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-hydrocarbyl 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, a C6-C10-aryl group, a heteroaryl group, or CH2-R21 wherein R21 is H or a C1-C10-hydrocarbyl group; n are independently the same or different from each other, and are integers from 1 to 5; 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 of each phenyl group present is not H and at least one R4 is not H; r < 5 > and R < 6 > are each independently a C1-C10-hydrocarbyl group or form together with an adjacent oxygen atom-O (R < 61 >) m-O-, where R < 61 > is independently a-CH2-,-CHR *-or-C (R *) 2-group, where R * is a C1-C2-alkyl group, and m is an integer from 2 to 4; r 5'and R 6 'are each independently a C1-C10-hydrocarbyl group or form, together with adjacent oxygen atoms, a-O (R 61') m-O-wherein R 61 'is independently a-CH2-,-CHR *-or-C (R *) 2-group wherein R * is a C1-C2-alkyl group and m is an integer from 1 to 4, R7 is H, Me, OMe or C6-C20-aryl group wherein the C6-C20-aryl group is substituted 1 to 5 times by R3 wherein at least one R3 of each said aryl group is not H. (I)

Description

Technical Field

[0001] This disclosure relates to novel indenyl ligands, bis-indenyl ligands comprising said inden, complexes thereof, and catalysts comprising these complexes. This disclosure also relates to the use of novel bis-indenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers (especially copolymers with ethylene) with high activity levels, high molecular weight, and thus low MFR, 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 catalyst systems with different substitution modes, to produce polyethylene and polypropylene.

[0003] WO2007116034 describes C2-symmetric complexes with 5-methoxy and 6-tert-butyl substituents, as well as straight-chain 2-substituents. Such catalysts produce hPP with relatively low melting points (148 to 150 °C).

[0004] WO2018091684 describes a C2-symmetric racemic-Me2Si(2-Me-4-(3,5-Me2Ph)-5-OMe-6-tBu-Ind)2ZrCl2 complex, which produces low Tg values ​​at 150-151 °C. m hPP.

[0005] While these existing catalysts have their advantages, they lack isoselectivity and produce hPP with relatively low melting and crystallization temperatures due to the formation of insertion region defects in the PP chain.

[0006] Therefore, the inventors seek new metallocene catalysts that can provide high selectivity and high molecular weight 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 melt 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 hPP is at least 157°C.

[0007] Surprisingly, it was found that specific modifications of metallocenes, either C2-symmetric or C1-symmetric (preferably C2-symmetric), with the introduction of specific dioxo substituents into the two indene moieties, provided the desired properties.

[0008] Dioxane has previously been disclosed in WO2006097500, which describes complexes containing indene ligands with cyclic substituents having one to four oxygen or sulfur atoms. The only illustrative structure is a C2-symmetric complex with two 8-(4-(tert-butyl)phenyl)-6-methyl-5H-indeno[5,6-d][1,3]dioxane ligands, which was obtained in a very low yield of only 13% and was not tested in propylene homopolymerization. Therefore, its isoselectivity is unknown. Furthermore, despite the low ethylene content (<20 wt%) in the copolymer, it produced a relatively low molecular weight (iV<2) C2C3 copolymer.

[0009] Compared to systems known in the art, when the identified metallocene complex is included in a polymerization catalyst, preferably a supported catalyst system, consisting of a specific class of metallocene complexes combined with an aluminum-containing co-catalyst, the identified novel metallocene complexes exhibit improved polymerization behavior, higher catalyst productivity, and improved performance in the production of propylene homopolymers, propylene random copolymers, and multiphase propylene copolymers. This enables the production of high-Mw propylene-ethylene copolymers, making it ideal for the production of propylene random copolymers, especially propylene-ethylene random copolymers and multiphase propylene copolymers. Compared to prior art catalyst systems, this specific catalyst system offers greater flexibility / freedom in the design of propylene polymers. Summary of the Invention

[0010] One object of this disclosure is to provide new ligands, metallocene complexes, and catalysts resulting therefrom to overcome the aforementioned problems.

[0011] The objective of this disclosure is achieved by a metallocene complex of formula (I), a polymerization catalyst comprising the metallocene complex of formula (I), and optionally a method for polymerizing polypropylene with a comonomer, characterized as described in the independent claim. Preferred embodiments of this disclosure are disclosed in the dependent claims.

[0012] This disclosure is based on the idea of ​​modifying the size and electron-donating ability of substituents at the 5 and 6 positions of the indenyl ligand in metallocene complexes.

[0013] One advantage of this disclosure is that these metallocenes allow for the production of propylene polymers with high selectivity, particularly after MAO activation, to produce polymers with high Tg. m Polypropylene homopolymer (hPP). Attached Figure Description

[0014] In the following, the present disclosure will be described in more detail with reference to the accompanying drawings, in which preferred embodiments are described,

[0015] Figure 1 The relationship between catalyst productivity and the MFR2 of hPP is shown;

[0016] Figure 2 The balance between the MFR2 and melting point of hPP is shown.

[0017] definition

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

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

[0020] It should be noted that straight-chain and branched hydrocarbon groups cannot contain cyclic units. Aliphatic hydrocarbon groups cannot contain aryl rings.

[0021] As used herein and below, the term "heteroaryl" refers to an aromatic monocyclic or bicyclic (preferably monocyclic) group with 5 to 10 ring members, wherein one or more (preferably one) ring members are heteroatoms belonging to groups 14-16 of the periodic table, preferably O, S, or N, and the remaining ring atoms are carbon. As defined in this specification, the heteroaryl group may optionally be coupled with 1 to 3 C1-C2 atoms. 10 - Hydrocarbon substitution.

[0022] The term “heteroatoms of groups 14-16 of the periodic table” includes, for example, Si, N, O, or S.

[0023] As used herein, the term “C4-C8 ring” with the addition of -R'2Si- refers to a cyclic group containing 4 to 8 carbon atoms and one Si atom, including, for example, siliconediyl groups, such as siliconebutane, siliconepentane, or 9-siliconium.

[0024] When it comes to the definition of coordination compounds, the term "halogen" includes fluorine, chlorine, bromine, and iodine groups, especially chlorine or fluorine groups.

[0025] 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.

[0026] 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.

[0027] The numbering of these rings will be evident from the structure shown in this article.

[0028] 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.

[0029] The term “molecular weight” as used in this article refers to weight-average molecular weight Mw, unless otherwise stated.

[0030] 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

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

[0032] Metallocene catalyst complexes

[0033] The complexes of this invention can be asymmetric or symmetric. Asymmetric refers only to the two indenyl ligands forming the metallocene being different, i.e., each indenyl ligand carries a set of substituents with different chemical properties or substituents located at different positions relative to the other indenyl ligand. Symmetrical complexes are based on two identical indenyl ligands.

[0034] The complexes of this invention are chiral, racemic, bridged bis-indenyl metallocenes. The metallocenes of this invention are C2-symmetrical or C1-symmetrical, preferably C2-symmetrical. When they are C1-symmetrical, they still retain pseudo-C2-symmetrical because they maintain C2-symmetrical near the metal center, although not around the ligands. Chemically, during the synthesis of the complexes, racemic and racemic enantiomer pairs (in the case of C2-symmetrical complexes) or trans and cis enantiomer pairs (in the case of C1-symmetrical complexes) are formed. For the purposes of this invention, racemic-trans refers to the two indenyl ligands oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-cis refers to the two indenyl ligands oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the figure below.

[0035]

[0036] racemic trans racemic cis racemic

[0037] The preferred metallocene catalyst complex is in the trans configuration.

[0038] The metallocene complexes of the present invention are preferably used in the form of racemic trans isomers. Therefore, ideally, at least 95%, for example at least 98%, and especially at least 99%, of the metallocene catalyst complexes are in the racemic trans isomer form.

[0039] The metallocene catalyst complex of the present invention requires a combination of two indenyl ligands having a 5,6-dialkoxy or 5,6-carbocyclic ring containing at least two O atoms and a substituted aryl ligand at the 4-position of each indenyl ligand.

[0040] Therefore, the present invention relates to metallocene complexes of formula (I).

[0041] (I)

[0042] in

[0043] Mt is either Zr or Hf;

[0044] X is a σ-ligand;

[0045] 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;

[0046] R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0047] n are independent of each other, either identical or different, and are integers from 1 to 5;

[0048] 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H;

[0049] R 5 and R 6 Each is independently C1-C 10 -Hydrocarbon group or together form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4;

[0050] R 5’ and R 6’ Each is independently C1-C 10 -Hydrocarbon group or together form -O(R) 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4;

[0051] R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

[0052] For the metallocene complex of formula (I) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0053] In the complex of formula (I), Mt is Zr or Hf, preferably Zr.

[0054] 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.

[0055] 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.

[0056] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R 2and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2 Each is either identical or different from the other, and is either methyl or ethyl.

[0057] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0058] Ideally, each n is independently the same or different from each other, and is an integer from 1 to 3, such as 1, 2 or 3.

[0059] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 20 -Aryl or -OR 31 , where R 31 It is a C1-C4-alkyl group; more preferably H, a straight-chain or branched C1-C4-alkyl group, or -OR. 31 , where R 31 It is a C1-C4-hydrocarbon group; or even more preferably, 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 methyl or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0060] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0061] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0062] In addition, it can include R3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0063] 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.

[0064] Advantageously, for all existing phenyl groups, each existing phenyl group has two R groups. 3 Not H, but more preferably R on all present phenyl groups. 3 Same as, e.g., 3',5'-dimethyl.

[0065] For the second indenyl moiety, the two R groups on the phenyl group 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.

[0066] As mentioned above, R 5 and R 6 Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -hydro group) or together to form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4.

