire sample is measured at high temperature to determine the iV [dl / g] and C2 [wt%] of the PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) accompanying the crystallization cycle are measured (wt% SF, wt% C2, iV).

[0326] Metallocene synthesis

[0327] Synthesis of MC-CE1

[0328] The synthesis of this metallocene has been carried out as described in WO2019179959, MC-2.

[0329] Synthesis of MC-CE2

[0330] The synthesis of this metallocene has been carried out as described in WO2005058916, Metallocene Example 1.

[0331] Synthesis of MC-IE2

[0332] Synthesis of 2-n-propyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0333]

[0334] Method 1

[0335] 2-Bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxyindan-1-ol

[0336]

[0337] Water (20 ml) was added to a solution of 61.29 g (0.2 mol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene in a mixture of 550 ml DMSO and 300 ml THF. Then, 37.38 g (210 mmol, 1.05 equivalent) of N-bromosuccinimide was added in portions over 90 min. The resulting mixture was then stirred overnight at room temperature. Next, 1200 ml of water and 600 ml of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted again with 2 × 150 ml of dichloromethane. The combined organic extracts were washed with 6 × 1000 ml of water, dried over Na₂SO₄, and evaporated to dryness. The residue was dissolved in 300 ml of hexane and allowed to crystallize at 5 °C for 30 min. The resulting white crystals (G3) were filtered off, washed with n-hexane, and dried under vacuum. The procedure yielded 64.89 g of the title product. The combined filtrate was evaporated to dryness, and the residue was recrystallized from 35 ml of n-hexane in the same manner. This procedure yielded an additional 8.07 g of the title product. Therefore, the total yield of 2-bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxyindan-1-ol isolated in this synthesis was 72.96 g (90.4%).

[0338] 1 H NMR (CDCl3): δ 7.34 (s, 1H), 6.99-6.94 (2s, 3H total), 5.29 (dd, J =6.2 Hz, J = 6.0 Hz, 1H), 4.17 (ddd, J = 7.7 Hz, J = 7.4 Hz, J = 6.0 Hz, 1H), 3.30 (dd, J = 16.4 Hz, J = 7.4 Hz, 1H), 3.24 (s, 3H), 3.06 (dd, J = 16.4 Hz,J = 7.7 Hz, 1H), 2.40 (d, J = 6.2 Hz, 1H), 2.35 (s, 6H), 1.42 (s, 9H). 13 C NMR(CDCl3): δ 158.21, 142.68, 137.99, 137.83, 136.83, 135.68, 131.99, 128.82,127.14, 121.07, 83.74, 60.37, 54.83, 39.88, 35.30, 30.73, 21.38.

[0339] 2-Bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene

[0340]

[0341] TsOH (2.0 g) was added to a solution of 2-bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-1H-indene (72.96 g, 180.88 mmol) preheated to approximately 60 °C in 600 mL of toluene. The mixture was refluxed using a Dean-Stark separatory for 7 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 200 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 = 2:1) to give 70.51 g (approximately 100%) of 2-bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene as a pale yellow glassy solid.

[0342] 1 H NMR (CDCl3): δ 7.24 (s, 1H), 7.05 (s, 2H), 6.99 (s, 1H), 6.87 (t, J= 1.6 Hz, 1H), 3.41 (d, J = 1.6 Hz, 2H), 3.26 (s, 3H), 2.36 (s, 6H), 1.43 (s,9H). 13 C NMR (CDCl3): δ 155.18, 141.55, 141.19, 138.79, 137.91, 137.46, 132.79,131.78, 128.82, 126.95, 123.25, 117.55, 60.65, 45.50, 35.19, 30.88, 21.40.

[0343] 5 / 6-tert-butyl-7 / 4-(3,5-dimethylphenyl)-6 / 5-methoxy-2-propyl-1H-indene

[0344]

[0345] [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](triphenylphosphine)nickel(II) dichloride (NiCl2(IPr)PPh3, 0.45 g, 0.57 mmol, 2.5 mol%) was added to 2-bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene (8.1 g, 21 mmol) and nA mixture of PrMgBr and THF (1.0 M, 105 mL, 5 equivalents) was added. The solution was refluxed for 30 min. The resulting dark solution was poured into a mixture of 200 g ice and 200 mL water. Then, 50 mL of 1.0 M hydrochloric acid was added. The organic layer was separated. The aqueous layer was extracted with 4 × 100 mL dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane-dichloromethane = 10:1, vol.). 7.0 g of a pale yellow oil was given. This product was a mixture of two isomers of indene and approximately 9% debromination byproduct impurities. To reduce the content of debromination byproducts, the crude product (7.0 g) was refluxed for 30 min with a mixture of 0.25 g TsOH in 100 mL toluene. After cooling the solution to room temperature, 200 ml of K2CO3 aqueous solution was added to separate the organic layer. The aqueous layer was extracted with 2 × 40 ml of toluene. The combined organic extracts were dried with K2CO3 and then evaporated to dryness. The resulting substance was distilled under reduced pressure to give 5.5 g (75%, purity approximately 97%) of a mixture of approximately 2:3 isomers as a colorless oil, bp 160-210℃ / 3 mm Hg.

[0346] minor isomers: 1 ¹H NMR (CDCl₃): δ 7.34 (s, 1H), 7.10 (s, 2H), 6.98 (broad singlet (br.s), 1H), 6.34 (s, 1H), 3.30 (s, 2H), 3.25 (s, 3H), 2.38–2.34 (m, 8H), 1.59–1.50 (m, 2H), 1.44 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ156.08, 151.14, 144.16, 137.87, 137.72, 137.53, 137.43, 131.86 128.28,127.84, 125.40, 120.81, 60.44, 41.13, 35.04, 33.52, 31.11, 22.44, 21.42,14.01.

[0347] Major isomers: 1¹H NMR (CDCl₃): δ 7.23 (s, 1H), 7.09 (s, 2H), 6.98 (broad singlet (br.s), 1H), 6.45 (m, 1H), 3.25 (s, 3H), 3.12 (s, 2H), 2.38–2.34 (m, 8H), 1.59–1.50 (m, 2H), 1.44 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ154.24, 149.97, 141.56, 140.85, 140.44, 138.30, 137.65, 131.87, 128.46,127.20, 126.05, 117.13, 60.65, 41.04, 35.12, 33.29, 31.00, 22.29, 21.42,13.94.

[0348] [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl]chlorodimethylsilane

[0349]

[0350] 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.

[0351] 1H 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.

[0352] Method 2

[0353] n-propylmalonic acid

[0354]

[0355] 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.

[0356] 2-n-Propylacrylic acid

[0357]

[0358] 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.

[0359] 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.