[0067] Preferably, R 5 and R 6 Each is independently a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C6-aryl group, or they may be combined to form -O(R) 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*, or -C(R*)2-, where R* is a C1-C2-alkyl group, and m is an integer from 2 to 4, with 2 being the most preferred.

[0068] As mentioned above, R 5’ and R 6’ Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -hydro group) or together to form -O(R) 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4.

[0069] Preferably, R 5’ and 6’ Each is independently a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C6-aryl group, or they may be combined to form -O(R) 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 1 to 4, with 2 being the most preferred.

[0070] Preferably, R 7 It is H or phenyl, wherein the phenyl is reacted with R 3 Substitution 1 to 5 times, wherein at least one R of each phenyl group 3 Not H.

[0071] Therefore, the present invention relates to metallocene complexes of formula (I).

[0072] (I)

[0073] in

[0074] Mt is either Zr or Hf;

[0075] X is a σ-ligand;

[0076] 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;

[0077] R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0078] n are independent of each other, either identical or different, and are integers from 1 to 5;

[0079] 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H;

[0080] R 5 and R 6 Each is independently C1-C 10 -The hydrocarbon group or the adjacent oxygen atom together form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 2 to 4;

[0081] R 5’ and R 6’ Each is independently C1-C 10 -The hydrocarbon group or the adjacent oxygen atom together form -O(R) 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4;

[0082] R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

[0083] For the metallocene complex of formula (I) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0084] In the complex of formula (I), Mt is Zr or Hf, preferably Zr.

[0085] 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.

[0086] 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.

[0087] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2’ Each is either identical or different from the other, and is either methyl or ethyl.

[0088] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0089] Ideally, each n is independently the same or different from each other, and is an integer from 1 to 3, such as 1, 2 or 3.

[0090] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 20 -Aryl or -OR 31 , where R 31 It is a C1-C4-alkyl group; more preferably H, a straight-chain or branched C1-C4-alkyl group, or -OR. 31 , where R 31 It is a C1-C4-hydrocarbon group; or even more preferably, 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 methyl or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0091] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0092] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0093] In addition, it can include R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0094] Therefore, one or two R are preferred. 3 and / or R 4 The group is H. If the two R groups are H, then... 3and / 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.

[0095] Advantageously, for all existing phenyl groups, each existing phenyl group has two R groups. 3 Not H, but more preferably R on all present phenyl groups. 3 Same as, e.g., 3',5'-dimethyl.

[0096] For the second indenyl moiety, the two R groups on the phenyl group 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.

[0097] As mentioned above, R 5 and R 6 Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -Hydrocarbon group) or together with the adjacent oxygen atom to form -O(R 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 2 to 4.

[0098] Preferably, R 5 and R 6 Each is independently a straight-chain C1-C6-alkyl, branched C3-C6-alkyl, or C6-aryl group, or forms a -O(R) group with an adjacent oxygen atom. 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4, with 2 being the most preferred.

[0099] As mentioned above, R 5’ and R 6’ Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -Hydrocarbon group) or together with the adjacent oxygen atom to form -O(R 61’ ) m -O-, where R 61’It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4.

[0100] Preferably, R 5’ and 6’ Each is independently a straight-chain C1-C6-alkyl, branched C3-C6-alkyl, or C6-aryl group, or forms a -O(R) group with an adjacent oxygen atom. 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 1 to 4, with 2 being the most preferred.

[0101] Preferably, R 7 It is H or phenyl, wherein the phenyl is reacted with R 3 Substitution 1 to 5 times, wherein at least one R of each phenyl group 3 Not H.

[0102] Therefore, the present invention relates to metallocene complexes of formula (Ia).

[0103]

[0104] in

[0105] Mt is either Zr or Hf;

[0106] X is a σ-ligand;

[0107] 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;

[0108] R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0109] R 3 and R 4 Each is independently identical or different from the others, and is a 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;

[0110] R 5 and R 6 Each is independently C1-C 10 -Hydrocarbon group or together form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4;

[0111] R 5’ and R 6’ Each is independently C1-C 10 -Hydrocarbon group or together form -O(R) 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4;

[0112] R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 The aryl group is substituted 1 to 5 times, wherein each of the aryl groups has at least two R groups. 3 Not H.

[0113] For the metallocene complexes of formula (Ia) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0114] In the complex of formula (Ia), Mt is Zr or Hf, preferably Zr.

[0115] 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.

[0116] 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-C10 -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.

[0117] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2 Each is independently identical or different from the others, and is either methyl or ethyl. R is preferred. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0118] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is a straight-chain or branched C1-C6-alkyl, or C6- 20 aryl or -OR 31 , where R 31It is a C1-C4-alkyl group; more preferably H, a straight-chain or branched C1-C4-alkyl group, or -OR. 31 , where R 31 It is a C1-C4-hydrocarbon group; or even more preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially methyl or tert-butyl.

[0119] It can have R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0120] Advantageously, on all existing phenyl groups, R 3 Similarly, for two phenyl groups, such as 3',5'-dimethyl.

[0121] Preferably, R 4 Same as, for example, 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0122] As mentioned above, R 5 and R 6 Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -hydro group) or together to form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4.

[0123] Preferably, R 5 and R 6 Each is independently a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C6-aryl group, or they may be combined to form -O(R) 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4.

[0124] As mentioned above, R 5’ and R 6’ Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -hydro group) or together to form -O(R) 61’ ) m-O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4.

[0125] Preferably, R 5’ and 6’ Each is independently a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C6-aryl group, or they may be combined to form -O(R) 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 1 to 4.

[0126] Preferably, R 7 It is H or phenyl, wherein the phenyl is reacted with R 3 Substitution 1 to 5 times, wherein at least one R of each phenyl group 3 Not H.

[0127] Therefore, the present invention relates to metallocene complexes of formula (Ia).

[0128]

[0129] in

[0130] Mt is either Zr or Hf;

[0131] X is a σ-ligand;

[0132] 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;

[0133] R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0134] R 3 and R 4 Each is independently identical or different from the others, and is a straight-chain or branched C1-C6-alkyl, C7-C 20 -Arylalkyl, C7-C 20 -alkylaryl, C6-C 20 -Aryl or -OR31 , where R 31 It is C1-C 10 -Hydrocarbon group;

[0135] R 5 and R 6 Each is independently C1-C 10 -The hydrocarbon group or the adjacent oxygen atom together form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 2 to 4;

[0136] R 5’ and R 6’ Each is independently C1-C 10 -The hydrocarbon group or the adjacent oxygen atom together form -O(R) 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4;

[0137] R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 The aryl group is substituted 1 to 5 times, wherein each of the aryl groups has at least two R groups. 3 Not H.

[0138] For the metallocene complexes of formula (Ia) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0139] In the complex of formula (Ia), Mt is Zr or Hf, preferably Zr.

[0140] 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.

[0141] 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-C10 -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.

[0142] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2 Each is either identical or different from the other, and is either methyl or ethyl.

[0143] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0144] Preferably, R 3 and R 4Each is independently identical or different from the others, and is a straight-chain or branched C1-C6-alkyl, or C6- 20 aryl or -OR 31 , where R 31 It is a C1-C4-alkyl group; more preferably H, a straight-chain or branched C1-C4-alkyl group, or -OR. 31 , where R 31 It is a C1-C4-hydrocarbon group; or even more preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially methyl or tert-butyl.

[0145] It can have R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0146] Advantageously, on all existing phenyl groups, R 3 Similarly, for two phenyl groups, such as 3',5'-dimethyl.

[0147] Preferably, R 4 Same as, for example, 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0148] As mentioned above, R 5 and R 6 Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -Hydrocarbon group) or together with the adjacent oxygen atom to form -O(R 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 2 to 4.

[0149] Preferably, R 5 and R 6 Each is independently a straight-chain C1-C6-alkyl, branched C3-C6-alkyl, or C6-aryl group, or forms a -O(R) group with an adjacent oxygen atom. 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 2 to 4.

[0150] As mentioned above, R 5’ and R6’ Each is independently C1-C 10 - Hydrocarbon group (e.g., straight-chain or branched C1-C) 10 -Hydrocarbon group) or together with the adjacent oxygen atom to form -O(R 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4.

[0151] Preferably, R 5’ and 6’ Each is independently a straight-chain C1-C6-alkyl, branched C3-C6-alkyl, or C6-aryl group, or forms a -O(R) group with an adjacent oxygen atom. 61 ) m -O- group, where R 61 Independently, it is -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group and m is an integer from 1 to 4.

[0152] Preferably, R 7 It is H or phenyl, wherein the phenyl is reacted with R 3 Substitution 1 to 5 times, wherein at least one R of each phenyl group 3 Not H.

[0153] Therefore, the present invention relates to metallocene complexes of formula (Ib).

[0154] (Ib)

[0155] in

[0156] Mt is either Zr or Hf;

[0157] X is a σ-ligand;

[0158] R 1 Each being independently the same or different from the others is C1-C. 20 - A 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;

[0159] R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0160] R3 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H;

[0161] m are independent of each other, either identical or different, and are integers from 2 to 4;

[0162] Each R 61 They may be independently identical or different from each other, and are -CH2-, -CHR*-, or -C(R*)2- groups, wherein R* is a C1-C2-alkyl group;

[0163] R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

[0164] For the metallocene complexes of formula (Ic) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0165] In the complex of formula (Ic), Mt is Zr or Hf, preferably Zr.

[0166] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, halogen, C1-C6-alkoxy, or R', wherein R' is C1-C6-alkyl, phenyl, or benzyl. 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.

[0167] Preferably, R 1 Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group, more preferably C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -Arylalkyl, C6-C 10 -Aryl or C7-C10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, or even more preferably two Rs 1 All are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In one embodiment, each R... 1 Independently identical or different from each other, is arbitrarily determined by C1-C. 10 -alkoxy-substituted C1-C 10 -alkyl group. Preferably two R groups. 1 The groups are identical. Most preferably, the two R groups are identical. 1 They are all methyl groups.

[0168] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2 Each is either identical or different from the other, and is either methyl or ethyl.

[0169] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0170] Preferably, R 3 and R 4 Each is independently the same as 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 R31 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.

[0171] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0172] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0173] In addition, it can include R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0174] Therefore, it is preferable that one or both R3 and / or R4 groups are H. If both R... 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 R3 and / or R4 groups are preferably in the meta position.

[0175] Advantageously, for all existing phenyl groups, each existing phenyl group has two R groups. 3 Not H, but more preferably R on all present phenyl groups. 3 Same as, e.g., 3',5'-dimethyl.

[0176] For the second indenyl moiety, the two R groups on the phenyl group 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.

[0177] Preferably, each m is independently the same or different from each other (preferably the same), and is an integer from 2 to 3, most preferably 2.

[0178] Preferably, each R61 Independently, it is -CH2-, -CHR*-, or -C(R*)2, wherein R* is a methyl group; more preferably, each R 61 It is -CH2-.

[0179] Preferably, R 7 It is H or phenyl, wherein the phenyl is reacted with R 3 Substitution 1 to 5 times, wherein at least one R of each phenyl group 3 Not H.

[0180] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ic).

[0181] (Ic)

[0182] in

[0183] Mt is either Zr or Hf;

[0184] X is a σ-ligand;

[0185] R 1 Each being independently the same or different from the others is C1-C. 20 - A 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;

[0186] R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0187] 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 at least one R 3 Not H and at least one R 4 Not H;

[0188] m are independent of each other, either identical or different, and are integers from 2 to 4;

[0189] Each R 61They may be independently identical or different from each other, and are -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group;

[0190] For the metallocene complexes of formula (Ic) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0191] In the complex of formula (Ic), Mt is Zr or Hf, preferably Zr.

[0192] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, halogen, C1-C6-alkoxy, or R', wherein R' is C1-C6-alkyl, phenyl, or benzyl. 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.

[0193] 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.

[0194] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2 Each is either identical or different from the other, and is either methyl or ethyl.

[0195] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0196] Preferably, R 3 and R 4 Each is independently the same as 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 the same as or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, wherein at least one of them is R. 3 Not H and at least one R 4 Not H.

[0197] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0198] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0199] In addition, it can include R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4The benzene ring of the substituent has different substitution modes.

[0200] 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 groups are preferably located at the meta position.

[0201] Advantageously, the two R's on the phenyl group 3 Not H, R is preferred 3 Same as, e.g., 3',5'-dimethyl.

[0202] For the second indenyl moiety, the two R groups on the phenyl group 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.

[0203] Preferably, each m is independently the same or different from each other (preferably the same), and is an integer from 2 to 3, most preferably 2.

[0204] Preferably, each R 61 Independently, it is -CH2-, -CHR*-, or -C(R*)2, wherein R* is a methyl group; more preferably, each R 61 It is -CH2-.

[0205] From another perspective, the present invention provides a metallocene catalyst complex of formula (Id).

[0206] (Id)

[0207] in

[0208] Mt is either Zr or Hf;

[0209] X is a σ-ligand;

[0210] R 1 Each being independently the same or different from the others is C1-C. 20 - A 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;

[0211] R 2 and R 2’Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group;

[0212] 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;

[0213] m are independent of each other, either identical or different, and are integers from 2 to 4;

[0214] Each R 61 They may be independently identical or different from each other, and are -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group;

[0215] For the metallocene complexes of formula (Id) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0216] In the complex of formula (Id), Mt is Zr or Hf, preferably Zr.

[0217] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, halogen, C1-C6-alkoxy, or R', wherein R' is C1-C6-alkyl, phenyl, or benzyl. 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.

[0218] 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.

[0219] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group; even more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2 Each is either identical or different from the other, and is either methyl or ethyl.

[0220] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl group or a branched C3-C6-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0221] Preferably, R 3 and R 4 Each is independently the same as 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 31It 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.

[0222] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0223] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0224] In addition, it can include R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The three benzene rings of the substituent have different substitution patterns.

[0225] 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.

[0226] Advantageously, for two phenyl groups, each phenyl group has two R groups. 3 Not H, but more preferably R on the two phenyl groups. 3 Same as, e.g., 3',5'-dimethyl.

[0227] For the second indenyl moiety, one or two R groups 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.

[0228] Preferably, each m is independently the same or different from each other (preferably the same), and is an integer from 2 to 3, most preferably 2.

[0229] Preferably, each R 61 Independently, it is -CH2-, -CHR*-, or -C(R*)2, wherein R* is a methyl group; more preferably, each R 61 It is -CH2-.

[0230] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ie).

[0231] (Ie)

[0232] in

[0233] Mt is either Zr or Hf;

[0234] X is a σ-ligand;

[0235] R 1 Each being independently the same or different from the others is C1-C. 20 - A 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;

[0236] 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;

[0237] 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H;

[0238] R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

[0239] For the metallocene complexes of formula (Ie) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0240] In the complex of formula (Ie), Mt is Zr or Hf, preferably Zr.

[0241] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, halogen, C1-C6-alkoxy, or R', wherein R' is C1-C6-alkyl, phenyl, or benzyl. 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.

[0242] 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.

[0243] 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-C3-alkyl or a branched C3-alkyl, such as methyl, ethyl, n-propyl, isopropyl; more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2’ Each is either identical or different from the other, and is either methyl or ethyl.

[0244] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0245] Preferably, R 3 and R 4 Each is independently the same as 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.

[0246] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0247] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0248] In addition, it can include R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0249] 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 R3 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.

[0250] Advantageously, for all existing phenyl groups, each existing phenyl group has two R groups. 3 Not H, but more preferably R on all present phenyl groups. 3 Same as, e.g., 3',5'-dimethyl.

[0251] For the second indenyl moiety, the two R groups on the phenyl group 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.

[0252] Preferably, R 7 It is H or phenyl, wherein the phenyl is reacted with R 3 Substitution 1 to 5 times, wherein at least one R of each phenyl group 3 Not H.

[0253] From another perspective, the present invention provides metallocene catalyst complexes of formula (If).

[0254] (If)

[0255] in

[0256] Mt is either Zr or Hf;

[0257] X is a σ-ligand;

[0258] R 1 Each being independently the same or different from the others is C1-C. 20 - A 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;

[0259] 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;

[0260] 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-C20 -alkylaryl, C6-C 20 -Aryl or -OR 31 , where R 31 It is C1-C 10 - hydrocarbon group, wherein at least one R 3 Not H and at least one R 4 Not H.

[0261] For the metallocene complexes of formula (Ie) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0262] In the complex of formula (Ie), Mt is preferably Zr or Hf, with Zr being more preferred.

[0263] Each X is a σ ligand. Preferably, each X is independently the same or different from each other and is H, halogen, C1-C6-alkoxy, or R', wherein R' is C1-C6-alkyl, phenyl, or benzyl. 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.

[0264] 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.

[0265] Preferably, 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, a straight-chain C1-C3-alkyl or a branched C3-alkyl, such as methyl, ethyl, n-propyl, isopropyl; more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2’ Each is either identical or different from the other, and is either methyl or ethyl.

[0266] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0267] Preferably, R 3 and R 4 Each is independently the same as 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.

[0268] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0269] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0270] In addition, it can include R 3 and R 4Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The benzene ring of the substituent has different substitution modes.

[0271] 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 groups are preferably located at the meta position.

[0272] Advantageously, the two R's on the phenyl group 3 Not H, R is preferred 3 Same as, e.g., 3',5'-dimethyl.

[0273] For the second indenyl moiety, the two R groups on the phenyl group 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.

[0274] From another perspective, the present invention provides a metallocene catalyst complex of formula (Ig).

[0275] (Ig)

[0276] in

[0277] Mt is either Zr or Hf;

[0278] X is a σ-ligand;

[0279] R 1 Each being independently the same or different from the others is C1-C. 20 - A 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;

[0280] 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;

[0281] R 3 and R 4Each 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.

[0282] For the metallocene complexes of formula (Ig) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0283] In the complex of formula (Ig), Mt is Zr or Hf, preferably Zr.

[0284] 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.

[0285] 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.

[0286] 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-C3-alkyl or a branched C3-alkyl, such as methyl, ethyl, n-propyl, isopropyl; more preferably, R 2 and R 2’ Each is independently identical or different from the others, and is a straight-chain C1-C3-alkyl group; most preferably, R 2 and R 2’ Each is either identical or different from the other, and is either methyl or ethyl.

[0287] Preferred R 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group, more preferably R. 2 and R 2’ Same, and is CH2-R 21 , where R 21 It is H or a straight-chain C1-C3-alkyl group. Most preferably, R 2 and R 2’ They are all methyl or all ethyl.

[0288] Preferably, R 3 and R 4 Each is independently the same as or different from the others, and is H, straight-chain or branched C1-C6-alkyl, or C6- 20 Aryl; more preferably H, straight-chain or branched C1-C4-alkyl, or -OR 31 , where R 31 It is a C1-4 hydrocarbon group; even more preferably, each R 3 and R 4 Each is 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.

[0289] Preferably, the R of each benzene ring 3 and R 4 The substituents are located at the 3', 4' and / or 5' positions of the ring, with the 1' position connected to the indene ring.

[0290] For example, the benzene ring can be substituted only at the para position (i.e., the 4' position), such as 4'-tert-butylphenyl, or disubstituted at the meta position (i.e., the 3' and 5' positions), such as 3',5'-dimethylphenyl or 3',5'-ditert-butylphenyl.