[0360] 6-tert-butyl-5-methoxy-2-n-propylindan-1-one

[0361]

[0362] At 50°C, 46.1 g (0.4 mol) of 2-n-propylacrylic acid was added to a mixture of 55 g P4O3 and 4-propylacrylic acid. 10 The mixture was added dropwise to Eaton's reagent obtained from 280 ml MeSO3H. 52.5 g (0.32 mol) of 1-tert-butyl-2-methoxybenzene was added dropwise to this mixture while vigorously stirring at 50–53 °C for about 1 h. 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%) of 6-tert-butyl-5-methoxy-2-n-propylindan-1-one as a pale yellow oil (bp 155–170 °C / 4 mm Hg).

[0363] 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.

[0364] 4-Bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one

[0365]

[0366] At 5°C, bromine (6.2 ml, 19.2 g, 120 mmol) was added dropwise over 15 min to 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 sodium acetate. n A mixture of Bu4NI, 100 ml dichloromethane, and 200 ml water was stirred vigorously. The mixture was stirred at 5 °C for 1 h, then a solution of 20 g sodium acetate in 100 ml water was added, followed by 3.1 ml (60 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 × 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 n-pentane at -15 °C to give 33.2 g of the title product (81.6%).

[0367] 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.

[0368] 6-tert-butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0369]

[0370] 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 of 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 with 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.

[0371] 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.

[0372] 5-tert-butyl-2-n-propyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0373]

[0374] NaBH4 (2.44 g, 64.6 mmol) was added to a solution of 6-tert-butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one (15.7 g, 43 mmol) in 180 mL THF cooled to 5 °C. 70 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 200 mL of dichloromethane and 200 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 × 50 mL of dichloromethane. The combined organic extracts were evaporated to dryness. TsOH (300 mg) was added to a solution of the residue in 300 mL of 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.

[0375] 1 ¹H 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 (sextile, 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.

[0376] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-indene-1-yl]dimethylsilane

[0377]

[0378] Will nA hexane solution of BuLi (2.5 M, 3.17 ml, 7.92 mmol) was added once to a suspension of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indenecyclopentadiene (3.0 g, 7.92 mmol) cooled to -50 °C in a mixture of 40 ml diethyl ether and 35 ml THF. 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indenecyclopentadiene was produced as described in WO 2019 / 189959 (Synthesis of MC-2). The resulting mixture was stirred overnight at room temperature, and the resulting pale orange solution with a large orange precipitate was then cooled to -50 °C, and 75 mg of CuCN was added. The resulting mixture was stirred at -25°C for 0.5 h, followed by a single addition of a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-propyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane (3.5 g, 7.93 mmol) in 50 mL THF. The mixture was stirred overnight at room temperature and then filtered through a silica gel 60 filter (40–63 µm), followed by washing 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 4.7 g (76%, approximately 98% purity) of the title product (a mixture of two stereoisomers in approximately 2:3 ratio) as a colorless, glassy solid.

[0379] trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (MC-IE2)

[0380]

[0381] At room temperature nA hexane solution of BuLi (2.5 M, 4.8 mL, 12.0 mmol) was added in a single batch to a solution of 4.7 g (6.0 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-isopropyl-1H-indene-1-yl]dimethylsilane in 50 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 1.4 g (6.0 mmol) of ZrCl4. The reaction mixture was stirred at room temperature for 24 h to give an orange-red suspension. The mixture was evaporated to dryness. The solid was extracted with 50 mL of hot toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of trans- and cis-zirconium dichloroethylene in a ratio of approximately 4:1. The extract was evaporated to dryness, and 30 ml of hexane was added. The yellow precipitate that formed from the resulting solution at room temperature was collected and dried under vacuum. This procedure yielded 3.1 g of trans-zirconium chloride and di-n-butyl ether impurities, which were further recrystallized from a mixture of about 5 ml toluene and 15 ml hexane to give 1.45 g of yellow trans-zirconium chloride powder containing 0.5 mol of toluene per mol of the complex. Therefore, the adjusted net weight of the isolated trans-complex was 1.38 g (24%). For C 56 H 64 Cl2OSiZr*0.5(C7H8), calculated values: C, 72.23; H, 6.93. Measured values: C, 72.15; H, 7.21. 1¹H NMR (CDCl₃): δ 7.42 (s, 1H), 7.25 (very broad singlet (br.s), 4H), 7.14 (s, 1H), 7.03 (s, 1H), 6.99 (s, 1H), 6.96 (s, 1H), 6.94 (s, 1H), 6.81 (s, 1H), 6.59 (s, 1H), 3.39 (s, 3H), 3.13–3.03 (m, 2H), 2.97–2.90 (m, 1H), 2.57–2.43 (m, 2H), 2.41 (s, 3H), 2.37 (s, 3H), 2.34 (12H), 2.29 (s, 3H), 2.18–2.11 (m, 1H), 2.05-1.97 (m, 1H), 1.81-1.70 (m, 1H), 1.35 (s, 9H), 1.30-1.18 (m, 2H), 1.14 (s, 3H), 0.82 (t, J = 7.3 Hz, 3H), -0.13 (s, 3H). 13 C NMR(CDCl3): δ 159.90, 144.63, 144.17, 143.25, 141.39, 139.87, 138.39, 138.06,137.74 (br. s), 137.22, 136.84, 134.70, 134.44, 132.03, 131.99, 131.72,130.56, 129.02, 128.81, 128.69, 127.90, 127.52, 126.91, 123.55, 123.38,121.17, 120.33, 81.89, 81.61, 62.65, 35.68, 34.06, 33.94, 32.39, 30.40, 26.97, 26.04, 21.56, 21.47, 21.41, 21.25, 19.86, 13.87, 3.83, 2.31.

[0382] Synthesis of MC-IE1

[0383] Synthesis of the second indene proligand: 2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene

[0384] Method A

[0385] 6-tert-butyl-5-methoxy-2-ethylindan-1-one

[0386]

[0387] At 50°C, 4.76 g (47.5 mmol, 1.27 equivalents) of 2-ethylacrylic acid was added to a mixture of 8.28 g of P4O 10 The mixture was prepared with Eaton's reagent and 52 ml of MeSO3H. 6.17 g (37.5 mmol) of 1-tert-butyl-2-methoxybenzene was added dropwise to the rapidly stirred mixture over approximately 1 h at 48–50 °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 0.4 L of cold water and 0.1 kg of ice. The crude product was extracted with 3 × 50 ml of dichloromethane, followed by the addition of 100 ml of hexane. The combined organic extracts were filtered through a silica gel 60 filter (40–63 μm, 20 ml) and washed with 2 × 25 ml of a 1:1 mixture of hexane and dichloromethane. The eluent was evaporated to dryness. The crude product was dissolved in 100 ml of dichloromethane; the resulting solution was washed with an aqueous K2CO3 solution, dried with K2CO3, and then evaporated to dryness to give 8.5 g (92%, approximately 90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one, which was a pale yellow oil.