[0291] In addition, it can include R 3 and R 4 Each benzene ring of the substituent has the same substitution pattern, or has R 3 and R 4 The three benzene rings of the substituent have different substitution patterns.

[0292] 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.

[0293] Advantageously, for two phenyl groups, each phenyl group has two R groups. 3 Not H, but more preferably R on the two phenyl groups. 3 Same as, for example, 3',5'-dimethyl or 4'-tert-butyl.

[0294] For the second indenyl moiety, one or two R groups 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.

[0295] Specific metallocene catalyst complexes applicable to this invention include:

[0296] Dimethylsilanediyl-bis[9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride Dimethylsilanediyl-bis[9-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride Dimethylsilanediyl[5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydroindo[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydroindo[5,6-b][1,4]dioxin-6-yl]zirconium dichloride

[0297] synthesis

[0298] The ligands required to form the complexes of this invention and the resulting catalysts can be synthesized by any method, and skilled organic chemists can devise a variety of synthetic schemes to produce the necessary ligand materials. For example, WO2007 / 116034 discloses the necessary chemical schemes. Synthetic schemes can also typically be found in WO2002 / 02576, WO2011 / 135004, WO2012 / 084961, WO2012 / 001052, WO2011 / 076780, WO2015 / 158790, WO2018 / 122134, WO2019 / 179959, and WO2012 / 058740. The Examples section also provides ample guidance for those skilled in the art.

[0299] Polymerization catalyst

[0300] From another perspective, the present invention provides a polymerization catalyst comprising, preferably substantially, the following:

[0301] (i) Metallocene complexes of formula (I);

[0302] (ii) a catalyst system comprising a catalyst containing a Group 13 element; and

[0303] (iii) Optional carrier.

[0304] co-catalyst

[0305] To form an active catalytic material, a co-catalyst well known in the art is typically required. Co-catalysts comprising one or more Group 13 metal compounds (such as organoaluminum, organoboron, and / or borate compounds used for activating metallocene catalysts) are suitable for this invention. Preferably, only aluminum-containing co-catalysts (such as organoaluminum compounds used for activating metallocene catalysts) are used in this invention.

[0306] 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.

[0307] Preferably, only aluminum-containing cocatalysts (such as organoaluminum compounds used to activate metallocene catalysts) are used in this invention.

[0308] In a preferred aspect of the invention, a cocatalyst system consisting essentially of an aluminoxane cocatalyst, preferably an aluminoxane cocatalyst, is advantageously used in combination with the metallocene catalyst complex defined above.

[0309] 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.

[0310] The appropriate amount of catalyst will be well known to those skilled in the art.

[0311] Preferably, the amount of co-catalyst is selected to achieve a molar ratio below the defined range.

[0312] 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.

[0313] 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) feed to metallocene metal ions (Mt) (preferably zirconium), B / Mt, is 0.5:1 to 2:1.

[0314] Aluminoxane co-catalyst

[0315] Aluminoxane co-catalysts can be one of formula (A):

[0316] (A)

[0317] Where n is typically 6 to 20, and R has the following meanings.

[0318] 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).

[0319] 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.

[0320] Boron-containing cocatalyst

[0321] According to the present invention, the aluminoxane cocatalyst can be used in combination with the boron-containing cocatalyst.

[0322] 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.

[0323] 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.

[0324] Meaningful boron-containing cocatalysts include those compounds of formula (B).

[0325] BY3 (B)

[0326] Where Y is the same or different, and is a hydrogen atom, C1- 10 - Haloalkyl or C6-C 20 - Halogenated aryl groups or fluorine, chlorine, bromine or iodine.

[0327] 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).

[0328] 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).

[0329] 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.

[0330] Tris(pentafluorophenyl)borane is particularly preferred.

[0331] However, borates, i.e., compounds containing borate anions, are preferred. These compounds have the formula (C):

[0332] Z4B –- W + (C)

[0333] Wherein Z is a substituted phenyl derivative, and the substituent is a halo-C1-C6-alkyl or halogen; W + It is a cationic counterion.

[0334] Preferably, the substituent of Z is fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0335] 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).

[0336] Preferred ionic compounds that can be used according to the present invention include:

[0337] Tributylammonium tetra(pentafluorophenyl)borate

[0338] Tributylammonium tetra(trifluoromethylphenyl)borate

[0339] Tributylammonium tetra(4-fluorophenyl)borate,

[0340] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid

[0341] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid

[0342] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0343] N,N-di(propylammonium) tetra(pentafluorophenyl)borate,

[0344] di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate,

[0345] Triphenylcarbomon tetra(pentafluorophenyl)borate

[0346] Or ferrocene tetra(pentafluorophenyl)borate.

[0347] Preferred is triphenylcarbium tetra(pentafluorophenyl)borate,

[0348] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0349] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0350] The preferred option is triphenylcarbium tetra(pentafluorophenyl)borate.

[0351] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0352] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0353] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0354] Catalyst manufacturing

[0355] The metallocene complexes described above are used in combination with suitable cocatalysts as described below.

[0356] 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.

[0357] 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 EP1828266, WO2020 / 239598, and WO2020 / 239603.

[0358] Alternatively, no support may be used at all. Such catalysts can be prepared in solution (e.g., in an aromatic solvent such as toluene) by contacting a metallocene (as a solid or as a solution) with a co-catalyst (e.g., methylaluminoxane, borane, or borate pre-dissolved in an aromatic solvent), or by sequentially adding the dissolved catalyst components to a polymerization medium.

[0359] In one aspect, no external support is used, but the catalyst still exists in solid particulate form. Therefore, no external support material, such as an inert organic or inorganic support (e.g., silica as described above), is used, but the solid catalyst is prepared using an emulsion curing method. Such catalysts can be prepared as described, for example, in WO 2003 / 051934, WO 2014 / 060540, and WO 2019 / 179959.

[0360] The catalyst system of the present invention is preferably used in a supported form. The particulate support material used is an inorganic porous support, such as silica, alumina, or a mixed oxide (e.g., silica-alumina), especially silica.

[0361] Silica carrier is preferred.

[0362] 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.

[0363] 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.

[0364] The average pore size of inorganic porous supports (e.g., silica supports) can range from 10 to 100 nm, and the pore volume can range from 1 to 3 mL / g. The pore diameter of inorganic porous supports (e.g., silica supports) can range from 20 to 40 nm.

[0365] 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.

[0366] 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.

[0367] The use of these carriers is common practice in this field.

[0368] 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).

[0369] The polymerization catalyst of the present invention can be produced by methods such as those described in WO2020 / 239603 or WO2020 / 239598.

[0370] Polymerization catalysts containing such metallocenes can be produced by a method comprising the following steps:

[0371] 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.

[0372] 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;

[0373] P1-c) Add the solution obtained in step b) to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0374] P1-d) The supported catalyst system thus obtained is dried.

[0375] 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.

[0376] In a preferred aspect of the invention, the method includes:

[0377] 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.

[0378] P2-b) Dissolve the metallocene in a hydrocarbon solvent, optionally adding a methylaluminoxane cocatalyst to the hydrocarbon solvent, 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;

[0379] P2-c) Add the metallocene solution to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0380] P2-d) The supported catalyst system thus obtained is dried.

[0381] 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%.

[0382] 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).

[0383] polymerization

[0384] 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, propylene-ethylene, and propylene-butene 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.

[0385] 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.

[0386] In a preferred aspect, the present invention relates to a method for preparing a multiphase polypropylene copolymer (hPP), comprising:

[0387] (I) Propylene is bulk polymerized in the presence of a polymerization catalyst as defined herein to form a polypropylene homopolymer matrix;

[0388] (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.

[0389] In another aspect, the present invention relates to a method for preparing a multiphase polypropylene copolymer, comprising:

[0390] (I) Propylene is subjected to bulk polymerization in the presence of a polymerization catalyst as defined herein to form a polypropylene homopolymer;

[0391] (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;

[0392] (III) In the presence of the matrix and the polymerization catalyst and in the gas phase, propylene and ethylene are polymerized to form a multiphase polypropylene copolymer comprising a homopolymer matrix and ethylene propylene rubber (EPR).

[0393] 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.

[0394] 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.

[0395] 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.

[0396] 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.

[0397] 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).

[0398] 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.

[0399] 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.

[0400] Furthermore, the random copolymerization behavior of the metallocene catalyst of the present invention shows a reduced tendency to transfer to the ethylene chain.

[0401] polymer

[0402] A feature of this invention is that the claimed catalyst is capable of forming propylene polymers with high molecular weights. These characteristics can be achieved at commercially meaningful polymerization temperatures (e.g., 60°C or higher, such as 60°C to 90°C). The polydispersity index (Mw / Mn) of the polymer depends on the polymerization conditions in each reactor and can be from 2.0 to 7.0. In a particular embodiment, the propylene polymer obtained using the catalyst of this invention has a narrow polydispersity index (Mw / Mn) of 2.0 to 4.0.

[0403] propylene homopolymer

[0404] Depending on the use and amount of hydrogen used as a Mw modifier, the Mw (weight average molecular weight) value of the propylene homopolymer prepared from the catalyst system containing the metallocene of the present invention can be in the range of 40 to 2000 kg / mol, preferably in the range of 50 to 1500 kg / mol. The catalyst of the present invention is capable of forming polypropylene homopolymers with high melting points. In a preferred embodiment, the propylene homopolymer formed by the method of the present invention has a melting point above 155°C, preferably above 157°C. propylene homopolymers with melting points up to 158°C or even up to 160°C can be formed.