[0388] 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one

[0389]

[0390] At 5°C, 6.95 ml (21.57 g, 135 mmol) of bromine was added dropwise over 5 min to 33.2 g (135 mmol) of 6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 41.7 g of sodium acetate, and 1.0 g of sodium acetate. n A mixture of Bu4NBr, 135 ml dichloromethane, and 230 ml water was added. The mixture was stirred at 5 °C for 1 h, followed by the addition of a solution of 19.0 g sodium acetate in 120 ml water, and then 3.5 ml (10.79 g, 67.5 mmol) bromine. The resulting mixture was stirred at this temperature for another 1 h, and then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 4 × 70 ml dichloromethane. The combined organic extracts were dried over K2CO3, filtered through a silica gel 60 filter (40–63 µm, 20 ml), the filtrate was evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 42.85 g (97.5%, 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.

[0391] 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0392]

[0393] A mixture of 41.2 g (126.5 mmol) 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 21.8 g (145.5 mmol, 1.15 equivalent) 3,5-Me₂C₆H₃B(OH)₂, 0.65 g (1 mol.%) Pd(PtBu₃)₂, 40.7 g Na₂CO₃, 210 ml 2-methyltetrahydrofuran, and 185 ml water was refluxed for 6 h. Then, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 50 ml dichloromethane. The combined organic extracts were evaporated to dryness, the residue was dissolved in 100 ml hexane, and the resulting solution was filtered through a silica gel 60 filter (40–63 µm, 20 ml). The eluent was evaporated to dryness, and the residue was crystallized from 50 ml pentane. The procedure yielded 21.6 g of pure 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one. The mother liquor was evaporated, and the resulting oil was then recrystallized from 10 ml of pentane at room temperature in the same manner. This procedure yielded 4.2 g of a white powder. The residue was crystallized from 20 ml of pentane at -15 °C to give 6.3 g of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one (90% purity). A total of 32.1 g (72.3%, approximately 98% purity) of pale yellow crystalline solid was obtained.

[0394] 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0395]

[0396] 0.81 g (21.4 mmol, 0.75 equivalent) of NaBH4 was added to a solution of 10.0 g (28.5 mmol) of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 14.0 mL of THF cooled to 17 °C. 10.7 mL of MeOH was added dropwise to the mixture over approximately 2 h, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 50 mL of dichloromethane and 100 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 3 × 30 mL of dichloromethane. The combined organic extracts were evaporated to dryness to give a gray oil. 0.045 g of TsOH was added to a solution of this oil in 75 mL of toluene. The mixture was refluxed using a Dean-Stark separator for 9 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 3 × 50 ml dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The residue was dissolved in 100 ml hexane, and the resulting solution was filtered through a silica gel 60 filter (40–63 µm, 10 ml) (washed again with 2 × 50 ml hexane). The eluent was evaporated to dryness, and the residue was dried under vacuum to give 9.3 g (98.6%) of 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene as a pale yellow oil.

[0397] [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane

[0398]

[0399] 5.53 ml (13.8 mmol) of 2.5 M nA hexane solution of BuLi was added in a single step to a solution of 4.59 g (13.7 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene in 100 ml of diethyl ether, cooled to -50 °C. The mixture was stirred overnight at room temperature, and the resulting orange-yellow solution was then cooled to -50 °C, followed by the addition of 8.25 ml (5.0 equivalents) of dichlorodimethylsilane in a single step. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3), with the filter cake washed with 2 × 20 ml of toluene. The combined filtrates were evaporated to dryness to give 5.7 g (97.5%) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]chlorodimethylsilane as a pale yellow viscous oil, which was ready for use without further purification.

[0400] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane

[0401]

[0402] 2.47 ml (6.17 mmol) 2.5 M n A hexane solution of BuLi was added in one step to a suspension of 2.33 g (6.15 mmol) of 4,8-bis(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indane in 27 ml of diethyl ether and 8 ml of THF, cooled to -50 °C. The resulting mixture was stirred overnight at room temperature, and then the resulting pale orange solution containing a large amount of orange precipitate was cooled to -50 °C, and 45 mg of CuCN was added. Over approximately 0.5 h, the temperature of the reaction mixture was raised to -17 °C, and then a solution of 2.65 g (6.2 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl](chloro)dimethylsilane in 45 ml of diethyl ether was added in one step to the suspension. The mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was dissolved in a mixture of 90 ml hexane and 10 ml dichloromethane. The resulting solution was filtered through a silica gel 60 filter (40–63 µm, 15 ml) (and then washed with a mixture of 2 × 25 ml hexane and dichloromethane (10:1)). The eluent was evaporated to dryness, and the residue was dried under vacuum to give 5.0 g of the title product (a mixture of approximately 60:40 stereoisomers) as a white powder, which was ready for use without further purification.

[0403] trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (MC-IE1)

[0404]

[0405] 5.0 ml (12.5 mmol) 2.5 M n BuLi's hexane solution was added in a single step at 0°C to 5.0 g (approximately 6.2 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane in 32 ml of [[6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane]. n The mixture was stirred overnight at room temperature in a pale yellow solution of Bu₂O. The resulting red turbid solution was then cooled to 0°C in an ice bath, and 1.45 g (6.2 mmol) of ZrCl₄ was added. The reaction mixture was stirred at room temperature for 24 h to give an orange-red suspension. This suspension was evaporated to dryness (to an orange powder state). 40 mL of pentane was added to the solid. The yellow precipitate that formed from the mixture at room temperature was collected and dried under vacuum. This procedure yielded 4.2 g of a 99:1 mixture of trans-zirconium chloride and cis-zirconium chloride, along with approximately 0.52 g of LiCl impurities. Thus, the title complex was obtained in approximately 63% yield.

[0406] Method B

[0407] 6-tert-butyl-5-methoxy-2-ethylindan-1-one

[0408]

[0409] At 50°C, 4.76 g (47.5 mmol, 1.27 equivalents) of 2-ethylacrylic acid was added to a mixture of 8.28 g P4O3. 10Add 6.17 g (37.5 mmol) of 1-tert-butyl-2-methoxybenzene to the rapidly stirred mixture at 48–50 °C over approximately 1 h. Stir the resulting mixture at this temperature for 1 h, then cool to room temperature and pour into a mixture of 0.4 L cold water and 0.1 kg ice. Extract the crude product with 3 × 50 mL of dichloromethane, adding 100 mL of hexane. Filter the combined organic extracts through a silica gel 60 filter (40–63 μm, 20 mL), wash with 2 × 25 mL of a 1:1 mixture of hexane and dichloromethane, and evaporate the resulting eluent to dryness. The crude product was dissolved in 100 ml of dichloromethane; the resulting solution was washed with an aqueous K2CO3 solution, dried with K2CO3, and then evaporated to dryness to give 8.5 g (92%, approximately 90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one, which was a pale yellow oil.

[0410] 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one

[0411]

[0412] At 5°C, 1.7 ml (5.26 g, 35.8 mmol) of bromine was added dropwise over 5 min to 8.1 g (32.9 mmol) of 6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 10.0 g of sodium acetate, and 0.3 g of... n A mixture of Bu4NBr, 30 ml dichloromethane, and 60 ml water was added. The mixture was stirred at 5 °C for 1 h, followed by the addition of a solution of 4.63 g sodium acetate in 26 ml water, and then 0.85 ml (2.63 g, 16.4 mmol) bromine. The resulting mixture was stirred at this 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 × 50 ml dichloromethane. The combined organic extracts were evaporated to dryness. The residue was dissolved in a mixture of 35 ml hexane and 35 ml dichloromethane, and the resulting solution was filtered through a silica gel 60 filter (40–63 µm, 20 ml) (and then washed with a 2 × 35 ml 1:1 mixture of hexane and dichloromethane). The eluent was evaporated to dryness, and the residue was dried under vacuum. The procedure yielded 9.67 g (90.4%, approximately 95% purity) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, a pale yellow oil that could be used without further purification.

[0413] 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0414]

[0415] 9.67 g (29.7 mmol) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 4.9 g (32.7 mmol, 1.1 equivalent) of 3,5-Me2C6H3B(OH)2, and 0.15 g (1 mol.%) of Pd (P t A mixture of Bu3)2, 9.57 g Na2CO3, 50 ml 2-methyltetrahydrofuran, and 44 ml water was refluxed for 6 h. Then, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 3 × 40 ml dichloromethane. The combined organic extracts were evaporated to dryness, the residue was dissolved in 100 ml hexane, and the resulting solution was filtered through a silica gel 60 filter (40–63 µm, 20 ml) (washed again with 2 × 35 ml hexane). The eluent was evaporated to dryness. 9.72 g (93.4%, approximately 94% purity) of a pale yellow oil was obtained.

[0416] 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0417]

[0418] NaBH4 (0.78 g, 20 mmol, 0.75 equivalent) was added to a solution of 9.62 g (27.4 mmol) of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 13.75 ml of THF cooled to 17 °C. 10.3 ml of MeOH was added dropwise to the mixture over approximately 2 h, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 50 ml of dichloromethane and 50 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 3 × 30 ml of dichloromethane. The combined organic extracts were evaporated to dryness to give 9.62 g of a gray oil. 0.043 g of TsOH was added to a solution of this oil in 72 ml of toluene. The mixture was refluxed using a Dean-Stark separator for 9 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 3 × 50 ml dichloromethane. The combined organic extracts were evaporated to dryness, and the residue was dissolved in 100 ml hexane. The resulting solution was dried over K₂CO₃ and filtered through a silica gel 60 filter (40–63 µm, 10 ml) (washed again with 2 × 50 ml hexane). The eluent was evaporated to dryness, and the residue was dried under vacuum to give 8.5 g (92.7%, approximately 97% purity) of 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene as a pale yellow oil.

[0419] The ligand was synthesized using 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indenium obtained by method B, and metallocene MC-IE1.

[0420] [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane

[0421]

[0422] Will n A hexane solution of BuLi (2.5 M, 0.444 ml, 1.11 mmol) was added in a single step to 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene (0.37 g, 1.1 mmol) cooled to 0 °C in 4 ml nThe mixture was stirred overnight at room temperature, and then 0.33 ml (2.5 equivalents) of dichlorodimethylsilane was added in a single batch. After 5 minutes, 0.86 ml of Et2O was added, and the resulting mixture was stirred overnight at room temperature. It was ready for use without further purification.

[0423] [4,8-Bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]dimethylsilane

[0424]

[0425] At -20°C, the substituted indene and... n BuLi was reacted in diethyl ether, and the mixture was stirred for 2 h. THF was then added, and the reaction mixture was allowed to stand overnight. Subsequently, a CuCN catalyst was added at -20 °C, and the reaction mixture was stirred at -20 °C for 30 min, followed by the addition of indenesilane at the same temperature. This procedure is very similar to the standard conditions, except that CuCN was added at -20 °C instead of -50 °C.

[0426] trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride

[0427]

[0428] 5.2 ml (13 mmol) 2.5 M n BuLi's hexane solution was added in a single step at 0°C to 5.05 g (approximately 6.5 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane in 32 ml of [[6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane]. nThe mixture was stirred overnight at room temperature in a pale yellow solution of Bu₂O. The resulting red turbid solution was then cooled to 0°C in an ice bath, and 1.51 g (6.5 mmol) of ZrCl₄ was added. The reaction mixture was stirred at room temperature for 24 h to give an orange-red suspension. The mixture was evaporated to dryness (to an orange powder state). 40 mL of pentane was added to the solid. The yellow solid precipitated from the mixture at room temperature was collected and dried under vacuum (4.0 g of a 99:1 mixture of trans and cis dichlorozirconia and approximately 0.54 g of LiCl impurities, therefore, the yield was approximately 57%).

[0429] Synthesis of MC-IE3

[0430] Synthesis of the second indene proligand: 4,8-bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indane

[0431] 2-Ethylacryloyl chloride

[0432]

[0433] One drop of DMF was added to a solution of 77.1 g (0.77 mol) 2-ethylacrylic acid in 600 mL of dichloromethane, cooled in an ice bath. Then, 108 g (0.85 mol) oxaloyl chloride was added dropwise to the resulting solution over 1 h, and the reaction mixture was stirred overnight at room temperature. The resulting mixture was concentrated, and the residue was distilled under vacuum to give 65 g (71.2%) 2-ethylacrylyl chloride as a colorless liquid, bp 55-75 °C / 100 mbar.

[0434] 1 H NMR (CDCl3): δ 6.55 (s, 1H), 6.02 (s, 1H), 2.39 (q, J = 7.4 Hz, 2H), 1.12 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 168.73, 146.60, 132.03, 25.33, 12.55.

[0435] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one, Method A

[0436] 2-Ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0437]

[0438] Over 15 min, a mixture of 65.0 g (548 mmol) of 2-ethylacrylyl chloride and 65.0 g (548 mmol) of indane was added dropwise to a suspension of 182 g (1.37 mol) of AlCl3 in 1000 mL of dichloromethane cooled to 0 °C. The cooling bath was then removed, and the solution was stirred overnight at room temperature. The reaction mixture was poured into 2 kg of crushed ice, the organic phase was separated, and the aqueous phase was extracted with 3 × 200 mL of dichloromethane. The combined organic extracts were washed with an aqueous K₂CO₃ solution, dried over K₂CO₃, and passed through a silica gel 60 short pad (40–63 µm). The eluent was evaporated to dryness. The resulting oil was vacuum distilled to give 80.92 g (approximately 74%, purity approximately 70%) of a pale yellow oil, bp 130–145 °C / 3 mm Hg. The 2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one thus obtained can be used without further purification.