[0405] propylene copolymer

[0406] Metallocene compounds prepared by the present invention containing ethylene or C4-C 10 Propylene copolymers of α-olefin comonomers can be prepared with high productivity and low solubility.

[0407] 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.

[0408] The invention will now be described with reference to the following non-limiting examples.

[0409] experiment

[0410] Measurement methods

[0411] Determination of Al, B and Zr (ICP method)

[0412] 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 steel secondary container equipped with an air inlet. The contents of the boat were then rinsed into a 20 mL Xpress microwave oven container with 5 mL of concentrated nitric acid (65%). The sample was then microwave-assisted digested at 150 °C for 35 min using a MARS 6 laboratory microwave apparatus. The digested sample was allowed to cool for at least 4 h and then transferred to a 100 mL glass volumetric flask. A standard solution containing 1000 mg / L LY and Rh (0.4 mL) was added. The flask was then filled with distilled water and shaken thoroughly. The solution was filtered through a 0.45 µm nylon syringe filter and analyzed using a Thermo iCAP 6300 ICP-OES and iTEVA software.

[0413] The instrument was calibrated using a blank solution (5% HNO3 solution) and six standard solutions (containing 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L of Al, B, Hf, Mg, Ti, and Zr, respectively, in a 5% HNO3 distilled aqueous solution). However, not every calibration point was used for every wavelength. Each calibration solution contained 4 mg / L of LY and Rh standards. Al at 394.401 nm was calibrated using the following calibration points: blank solution, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L. The calibration method for Al 167.079 nm is consistent with that for Al 394.401 nm, but 100 mg / L is excluded, and Zr 339.198 nm is calibrated using blank solution, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L standard solutions. Curve fitting and 1 / concentration weighting are used for the calibration curve.

[0414] 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.

[0415] 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.

[0416] 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.

[0417] Catalyst activity

[0418] Catalyst activity is calculated based on the following formula:

[0419]

[0420] Catalyst productivity is calculated based on the following formula:

[0421]

[0422] Polymer powder bulk density

[0423] Instrument: Electronic balance: measuring range 0.1g-11000g

[0424] Glass graduated cylinder: Volume = Maximum 250ml

[0425] Plastic medicine spoon: Volume = 125ml

[0426] Plastic funnel: D=105mm

[0427] 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.

[0428] Calculation: Polymer mass (g) / Measurement volume (ml)

[0429] XS

[0430] The xylene soluble fraction (XS) was determined according to ISO 16152 as follows: 2.5 ± 0.1 g of polymer was dissolved in 250 ml of o-xylene under reflux and continuous stirring in a nitrogen atmosphere. After 30 minutes, the solution was 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 was then filtered through filter paper. To determine the xylene soluble content, an equal fraction of the filtrate (100 ml) was taken. This fraction was evaporated in a nitrogen stream, and the residue was vacuum dried at 100 °C until constant weight was achieved.

[0431] The soluble fraction (weight percentage) of xylene can then be determined as follows:

[0432] XS% = (100 xm 1 xv 0 ) / (m 0 xv 1 ),

[0433] 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.

[0434] 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.

[0435] GPC: Average molecular weight, molecular weight distribution, and polydispersity index (Mn, Mw, Mw / Mn)

[0436] The molecular weight distribution (MWD) and corresponding average molecular weight (M) of polymer samples were determined by gel permeation chromatography (GPC) at 160 °C. n M w M v and M z All samples were placed in a low M... wIntegrate until the third-to-last calibration point of the calibration curve (PS = 1820 g / mol ~ 1340 g / mol PP equivalent).

[0437] A high-temperature GPC was used, 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). 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. The temperature was 160 °C, and the flow rate was constant at 1 mL / min. 200 μL of sample solution was injected for each analysis. All samples were prepared by dissolving 8.0–10.0 mg of polymer in 10 mL (at 160 °C) of stabilized TCB (same as the mobile phase), and continuously gently agitated 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.

[0438]

[0439] Where: w 25 (Polymer weight) and V 25 (Volume of TCB at 25℃).

[0440] 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:

[0441] K PS = 19 x 10 -5 ml / g, α PS = 0.655

[0442] K PP = 39 x 10 -5 ml / g, α PP= 0.725

[0443] Third-order polynomial fitting was used to fit the calibration data.

[0444] 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.

[0445] The average molecular weight (M) is determined using the following formula. n M w M v and M z Molecular weight distribution (MWD) and its width (derived from the polydispersity index PD=M) w / M n (where M) n It is the number average molecular weight, M w (This is a description of weight-average molecular weight).

[0446] (1)

[0447] (2)

[0448] (3)

[0449] (4)

[0450] DSC

[0451] 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.

[0452] melt flow rate

[0453] Melt flow rate (MFR) is determined according to ISO 1133 and expressed in g / 10 min. MFR is an indicator of polymer flowability and therefore also an indicator of processability. 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)).

[0454] Comonomer content determined by FTIR

[0455] Quantitative infrared (IR) spectroscopy was used to estimate the C2 content of the copolymer by calibrating the primary method (NMR spectroscopy).

[0456] 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%.

[0457] 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.

[0458] 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:

[0459] Equation 1

[0460] Here, C1 is the slope of the calibration curve, where 0.96 > C1 > 1, and the intercept is -0.02 > C0 > 0.06. Use the usual determination confidence level (COD) or R0. 2 Assess calibration quality. COD is approximately 0.998.

[0461] NMR

[0462] 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. 13 Recordings were taken using a C-optimized 10 mm selective excitation probe, with all pneumatic devices using nitrogen. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). This device 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{ 1The 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.

[0463] 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.

[0464] 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). No characteristic signals corresponding to other types of regional irregularities were 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].

[0465] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the ethylene content and isotactic regularity of copolymers.

[0466] 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. 13Recorded 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.

[0467] 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. In the absence of a NOE, standard single-pulse excitation was employed 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.

[0468] Quantitative 13 C{ 1 The 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.

[0469] 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.

[0470] 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:

[0471] fE = (E / (P + E))

[0472] 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.

[0473] The molar percentage introduced by the comonomer is calculated from the mole fraction:

[0474] E [mol%] = 100 * fE

[0475] The weight percentage of comonomers introduced is calculated as a mole fraction:

[0476] E [wt%] = 100 * ( fE * 28.06 ) / ( (fE * 28.06) + ((1-fE) * 42.08) )

[0477] The isotactic regularity of the copolymer was determined according to known methods, for example as described in Macromolecules 2005, Vol. 38, pp. 3054-3059.

[0478] Crystallinity tester method

[0479] 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).

[0480] The IR4 detector is a multi-wavelength detector that detects IR absorbance at two different wavelength bands (CH3 and CH2) and is used 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.% (from...). 13 EP copolymer calibration (measured by C-NMR).

[0481] 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%.

[0482] 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).

[0483] Calibration was performed using a variety of commercial EP / PP copolymers with iV = 2-4 dL / g.

[0484] 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.

[0485] 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).

[0486] Metallocene synthesis

[0487] Comparison of the synthesis of metallocene 1 (CM1)

[0488] CM1 was prepared as described in WO2018091684 MC-IE1.

[0489] Comparison of the synthesis of metallocene 2 (CM2)

[0490] 4-(3,5-Dimethylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indah

[0491]

[0492] A THF solution of 3,5-dimethylphenyl magnesium bromide (1.0 M, 200 mL, 200 mmol, 1.4 equivalences) was added to a mixture of 2.0 g (2.56 mmol, 1.8 mol.%) NiCl2(PPh3)IPr and 40.0 g (142.3 mmol) 4-bromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indigo. The resulting solution was refluxed for 3 h, then cooled to room temperature, and 400 mL of water was added, followed by 500 mL of 1.0 M HCl solution. The mixture was then extracted with 600 mL of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 2 × 100 mL of dichloromethane. The combined organic extracts were evaporated to dryness to give a slightly green oily substance. The product was separated by rapid chromatography on silica gel 60 (40–63 µm; eluent: hexane-dichloromethane = 2:1, vol., then 1:2, vol.). This procedure yielded 43.02 g (99%) of 4-(3,5-dimethylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indigo, as a colorless, viscous oil, a mixture of two diastereomers.

[0493] C 22 H 26 Analytical values ​​for O: C, 86.23; H, 8.55. Measured values: C, 86.07; H, 8.82.

[0494] 1¹H NMR (CDCl₃), cis isomer: δ 7.21 (s, 1H), 6.94 (br.s, 1H), 6.90 (br.s, 2H), 4.48 (d, J = 5.5 Hz, 1H), 3.43 (s, 3H), 2.94 (t, J = 7.5 Hz, 2H), 2.87–2.65 (m, 3H), 2.63–2.48 (m, 2H), 2.33 (s, 6H), 2.02 (quin, J = 7.5 Hz, 2H), 1.07 (d, J = 6.7 Hz, 3H); trans isomer: δ 7.22 (s, 1H), 6.94 (br.s, 1H), 6.89 (br.s, 2H). 4.38 (d, J = 4.0 Hz, 1H), 3.48 (s, 3H), 3.06 (dd, J = 16.0Hz, J = 7.5 Hz, 1H), 2.93 (t, J = 7.3 Hz, 2H), 2.75 (td, J = 7.3 Hz, J = 3.2Hz, 2H), 2.51-2.40 (m, 1H), 2.34 (s, 6H), 2.25 (dd, J = 16.0 Hz, J = 5.0 Hz, 1H), 2.01 (quin, J = 7.3 Hz, 2H), 1.11 (d, J = 7.1 Hz, 3H). 13 C{ 1 ¹H NMR (CDCl₃), cis isomers: δ 142.69, 142.49, 141.43, 139.97, 139.80, 137.40, 135.46, 128.34, 126.73, 120.09, 86.29, 56.76, 39.43, 37.59, 33.11, 32.37, 25.92, 21.41, 13.73; trans isomers: δ 143.11, 142.72, 140.76, 139.72, 139.16, 137.37, 135.43, 128.29, 126.60, 119.98, 91.53, 56.45, 40.06, 37.65, 33.03, 32.24, 25.88, 21.36, 19.36.