[0439] 1 H NMR (CDCl3): δ 7.52 (s, 1H), 7.24 (s, 1H), 3.20 (dd, J1 = 7.8 Hz, J2 = 17.1 Hz, 1H), 2.94-2.86 (m, 4H), 2.71 (dd, J1 = 3.6 Hz, J2 = 17.0 Hz,1H), 2.59-2.54 (m, 1H), 2.13-2.05 (m, 2H), 1.96-1.90 (m, 1H), 1.56-1.45 (m,1H), 0.98 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 208.05, 152.68, 152.60, 143.74, 135.46, 121.77, 118.67, 48.89, 32.79, 31.74, 25.52, 24.31, 11.30.

[0440] 4,8-Dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0441]

[0442] At -10 °C, 80.9 g (approximately 404 mmol) of 2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one (prepared as above, approximately 70% purity) was added dropwise over 15 min to a suspension of 134.7 g (1.01 mol, 2.5 equivalents) of AlCl3 in 400 mL of dichloromethane. The reaction mixture was stirred at this temperature for 10 min, followed by the dropwise addition of 41.7 mL (129.4 g, 809 mmol, 2.0 equivalents) of bromine over 1 h. The resulting mixture was stirred overnight at room temperature and then poured into 1000 cm³ of crushed ice. The organic layer was separated, and the aqueous layer was extracted again with 3 × 300 mL of dichloromethane. The combined organic extracts were washed with an aqueous solution of K₂CO₃, dried over K₂CO₃, and the resulting eluent was evaporated to dryness through a silica gel 60 short pad (40–63 µm). The crude product was purified by crystallization from 500 ml of n-hexane to obtain 89.5 g of crude product. This crude product was then crystallized from 500 ml of n-hexane to obtain an analytically pure product. The mother liquor from the final crystallization was evaporated to approximately 200 ml, yielding a white suspension in hexane. This suspension was heated to its boiling point (~65-70°C) and then filtered (while hot) through a glass frit funnel (G3). The resulting precipitate was dried under vacuum to give another batch of the title product. The total yield was 59.9 g (41%). 1 H NMR(CDCl3): δ 3.17-3.05 (m, 5H), 2.70-2.60 (m, 2H), 2.17 (quin, J = 7.7 Hz, 2H), 2.03-1.93 (m, 1H), 1.59-1.48 (m, 1H), 1.02 (t, J = 7.4 Hz, 3H). 13 C NMR(CDCl3): δ 204.94, 154.85, 152.52, 146.90, 134.22, 117.80, 115.17, 49.83, 35.64, 34.60, 32.30, 24.53, 23.18, 11.47.

[0443] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0444]

[0445] 59.9 g (167 mmol) of 4,8-dibromo-2-ethyl-1-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one, 56.4 g (376 mmol, 2.25 equivalents) of 3,5-dimethylphenylboronic acid, and 1.34 g of Pd(P t A mixture of Bu3)2, 95.8 g Na2CO3, 600 ml 2-methyltetrahydrofuran, and 420 ml water was refluxed for 7 h. Then, 600 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 mass. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 400 mm, eluent: hexane-dichloromethane = 1:3, vol.). The eluent was evaporated to dryness, and the residue was then ground with 300 ml n-hexane. The resulting suspension was filtered through a glass frit funnel (G3), and the resulting white precipitate was washed with 2 × 30 ml n-hexane and then dried under vacuum. The yield was 61.47 g (90%). 1 H NMR (CDCl3): δ 7.03 (s, 1H), 6.99 (s, 1H), 6.95 (s, 2H), 6.92 (s, 2H), 3.08 (dd, J1 = 8.7 Hz, J2 = 18.0 Hz, 1H), 2.88-2.68 (m, 4H), 2.57-2.49(m, 2H), 2.39 (s, 6H), 2.36 (s, 6H), 2.04-1.84 (m,3H), 1.47-1.36 (m, 1H), 0.91 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 207.37,151.81, 149.90, 143.55, 138.22, 137.93, 137.23, 136.88, 135.89, 135.43,132.40, 128.93, 126.74, 126.49, 49.72, 33.03, 31.96, 31.06, 25.64, 24.30,21.46, 21.41, 11.66.

[0446] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one, Method B

[0447] 2-Ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0448]

[0449] At 50°C, 4.76 g (47.5 mmol, 1.27 equivalents) of 2-ethylacrylic acid was added to a mixture of 8.28 g of P4O 10 Add 4.43 g (37.5 mmol) of indane (~95% purity) to the rapidly stirred mixture at 48–50 °C over approximately 45 min. Stir the resulting mixture at this temperature for 1 h, then cool to room temperature and pour into a mixture of 0.4 L cold water and 0.1 kg ice. Extract the crude product with 3 × 50 mL of dichloromethane, adding 75 mL of hexane. Filter the combined organic extracts through a silica gel 60 filter (40–63 μm, 20 mL) and wash with 2 × 40 mL of a 1:2 mixture of hexane and dichloromethane. Evaporate the eluent to dryness. The crude product was dissolved in 100 ml of dichloromethane; the resulting solution was washed with an aqueous K2CO3 solution, dried with K2CO3, and then evaporated to dryness to give 7.15 g (95%, about 60% purity) of 2-ethyl-3,5,6,7-tetrahydro-s-indane-1(2H)-one as a yellow oil.

[0450] 4,8-Dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0451]

[0452] At -10 °C, a solution of 7.0 g (approximately 35 mmol) of 2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one (prepared as above, approximately 60% purity) in 10 mL of dichloromethane was added dropwise to a suspension of 11.6 g (87 mmol) of AlCl3 in 40 mL of dichloromethane over 15 min. The reaction mixture was stirred at this temperature for 10 min, and then 4.0 mL (12.4 g, 77.5 mmol, 2.2 equivalents) of bromine was added dropwise over 1 h at -10 °C. The resulting mixture was stirred overnight at room temperature and then poured into a 100 cm³ container. 3In crushed ice. Separate the organic layer and extract the aqueous layer with 3 × 30 ml dichloromethane. Pass the combined organic extracts through a silica gel 60 short pad (40–63 µm, 40 ml), wash the silica gel layer with 2 × 30 ml dichloromethane, and evaporate the resulting eluent to dryness. Dissolve the resulting oily substance in 50 ml hexane. After 5 min, filter off the black precipitate that forms. Crystallize the filtrate overnight at -15 °C to give 6.4 g of crude solid product. Dissolve the crude product under reflux in a mixture of 25 ml n-hexane and 6 ml toluene. Then crystallize (from boiling point to RT) to give 4 g of the desired product and trace amounts of polymerization byproduct impurities. Evaporate the mother liquor from the last crystallization to dryness. Crystallize the residue from a mixture of 10 ml hexane and 1 ml toluene to give another batch (0.9 g) of product. The 4.9 g solid product thus obtained was dissolved in 20 ml of a 1:1 mixture of hexane and dichloromethane, and the solution was passed through a silica gel 60 short-shield layer (40–63 µm, 15 ml). The silica gel layer was then washed with 2 × 20 ml of a 1:1 mixture of hexane and dichloromethane. The combined eluents were evaporated to dryness to give 4.6 g (37%) of the title product as a pale yellow solid.