[0495] 4-(3,5-Dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indah

[0496]

[0497] TsOH (200 mg) was added to a solution of 4-(3,5-dimethylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indane (43.02 g, 140.4 mmol) in 600 mL toluene, and the resulting solution was refluxed for 15 min using a Dean-Stark separatory water separator. After cooling to room temperature, the reaction mixture was washed with 200 mL of 10% NaHCO3. The organic layer was separated, and the aqueous layer was extracted with 300 mL of dichloromethane. The combined organic extracts were evaporated to dryness to give a light orange oil. The product was separated by rapid chromatography on silica gel 60 (40–63 µm; eluent: hexane, then hexane-dichloromethane = 10:1, vol.). The procedure yielded 35.66 g (93%) of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indigo, a pale yellow oil that spontaneously solidified to form white lumps.

[0498] C 21 H 22 Analytical values: C, 91.92; H, 8.08. Measured values: C, 91.78; H, 8.25.

[0499] 1 H NMR (CDCl3): δ 7.09 (s, 1H), 6.98 (br.s, 2H), 6.96 (br.s, 1H), 6.44(m, 1H), 3.14 (s, 2H), 2.95 (t, J = 7.3 Hz, 2H), 2.76 (t, J = 7.3 Hz, 2H), 2.35 (s, 6H), 2.07 (s, 3H), 2.02 (quin, J = 7.3 Hz, 2H). 13 C{ 1 H} NMR (CDCl3): δ145.46, 144.71, 142.81, 140.17, 139.80, 137.81, 137.50, 134.33, 128.35,127.03, 126.48, 114.83, 42.00, 33.23, 32.00, 25.87, 21.38, 16.74.

[0500] Racemic-dimethylsilanediyl-bis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride

[0501]

[0502] At -50℃, n A hexane solution of BuLi (2.5 M, 31.5 mL, 78.75 mmol) was added in a single step to a solution of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indane (21.58 g, 78.64 mmol) in 500 mL of diethyl ether. The mixture was stirred at room temperature for 3 h, then the resulting pale yellow suspension was cooled to -50 °C, and 250 mg of CuCN was added. The resulting mixture was stirred at -25 °C for 15 min, and then dichlorodimethylsilane (5.08 g, 39.36 mmol) was added in a single step. The mixture was stirred overnight at ambient temperature, then filtered through a glass frit (G4) funnel, and the resulting pale yellow solution was used for the next step without further purification. 1 1H NMR spectroscopy revealed the presence of the target bis[4-(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl]dimethylsilane (a mixture of approximately 3:2 stereoisomers) and approximately 10% of the initiating 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indarsen. n A hexane solution of BuLi (2.5 M, 31.5 ml, 78.75 mmol) was added in a single step to a solution thus obtained and cooled to -50 °C containing 39.32 mmol (assuming the quantitative yield from the previous step) of bis[4-(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl]dimethylsilane. The mixture was stirred overnight at room temperature. The resulting pale yellow suspension was cooled to -50 °C, and ZrCl4 (9.17 g, 39.35 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give an orange suspension. The mixture was evaporated to dryness, and the residue was treated with 250 ml of hot toluene. The mixture was filtered hot through a glass frit funnel (G4). The filtrate was evaporated to 130 ml, and the resulting suspension was heated to dissolve the precipitate. The orange powder precipitated overnight from the solution at room temperature was collected and dried under vacuum. The procedure yielded 9.2 g of pure racemic dimethylsilanediylbis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride as a 1:1 solvate with toluene. The mother liquor was evaporated to approximately 80 ml. The orange powder precipitated overnight from this solution at room temperature was collected and dried under vacuum. This procedure yielded 0.12 g of racemic zirconium decanoate as a 1:1 solvate with toluene.

[0503] Racemic dimethylsilanediyl-bis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride forms a 1:1 solvate with toluene:

[0504] C 44 H 46 Analytical values ​​of Cl2SiZr*C7H8: C, 71.46; H, 6.35. Measured values: C, 71.69; H, 6.50.

[0505] 1 H NMR (CDCl3): δ 7.39 (s, 2H), 7.27-7.10 (m, 4H), 6.93 (s, 2H), 6.68(s, 2H), 3.12-2.73 (m, 8H), 2.32 (s, 12H), 2.21 (s, 6H), 2.08-1.89 (m, 4H), 1.27 (s, 6H). 13 C{ 1 H} NMR (CDCl3,): δ 144.51, 142.89, 138.26, 137.57, 134.30,132.88, 132.39, 128.84, 126.93, 126.70, 121.99, 118.01, 81.33, 33.18, 32.10,26.51, 21.36, 18.33, 2.78.

[0506] Comparison of the synthesis of metallocene 3 (CM3)

[0507] 4,8-Bis(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indah

[0508]

[0509] 36.3 g (105 mmol) of 4,8-dibromo-2-methyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one, 35.6 g (237 mmol, 2.25 equivalents) of 3,5-dimethylphenylboronic acid, 60.4 g (570 mmol) of Na2CO3, and 1.07 g (2.09 mmol, 2 mol.%) of Pd(P tA mixture of Bu3)2, 275 ml of water, and 680 ml of 2-methyltetrahydrofuran was refluxed for 7 h. After cooling to room temperature, the organic layer was separated, dried with K2CO3, and filtered through a silica gel 60 short pad (40–63 µm). The resulting solution was ready for further use without further purification. NaBH4 (10.0 g, 264 mmol) was added to this solution cooled to 5 °C. Then, 100 ml of methanol was added dropwise to the mixture over approximately 3 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 1000 ml of dichloromethane and 1000 ml of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 ml of dichloromethane. The combined organic extracts were passed through a silica gel 60 pad (40–63 µm; eluent: dichloromethane) (~30 ml) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a slightly brown oil. TsOH (500 mg) was added to this oil in 500 ml of toluene. The mixture was refluxed using a Dean-Stark separator for 10 min, then cooled to room temperature in a water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 400 ml of dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The residue was dissolved in 600 ml of a 1:1 mixture of n-hexane and dichloromethane, and the resulting solution was passed through a 600 ml column packed with silica gel 60 (40–63 µm; eluent: n-hexane / dichloromethane = 1:1, vol.) to remove excess boric acid and residual palladium black. The combined organic eluents (2 × 500 ml) were evaporated to dryness, and the residue was milled with 100 ml of n-hexane. The precipitate formed by (G3) was filtered off, washed with 3 × 30 ml of n-hexane, and then dried under vacuum to obtain 35.93 g (90.0%) of 4,8-bis(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indaragenin as a white powder. The mother liquor was evaporated to dryness, ground with 20 ml of n-hexane, and the precipitate formed by (G3) was filtered off. The filter cake was washed with 3 × 10 ml of n-hexane to obtain another 1.02 g of 4,8-bis(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indaragenin.

[0510] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarin-1-yl]chlorodimethylsilane

[0511]

[0512] Will nA hexane solution of BuLi (2.43 M, 10.3 mL, 25.0 mmol) was added in a single addition to a suspension of 4,8-bis(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indane (9.46 g, 24.99 mmol) in a mixture of 200 mL diethyl ether and 40 mL THF, cooled to -50 °C. The mixture was stirred overnight at room temperature, and the resulting pale orange suspension was then cooled to -50 °C, and dichlorodimethylsilane (16.1 g, 125 mmol, 5 equivalents) was added in a single addition. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3), the filter cake being washed with 2 × 50 mL hot toluene. The combined filtrates were evaporated to dryness to give the title product as a white solid, which was ready for use without further purification.

[0513] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][4-(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl]dimethylsilane

[0514]

[0515] Will n A hexane solution of BuLi (2.43 M, 10.3 ml, 25.0 mmol) was added in a single addition to a solution of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indargen (6.86 g, 25.0 mmol) cooled to -50 °C in a mixture of 150 ml diethyl ether and 19 ml THF. The resulting mixture was stirred overnight at room temperature, and then the resulting red solution was cooled to -50 °C and 300 mg CuCN was added. The resulting mixture was stirred at -25 °C for 0.5 h, and then a solution of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indargen-1-yl]chlorodimethylsilane (prepared as above, 25.0 mmol) in 170 ml THF was added in a single addition. The mixture was stirred overnight at room temperature, then filtered through a silica gel 60 filter pad (40–63 µm) and washed with 2 × 50 mL diethyl ether. The combined organic eluents were evaporated to dryness, the residue was dissolved in 200 mL n-hexane, and the resulting solution was passed through a silica gel 60 filter pad (40–63 µm) and washed with 2 × 50 mL n-hexane. The eluent was evaporated to dryness, and the residue was melt-dried under vacuum to give 16.6 g (93.7%) of the title product as a pale yellow glassy substance, which was ready for use without further purification.

[0516] 1 ¹H NMR (CDCl₃): δ 7.26 and 7.24 (2 br.s, sum 2H), 7.05 and 7.04 (2 br.s, sum 2H), 7.00–6.90 (m, sum 5H), 6.84 and 6.83 (2s, sum 1H), 6.48 and 6.47 (2m, sum 1H), 6.31 and 6.27 (2s, sum 1H), 4.32 and 4.20 (2s, sum 1H), 3.31–3.09 (m, 1H), 3.02–2.51 (m, 7H), 2.38, 2.35, 2.34 (2s) and 2.31 (5s, sum 18H), 2.09, 2.07, 2.05 and 1.83 (4s, sum 18H). 6H), 2.13-1.87 (m, 4H), -0.54, -0.55, -0.62 and -0.66 (4s, sum6H).

[0517] trans-dimethylsilanediyl[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride

[0518]

[0519] Will nA hexane solution of BuLi (2.43 M, 19.3 ml, 46.9 mmol) was added in a single step to a solution of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][4-(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl]dimethylsilane (16.6 g, 23.4 mmol, prepared as above) in 200 ml of diethyl ether, cooled to -50 °C. The mixture was stirred overnight at room temperature, and the resulting red solution was then cooled to -50 °C and ZrCl4 (5.46 g, 23.4 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give a yellow multiphase mixture: a pale red solution containing a large amount of yellow precipitate. The mixture was evaporated to dryness, and the residue was extracted with 100 ml of warm toluene. The resulting suspension was filtered through a glass frit funnel (G4), and the filter cake was washed with 2 × 10 ml of warm toluene. Based on NMR spectral evidence, the resulting filtrate contained a mixture of approximately 75 / 25 trans- and cis-zirconium dichlorodichloroethylene. The filtrate was evaporated to approximately 35 ml, and 30 ml of n-hexane was added. The yellow solid precipitated overnight from this solution at room temperature was filtered off, washed with a 2 × 20 ml mixture of n-hexane / toluene (3:1, vol.), and then dried under vacuum. This procedure yielded 6.0 g (29.5%) of trans-dimethylsilanediyl[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride containing 3% of the cis isomer.

[0520] By crystallizing the above-obtained 6.0 g sample of a mixture of approximately 97:3 trans- and cis-zirconium dichloride from a mixture of 40 ml toluene and 15 ml n-hexane, analytically pure trans-dimethylsilanediyl[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride was obtained. This procedure yielded 2.4 g of pure trans-zirconium dichloride.

[0521] trans-dimethylsilanediyl[η5-4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][η5-4-(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride:

[0522] C 52 H 54Analytical values ​​of Cl₂SiZr: C, 71.85; H, 6.26. Measured values: C, 72.11; H, 6.40.

[0523] 1 H NMR (CDCl3): δ 7.33 (s, 1H), 7.36-6.90 (very br.s., 4H), 7.10 (s,1H), 7.01 (s, 1H), 6.98 (s, 1H), 6.94 (s, 2H), 6.75 (s, 1H), 6.71 (s, 1H), 3.13-2.75 (m, 7H), 2.50-2.40 (m, 1H), 2.39, 2.36, 2.33 and 2.32 (4s, sum 21H), 2.06 (s, 3H), 2.06-1.90 (m, 3H), 1.86-1.72 (m, 1H), 1.15 (s, 3H), -0.13 (s,3H). 13 C{ 1 H} NMR (CDCl3,): δ 144.63, 144.55, 143.07, 142.93, 141.43, 138.39,138.36, 138.04, 137.56 (br.s), 137.43, 135.17, 133.81, 133.30, 132.07,132.01, 131.92, 131.79,131.17, 128.90, 128.78, 128.76, 127.70, 127.00, 126.97(br.s), 123.76, 121.91, 118.35, 82.16, 81.95, 33.82, 33.12, 32.19, 32.07, 26.52, 25.98, 21.52, 21.39, 21.37, 21.21, 19.77, 18.77, 3.86, 1.82.

[0524] Comparison of the synthesis of metallocene CM5

[0525] Ethylmalonic acid

[0526]

[0527] 196.4 g (3.5 mol) of potassium hydroxide was heated at 1000 cm⁻¹ 3The aqueous solution was added to a solution of 188.2 g (1.0 mol) diethyl malonate in 500 mL of methanol. The resulting mixture was refluxed for 5 h, and then the ethanol and methanol were distilled off. Then 1000 cm⁻¹ of the aqueous solution was added. 3 The resulting mixture was acidified to pH 1.0 with 12 M HCl. Ethylmalonic acid was extracted with 5 × 300 mL of diethyl ether. The combined extracts were evaporated to dryness and the residue was dried under vacuum. This procedure yielded 120.2 g (91.0%) ethylmalonic acid as a white solid.

[0528] 1 H NMR (DMSO-d6): δ 4.28 (br.s, 2H), 3.12 (d, J = 7.4 Hz, 1H), 1.71 (quin, J = 7.40 Hz, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 171.12, 53.36, 22.01, 11.95.

[0529] 2-Ethylacrylic acid

[0530]

[0531] Diethylamine (108.2 ml, 76.82 g, 1.05 mol) was added dropwise to a solution of ethylmalonic acid (118.8 g, 899.2 mmol) in 1300 ml of ethyl acetate at 5 °C. Paraform (38.4 g, 1.28 mol) was added to the resulting suspension. The mixture was refluxed for 5 h, then cooled to 5 °C, and then 600 ml of diethyl ether and 1700 cm⁻¹ of ethyl acetate were added. 3 2M HCl. After mixing, separate the organic layer and extract the aqueous layer with 2 × 700 ml diethyl ether. Dry the combined organic extracts with Na₂SO₄ and then carefully evaporate to dryness. Purify the residue by vacuum distillation to give 2-ethylacrylic acid, bp 75-77℃ / 6 mm Hg. 79.8 g (88.6%) of colorless liquid was obtained.

[0532] 1 H NMR (CDCl3): δ 12.55 (br.s, 1H), 6.28 (m, 1H), 5.64 (m, 1H), 2.32(qm, J = 7.5 Hz, 2H), 1.08 (t, J = 7.5 Hz, 3H).

[0533] 6-tert-butyl-5-methoxy-2-ethylindan-1-one

[0534]

[0535] At 50°C, 47.6 g of 2-ethylacrylic acid (475.5 mmol, 1.27 equivalents) was added to a mixture of 103.5 g of P4O. 10 The mixture was added dropwise to Eaton's reagent obtained from 520 ml MeSO3H over approximately 1 h at 50–53 °C (hot water bath). The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 1.0 L cold water and 1 kg ice. The crude product was extracted with 3 × 400 ml dichloromethane. The combined organic extracts were washed with an aqueous K2CO3 solution, dried over K2CO3, filtered through a silica gel 60 short pad (40–63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 81.18 g (87.7%, approximately 90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one as a pale yellow oil (bp 150–170 °C / 5 mm Hg).

[0536] 1 H NMR (CDCl3): δ 7.65 (s, 1H), 6.85 (s, 1H), 3.90 (s, 3H), 3.20 (dd,J= 17.2 Hz, J = 7.7 Hz, 1H), 2.71 (dd,J = 17.2 Hz, J = 3.6 Hz, 1H), 2.59-2.51(m, 1H), 1.99-1.87 (m, 1H), 1.54-1.41 (m, 1H), 1.35 (s, 9H), 0.97 (t, J = 7.4Hz, 3H). 13 C NMR (CDCl3): δ 207.59, 164.52, 154.75, 138.65, 129.31, 121.87,107.72, 55.15, 48.86, 35.00, 31.93, 29.54, 24.61, 11.56.

[0537] 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one

[0538]

[0539] At 5 °C, bromine (18.5 ml, 57.4 g, 359.1 mmol) was added dropwise over 5 min to 6-tert-butyl-2-ethyl-5-methoxyindan-1-one (81.18 g, 329.5 mmol), 100.4 g sodium acetate, and 3.0 g sodium acetate. n A mixture of Bu4NI, 280 ml dichloromethane, and 570 ml water was added. The mixture was stirred at 5 °C for 2 h, then a solution of 46.3 g sodium acetate in 260 ml water was added, followed by 9.7 ml (30.1 g, 188.3 mmol) bromine. The resulting mixture was stirred at this temperature for another 1 h, then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 3 × 250 ml dichloromethane. The combined organic extracts were dried over K2CO3, evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 105.3 g (98.1%, approximately 90% purity) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one as a pale yellow oil, which was ready for use without further purification.

[0540] 1 H NMR (CDCl3): δ 7.69 (s, 1H), 4.03 (s, 3H), 3.21 (dd,J = 17.6 Hz, J= 7.8 Hz, 1H), 2.70 (dd, J = 17.6 Hz, J = 3.7 Hz, 1H), 2.66-2.58 (m, 1H), 2.03-1.91 (m, 1H), 1.60-1.47 (m, 1H), 1.40 (s, 9H), 1.03 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 207.14, 162.57, 154.07, 145.20, 133.07, 121.13, 116.50, 61.45, 48.79, 35.46, 33.36, 30.45, 24.34, 11.43.

[0541] 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0542]

[0543] 64.08 g (197.0 mmol) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 37.32 g (248.8 mmol, 1.26 equivalents) of 3,5-dimethylphenylboronic acid, and 1.02 g (2.0 mmol, 1 mol.%) of Pd (P t A mixture of Bu3)2, 63.4 g Na2CO3, 325 ml 2-methyltetrahydrofuran, and 290 ml water was refluxed for 6 h. Then 500 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 200 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a pale yellow oil. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane-dichloromethane = 1:1, then 1:5, vol.). 62.95 g (91.2%, approximately 95% purity) of a pale yellow oil was obtained.

[0544] 1 H NMR (CDCl3): δ 7.73 (s, 1H), 7.03 (s, 1H), 7.02 (s, 2H), 3.32 (s,3H), 3.06 (dd,J = 18.3 Hz, J = 8.6 Hz, 1H), 2.57-2.47 (m, 2H), 2.39 (s, 6H), 2.00-1.87 (m, 1H), 1.54-1.40 (m, 1H), 1.42 (s, 9H), 0.95 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 208.30, 163.42, 153.15, 143.21, 138.06, 136.27, 132.68,131.42, 129.07, 127.17, 121.11, 60.47, 49.00, 35.33, 31.69, 30.49, 24.48,21.36, 11.67.