[0453] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0454]

[0455] 4.3 g (12 mmol) of 4,8-dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one, 4.14 g (27.6 mmol, 2.3 equivalents) of 3,5-dimethylphenylboronic acid, and 0.1 g of Pd(P tA mixture of Bu3)2, 6.9 g Na2CO3, 43 ml 2-methyltetrahydrofuran, and 30 ml water was refluxed for 7 h. Then 50 ml dichloromethane was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 30 ml dichloromethane. The combined organic extracts were dried with K2CO3 and then evaporated to dryness. The solid mass was dissolved in 30 ml of a 2:3 mixture of hexane and dichloromethane, and the resulting solution was passed through a silica gel 60 short-shield layer (40–63 µm, 20 ml). The silica gel layer was washed with 3 × 20 ml of a 1:1 mixture of hexane and dichloromethane, and the resulting eluent was evaporated to dryness. The solid residue was treated with 20 ml pentane, and the resulting suspension was filtered through a glass frit funnel (G3). The precipitate was dried under vacuum to give 3.8 g of the title product. The mother liquor filtrate was evaporated to about 10 ml to form a suspension, which was then filtered through a glass frit funnel (G3). The residue was vacuum dried to obtain another batch (0.95 g) of the title product. The total yield was 4.75 g (97%, 98% purity).

[0456] 4,8-Bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indah.

[0457]

[0458] Methanol (100 ml) was added dropwise over 5 h at 0–5 °C to a mixture of 20.0 g (49 mmol) of 4,8-bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one and 4.28 g (109 mmol) of NaBH4 in 300 ml of THF. The resulting mixture was stirred overnight at room temperature and then evaporated to dryness. 400 ml of dichloromethane and 1000 ml of water were added to the residue, and 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 × 200 ml of dichloromethane. The combined organic extracts were dried over Na2SO4 and evaporated to dryness to give a white solid block. TsOH (1.0 g) was added to a solution of this solid block in 350 ml of toluene preheated to approximately 60 °C. The mixture was refluxed using a Dean-Stark separatory for 12 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 100 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, d 50 mm, l 30 mm, hexane-dichloromethane = 10:1, vol.). This procedure yielded 19.4 g (100%) of the title product as a white solid. 1 H NMR (CDCl3): δ 7.05 (s, 2H), 7.03 (s, 2H), 6.98 (s, 2H), 6.44 (m,1H), 3.25 (s, 2H), 2.89 (t, J =7.3 Hz, 2H), 2.83 (t, J =7.3 Hz, 2H), 2.42-2.33 (m, 14H), 1.98 (quin, J =7.3 Hz, 2H), 1.10 (t, J =7.4 Hz, 3H). 13 C NMR(CDCl3): δ 151.79, 142.60, 140.88, 140.24, 140.19, 139.83, 138.42, 137.55,137.39, 133.53, 129.79, 128.39, 128.18, 127.32, 126.60, 124.41, 40.59, 32.78,32.51, 26.09, 24.45, 21.42, 13.44.

[0459] [4,8-Bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]dimethylsilane

[0460]

[0461] At -50℃, n A hexane solution of BuLi (2.5 M, 3.84 mL, 9.6 mmol) was added in a single addition to a solution of 4,8-bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indane (3.77 g, 9.6 mmol) in a mixture of 40 mL diethyl ether and 40 mL THF. The mixture was stirred overnight at room temperature, and the resulting greenish-yellow suspension was cooled to -50 °C, and 100 mg CuCN was added. The resulting mixture was stirred at -20 °C for 0.5 h, and then a single addition of 4.1 g (9.6 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl](chloro)dimethylsilane in 50 mL THF was added. The resulting mixture was stirred at room temperature for 12 h, then filtered through a silica gel 60 filter (40–63 μm) 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 5.10 g (6.5 mmol, yield approximately 67.8%, purity approximately 98%) of the title product (a mixture of approximately 40:60 stereoisomers) as a glassy solid.

[0462] transdimethylsilanediol [η] 5 -4,8-Bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][η 5 [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxyindene-1-yl]zirconium dichloride (MC-IE3)

[0463]

[0464] At room temperature nA hexane solution of BuLi (2.5 M, 5.1 mL, 12.75 mmol) was added in a single step to a solution of [4,8-bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]dimethylsilane (5.00 g, 6.38 mmol) in 50 mL of di-n-butyl ether. The mixture was stirred at room temperature for 5 h, and then the resulting solution was cooled to 0 °C in an ice bath, and ZrCl4 (1.49 g, 6.39 mmol) was added. The resulting mixture was stirred at room temperature for 24 h to give a yellow suspension. The suspension was evaporated to dryness, and the residue was extracted with 50 mL of warm toluene. The precipitate (G4) was filtered off. Based on NMR spectral evidence, the resulting filtrate contained approximately 95 / 5 of a mixture of trans- and cis-zirconium dichloroethylene. The filtrate was evaporated to dryness, and 30 mL of hexane was added. The orange precipitate (G3) that fell from the solution overnight at room temperature was filtered off, washed with 10 mL of n-hexane, and then dried under vacuum. This procedure yielded 4.8 g of trans-zirconium dichloroethylene (and approximately 0.6% cis isomer impurities) containing 0.02 mol ether / mol Zr and 0.08 mol n-hexane / mol Zr, thus the adjusted net weight of the isolated complex was approximately 4.75 g (yield approximately 79%).

[0465] For C 56 H 64 Cl2OSiZr., Analytical values: C, 71.30; H, 6.84. Measured values: C, 71.45; H, 7.02. 1 ¹H NMR (CDCl₃): δ 7.65–6.7 (very broad singlet (br.s), 4H), 7.38 (s, 1H), 7.09 (s, 1H), 7.02 (s, 1H), 6.99 (s, 1H), 6.96 (s, 1H), 6.95 (s, 1H), 6.86 (s, 1H), 6.60 (s, 1H), 3.40 (s, 3H), 3.11–2.86 (m, 4H), 2.60–2.25 (m, 22H), 1.99 (m, 1H), 1.82–1.70 (m, 1H), 1.35 (s, 9H), 1.14–1.10 (m, 6H), 0.90 (t, J = 7.4). Hz, 3H), -0.16 (s, 3H). 13C NMR (CDCl3): δ 159.82, 144.81, 144.09, 143.11, 141.75,141.49, 141.12, 138.40, 138.16, 137.77 (br.s), 137.38, 136.92, 134.52,132.25, 132.12, 131.74, 130.93, 128.96, 128.85, 128.79, 128.70, 127.89,127.50 (br.s), 126.85, 122.95, 121.18, 120.77, 119.34, 81.54, 80.54, 62.68, 35.63, 33.91, 32.38, 30.39, 26.52, 26.07, 25.86, 21.46, 21.41, 21.27, 17.00, 16.59, 4.20, 2.38.

[0466] Catalyst synthesis, the chemicals used

[0467] The 30 wt% MAO Axion CA1330 toluene solution was purchased from Chemtura / Lanxess and was ready to use upon receipt and stored at -20°C for no more than 6 months.

[0468] Using Schlenk and glove box technology, all chemicals and chemical reactions are handled in an inert gas atmosphere using dried glassware, syringes, needles, or cannulas.

[0469] All catalysts were prepared using Sunspera AGC DM-L-303 silica calcined at 600°C.

[0470] All catalysts were prepared using Sunspera AGC DM-L-303 silica calcined at 600°C.

[0471] Catalyst preparation

[0472] 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 was a second portion of MAO added to the metallocene / toluene slurry to promote complete dissolution of the metallocene.

[0473] Preparation of SiO2 / MAO Activated Support

[0474] 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).

[0475] SiO2 / MAO / MC-CE1 = Synthesis of Comparative Catalyst 1 (CE1)

[0476] In a nitrogen-filled glove box, dry toluene (2.5 ml) was added to an equal volume of metallocene MC-CE1 (32.3 mg). The mixture was stirred at room temperature for 30 minutes. Next, 2.0 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 light red, free-flowing powder.

[0477] SiO2 / MAO / MC-CE2 = Synthesis of Comparative Catalyst 2 (CE2)

[0478] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 26.4 mg of metallocene C in a diaphragm flask. The solution was stirred at room temperature for 30 minutes, but no dissolution was observed. Then, 0.1 ml of MAO was added, and the mixture was stirred for another 30 minutes until completely dissolved. Next, 2.0 g of SiO2 / MAO was placed in a diaphragm flask. The toluene solution of 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 a light red, free-flowing powder (1.96 g).

[0479] SiO2 / MAO / MC-IE1 = Synthesis of Catalyst 1 (IE1-1) of the Invention

[0480] In a nitrogen-filled glove box, 5 ml of dry toluene was added to 60.2 mg of metallocene trans-MC-IE1 in a diaphragm flask. The solution was stirred at room temperature for 30 min. Next, 0.2 ml of a 30 wt% toluene solution of methylaluminoxane (MAO) (Axion Ca1330) was added, and the solution was stirred again for 30 min. Then, the toluene solution of metallocene and MAO was added dropwise over 10 min using a syringe to 4.003 g of SiO2 / MAO in the diaphragm flask support 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 and 45 min to obtain the catalyst as a light red free-flowing powder.

[0481] SiO2 / MAO / MC-IE1 = Synthesis of Catalyst 2 (IE1-2) of the Invention

[0482] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 16.20 mg of metallocene trans-MC-IE1 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes, but remained hazy. Then, 0.1 ml of MAO was added, and the mixture was stirred for another 30 minutes until completely dissolved. Next, 2.009 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 pink, free-flowing powder.

[0483] SiO2 / MAO / MC-IE1 = Synthesis of Catalyst 3 (IE1-3) of the Invention

[0484] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 40.7 mg of metallocene trans-MC-IE1 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes, but remained turbid. Then, 0.1 ml of MAO was added, and the mixture was stirred for another 30 minutes until completely dissolved. Next, 2.002 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 pink, free-flowing powder.

[0485] Synthesis of SiO2 / MAO / MC-IE1 = Catalyst 4 (IE1-4) of this invention

[0486] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 20.3 mg of metallocene trans-MC-IE1 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes, but remained turbid. Then, 0.1 ml of MAO was added, and the mixture was stirred for another 30 minutes until completely dissolved. 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 pink, free-flowing powder.

[0487] Synthesis of SiO2 / MAO / MC-IE2 = Catalyst 5 (IE5) of the present invention

[0488] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 28.4 mg of metallocene trans-MC-IE2 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes. 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 red, free-flowing powder.

[0489] Synthesis of SiO2 / MAO / MC-IE3 = Catalyst 6 (IE6) of the present invention

[0490] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 28.4 mg of metallocene trans-MC-IE3 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes. 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 red, free-flowing powder.

[0491] The metallocene content in each catalyst was calculated using mass balance. Table 3 lists these values:

[0492] Table 3: Catalysts tested and their metallocene content

[0493]

[0494] * MC = Metallocene; the metallocene content in the dried catalyst is calculated using mass balance.

[0495] Aggregate Examples

[0496] monomers and gases

[0497] Hydrogen (6.0g by mass) was supplied by Air Liquide and was ready for use upon receipt. Propylene (2.3g by mass) and ethylene were purified by chromatographic column packed with PolyMax301 T-4427B (60°C; Cu / CuO), MS13X-APG 1 / 16 molecular sieve, and SelexsorbCOS 1 / 8.

[0498] Propylene and propylene / ethylene two-step polymerization process (20-L reactor, liquid phase + gas phase)

[0499] Step 1: Homopolymerization of propylene in bulk, 20-L reactor

[0500] Add 4.45 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 (R1) or 21.2 dm³ (R2). Add triethylaluminum (0.8 ml of 0.62 mol / L n-heptane solution) using a 250 g propylene feed stream, followed by the addition of the selected amount of H2 over one minute via a mass flow controller (see table). Stabilize the reactor temperature at 25 °C (HB-Therm) and stir the solution at 250 rpm for at least 20 min.

[0501] Then the catalyst is injected as described below.

[0502] Load the required amount of solid catalyst into a 5 ml stainless steel vial; alternatively, after shaking in a glass vial for approximately 5 minutes, use a syringe to extract a selected amount of catalyst slurry from the oil and load it into a 5 ml stainless steel vial. Then attach the catalyst vial to the port on the reactor cap. Feed the catalyst into the reactor by rinsing 350 g of propylene from a balance through the catalyst vial. Maintain the stirring speed at 250 rpm and proceed with prepolymerization at 25°C or 30°C for 10 minutes. Then raise the polymerization temperature to the set value. At 60°C, add the second portion of H2 over 2 minutes.

[0503] The reactor temperature was kept constant throughout the polymerization process. Polymerization time was measured when the temperature dropped 2°C below the set polymerization temperature. When the set polymerization time elapsed, the reaction was stopped by injecting 5 ml of ethanol, cooling the reactor, and simultaneously flash-evaporating volatile components. After purging the reactor three times with N2 and performing one vacuum / N2 cycle, the reactor was opened, the polymer powder was removed, and dried overnight in a fume hood. 0.5 wt% Irganox B225 (dissolved in acetone) was added to 100 g of polymer, and the mixture was then dried overnight in a fume hood and then further dried for 1 hour in a vacuum drying oven at 60°C.

[0504] Step 2: Ethylene-propylene gas-phase copolymerization, 20-L reactor

[0505] Proceed to step 2 as follows. After the bulk homopolymerization step is complete, reduce the stirrer speed to 50 rpm and the pressure to 0.4 bar-g by discharging the monomer. Set the stirrer speed to 180 rpm and the reactor temperature to 70°C. Then increase the reactor pressure to 20 bar-g by feeding a specified C3 / C2 gas mixture (see table). The C3 / C2 ratio is defined as follows.

[0506]

[0507] Where C2 / C3 is the weight ratio of the two monomers, and R is their relative reactivity ratio, which were determined experimentally. In this experiment, the value of R was set to 0.40.

[0508] The temperature is kept constant by a thermostat, and the pressure is kept constant by feeding a C3 / C2 gas mixture corresponding to the target polymer composition via a mass flow controller and by a thermostat until the set time for this step ends.

[0509] The reactor was then cooled (to approximately 30°C) to flash-evaporate volatile components. After purging the reactor three times with N2 and performing one vacuum / N2 cycle, the product was removed and dried overnight in a fume hood. 0.5 wt% Irganox B225 (acetone solution) was added to 100 g of the polymer, and the mixture was dried overnight in a fume hood, followed by drying in a vacuum drying oven at 60°C for 2 hours.

[0510] Multiphase polymerization results

[0511] The performance of catalysts prepared from different metallocenes in liquid propylene polymerization was compared. The conditions are described in Table 4A, and the results are shown in Table 4B.

[0512] Table 4A: Propylene Polymerization Conditions

[0513]

[0514]

[0515] Table 4B: Results of Overall Material

[0516]

[0517] Table 4B (continued)

[0518]

[0519] Table 4C: Results of the soluble fraction

[0520]

[0521]

[0522] We have discovered that the borate-free catalysts based on the metallocenes of this invention can produce multiphase copolymers with an improved overall balance of rubber iV / matrix Tm / productivity compared to catalysts based on prior art catalysts (CE1, CE2 metallocenes). In particular, we can produce multiphase copolymers with higher matrix melting points (and therefore higher stiffness) while maintaining the highest iV capacity, thereby improving the stiffness / impact balance of the material.

Claims

1. Metallocene complexes of formula (I) in Mt is either 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 as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, provided that R is present. 2 and R 2’ Not all of them are methyl groups; 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, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 aryl or -OR 31 , where R 31 It is C1-C 10 - Hydrocarbon group, wherein each phenyl group has at least one R 3 Not H and at least one R 4 Not H; R 5 and R 6 Each being independently the same or different from the others is C1-C. 10 Hydrocarbon groups, or they can form C5-C7 carbon rings together with the C atoms they are attached to; 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; X is a σ-ligand; n is 1 to 3, for example 1, 2 or 3, preferably 3; 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 as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, provided that R is present. 2 and R 2’ Not all of them are methyl groups; 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, C7- 20 -Arylalkyl, C7- 20 -alkylaryl, C6- 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - Hydrocarbon group, wherein each phenyl group has at least one R 3 Not H and at least one R 4 Not H; 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.

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; 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 as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl group, provided that R 2 and R 2’ Not all of them are methyl groups; 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, C7- 20 -Arylalkyl, C7- 20 -alkylaryl, C6- 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - Hydrocarbon group, wherein each phenyl group has at least one R 3 Not H and at least one R 4 Not H.

4. The metallocene complex according to any one of claims 1 to 3, 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.

5. The metallocene complex according to claim 4, wherein... Two Rs for each phenyl 3 It is not H, and R is on both phenyl groups. 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and The two R's on the phenyl group 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

6. The metallocene complex according to any one of the preceding claims, wherein R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6 alkyl group; preferably H or a straight-chain C1-C6 alkyl group; preferably H or a straight-chain C1-C4 alkyl group, more preferably H, methyl or ethyl, provided that R 2 and R 2’ Not all of them are methyl.

7. The metallocene complex according to any one of the preceding claims, wherein R 2 and R 2’ One of them is methyl, and the other is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl; preferably a straight-chain or branched C1-C4-alkyl; more preferably methyl or ethyl.

8. The metallocene complex according to any one of claims 1 to 6, wherein R 2 and R 2’ Neither of them are methyl.

9. The metallocene complex according to claim 8, wherein R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

10. The metallocene complex according to any one of the preceding claims, wherein R 1 Each being independently the same or different from the others is C1-C. 10 Hydrocarbon group, preferably C1-C6 alkyl, preferably methyl.

11. The metallocene complex according to claim 10, wherein R 1 They are the same, C1-C. 10 Hydrocarbon group, preferably C1-C6 alkyl, preferably methyl.

12. A polymerization catalyst, comprising, preferably, the following: (i) Metallocene complexes of formula (I); (ii) A catalyst system containing a catalyst containing a group 13 element; as well as (iii) Optional carrier.

13. The polymerization catalyst according to claim 12, wherein the co-catalyst (ii) is an aluminoxane co-catalyst, preferably without any other co-catalyst.

14. The polymerization catalyst according to claim 12 or 13, wherein it is supported on silica.

15. A method for polymerizing propylene, comprising reacting propylene and optionally selected from ethylene or C4-C in the presence of a polymerization catalyst according to any one of claims 12 to 14. 10 The copolymer is polymerized from at least one comonomer of an α-olefin comonomer.

16. A method for preparing a multiphase polypropylene copolymer, comprising: (I) Propylene is bulk polymerized in the presence of the polymerization catalyst according to claims 12 to 14 to form a polypropylene homopolymer matrix; (II) In the presence of the polypropylene homopolymer matrix and the polymerization catalyst and in the gas phase, propylene and ethylene are polymerized to form a multiphase polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber.

17. A method for preparing a multiphase polypropylene copolymer, comprising: (I) Propylene is subjected to bulk polymerization in the presence of the polymerization catalyst according to claims 12 to 14 to form a polypropylene homopolymer; (II) In the presence of the polypropylene homopolymer and the polymerization catalyst and in the gas phase, propylene is polymerized to form a polypropylene homopolymer matrix; (III) In the presence of the polypropylene homopolymer matrix and the polymerization catalyst and in the gas phase, propylene and ethylene are polymerized to form a multiphase polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber (EPR).

18. Indene in formula (II) (II) in The dashed lines represent double bonds present between carbon 1 and 2 or carbon 2 and 3 in the indanyl ring; R 2’ It is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group; R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - hydrocarbon group, wherein at least one R 4 Not H; 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.

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