[0545] 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0546]

[0547] NaBH4 (10.2 g, 269.6 mmol, 1.5 equivalents) was added to a solution of 62.95 g (179.6 mmol) of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 300 ml of THF cooled to 5 °C. 150 ml of MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 700 ml of dichloromethane and 700 ml of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 ml of dichloromethane. The combined organic extracts were passed through a silica gel 60 filter (40–63 µm; eluent: dichloromethane) (~30 ml) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a gray oil. The oily substance was dissolved in 300 ml of toluene, and TsOH (0.3 g) was added to it. The mixture was refluxed using a Dean-Stark separatory for 10 min, and then cooled to room temperature using a water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 150 ml of dichloromethane. The combined organic extracts were dried over K₂CO₃ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, hexane-dichloromethane = 10:1), followed by vacuum distillation, to give 53.14 g (88.5%) of 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene as a pale yellow oil (bp 175–195 °C / 2 mm Hg).

[0548] 1 H NMR (CDCl3): δ 7.22 (s, 1H), 7.09 (s, 2H), 6.99 (s, 1H), 6.45 (t,J= 1.4 Hz, 1H), 3.25 (s, 3H), 3.13 (s, 2H), 2.41 (q, J = 7.4 Hz, 2H), 2.37 (s,6H), 1.44 (s, 9H), 1.14 (d, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 154.25,151.76, 141.51, 140.88, 140.43, 138.31, 137.66, 131.91, 128.46, 127.20,124.97, 117.17, 60.66, 41.00, 35.13, 31.01, 24.25, 21.43, 13.47.

[0549] bis[6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-inden-1-yl]dimethylsilane

[0550]

[0551] At -50℃, n A hexane solution of BuLi (2.5 M, 16.7 ml, 41.75 mmol) was added in a single batch to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene (13.96 g, 41.74 mmol) in 250 ml of diethyl ether. The mixture was stirred overnight at room temperature, and the resulting orange-yellow solution was then cooled to -50 °C, and 200 mg of CuCN was added. The resulting mixture was stirred at -25 °C for 15 min (forming a large amount of yellow precipitate), and then 2.69 g (20.84 mmol) of dichlorodimethylsilane was added in a single batch. The mixture was stirred at room temperature for 5 h, then filtered through a silica gel 60 filter (40–63 µm) and washed with 20 ml of n-hexane. The combined eluent was evaporated to dryness, and the residue was vacuum dried at high temperature to give 15.17 g (approximately 100%, approximately 85% purity) of a mixture of racemic-pro-ligand and meso-pro-ligand in a ratio of approximately 30:70, as a pale yellow glassy solid that could be used without further purification.

[0552] 1 ¹H NMR (CDCl₃): δ 7.56 and 7.32 (2s, sum 2H), 7.12 (s, 4H), 6.99 (s, 2H), 6.46 and 6.44 (2s, sum 2H), 3.79 and 3.59 (2s, sum 2H), 3.26 (2s, sum 6H), 2.57–2.25 (m, 16H), 1.45 and 1.44 (2s, sum 18H), 1.13 and 1.09 (2t, J = 7.4 Hz, sum 6H), -0.10, -0.18 and -0.25 (3s, sum 6H).

[0553] 13C NMR (CDCl3): δ 155.32, 154.45, 153.98, 143.49, 143.40, 139.23,139.16, 138.16, 137.52, 137.50, 137.16, 137.07, 128.24, 127.94, 127.68,127.65, 123.72, 123.50, 120.58, 120.32, 60.48, 45.73, 45.70, 35.15, 35.13,31.29, 31.20, 24.88, 24.82, 21.45, 13.85, 13.81, -4.08, -4.24, -5.60.

[0554] Racemic-dimethylsilanediyl-bis[2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

[0555]

[0556] At room temperature n BuLi's hexane solution (2.5 M, 16.2 ml, 40.5 mmol) was added in a single step to bis[6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-inden-1-yl]dimethylsilane (14.62 g, about 20.16 mmol) in 100 ml nThe mixture was stirred in a pale yellow solution of Bu₂O. The mixture was stirred at room temperature for 15 h, and the resulting yellow suspension was cooled to 0 °C in an ice bath. ZrCl₄ (4.7 g, 20.17 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give a red suspension. The mixture was evaporated to dryness (to an orange-red foamy state). The solid was extracted with 200 mL of hot n-hexane, and the resulting suspension was filtered through a glass frosted funnel (G4) to remove LiCl. The resulting filtrate was evaporated to approximately 125 mL. The orange solid precipitated overnight from this solution at room temperature was collected and dried under vacuum. This procedure yielded 9.3 g of a mixture of approximately 1:1 racemic and meso isomers, with 0.5 mol of n-hexane per mol of Zr. The mother liquor was evaporated to an oily state, the residue was dissolved in 20 mL of n-pentane, and the resulting solution was stirred overnight at room temperature. The orange solid precipitated from this solution was collected and dried under vacuum. The procedure yielded 2.9 g of a mixture of approximately 1:1 racemic and meso isomers, with 0.5 mol of n-pentane per mol of Zr. LiCl (662 mg, 15.6 mmol, 2.0 equivalent) and 12 ml of THF were added to the approximately 1:1 mixture of racemic and meso isomers, and the resulting mixture was stirred at 90 °C for 4 days. Based on NMR spectral evidence, the resulting mixture contained approximately 76:24 of racemic and meso isomers. The THF was then evaporated under vacuum, and 30 ml of toluene was added to the residue. The resulting mixture was evaporated under vacuum to remove residual THF. 100 ml of toluene was added to the residue, and the mixture was heated to approximately 90 °C and then filtered through a glass filter (G4) to remove insoluble inorganic salts. The filtrate was evaporated to 40 ml and filtered again through a glass frit funnel (G4). The filtrate thus obtained was evaporated to approximately 15 ml, heated to approximately 60 °C, and 5 ml of n-hexane was added. After stirring for 5 min, the yellow solid precipitated as (G4) was filtered off, washed with 8 ml of toluene / n-hexane (1:5, vol.), and dried under vacuum. This procedure yielded 1.08 g of pure racemic isomer.

[0557] Racemic isomers:

[0558] 1H NMR (CDCl3): δ 7.48 (s, 2H), 7.45-7.00 (very br.s, 4H), 6.97 (s,2H), 6.61 (s, 2H), 3.43 (s, 6H), 2.75-2.63 (m, 2H), 2.40-2.27 (m, 2H), 2.36(s, 12H), 1.38 (s, 18H), 1.27 (s, 6H), 1.04 (t, J = 7.5 Hz, 6H).

[0559] 13 C NMR (CDCl3): δ 159.74, 144.10, 142.06, 137.84 (br.s), 136.83,133.67, 128.81, 127.44, 127.18, 123.05, 120.94, 119.00, 80.51, 62.68, 35.73, 30.38, 25.97, 21.50, 16.85, 2.74.

[0560] Synthesis of indene from IM1, IM2, IM3, and CM4

[0561] The common intermediate 2,3-dihydrobenzodioxin (CAS# 493-09-4, purity 97%) was purchased from ABCR.

[0562] 7-Methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0563]

[0564] Methacrylamide chloride (94.39 g, 903.0 mmol) was added dropwise over 15 min to a suspension of AlCl3 (126.4 g, 947.7 mmol) cooled to -78 °C in 750 mL of dichloromethane, followed by the dropwise addition of benzo-1,4-dioxane (123.0 g, 903.4 mmol). The reaction mixture was heated to room temperature over 1 hour, and then stirred at room temperature for 19 h. The resulting mixture was poured into a 2000 cm³ container. 3Place on crushed ice. Separate the organic layer and extract the aqueous layer with 300 ml of dichloromethane. Wash the combined organic extracts with an aqueous K₂CO₃ solution, dry with K₂CO₃, and pass through a silica gel 60 short pad (40–63 µm), then wash again with 200 ml of dichloromethane. Evaporate the combined organic eluent to dryness to give 167.5 g (90.8%, approximately 90% purity) of 7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one as a white solid block, which can be used without further purification.

[0565] 9-Bromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0566]

[0567] 93.3 g (456.9 mmol) of 7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 139.0 g of NaOAc, and 3.5 g of... n A mixture of Bu4NBr, 400 ml dichloromethane, and 800 ml water was cooled to +5 °C, and bromine (23.5 ml, 73.3 g, 458.7 mmol) was added dropwise over 20 min at this temperature. The resulting mixture was stirred at this temperature for 1 h, followed by the addition of a solution of 63.6 g NaOAc in 400 ml water, and then 11.0 ml (34.3 g, 214.7 mmol) of bromine over 10 min. The mixture was stirred at 5 °C for another 1 h, and then washed with an aqueous solution of Na2SO3 to neutralize any excess bromine. The organic layer was separated, and the aqueous phase was extracted again with 2 × 200 ml dichloromethane. The combined organic extracts were filtered through a silica gel 60 filter (40–63 μm) and washed again with 200 ml dichloromethane. The combined organic eluent was evaporated to approximately 200 ml, and 200 ml of n-hexane was added. The white solid precipitate (G3) was filtered off and dried under vacuum to give 56.56 g (43.7%) of pure 9-bromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one. The mother liquor was evaporated to give a semi-solid residue. The residue was ground with 65 ml of dichloromethane, and then 65 ml of n-hexane was added. The white solid precipitate (G3) was filtered off and dried under vacuum to give 34.54 g of a mixture of 2:1 9-bromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one and 5,9-dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one.1 H NMR (CDCl3): δ 7.22 (s, 1H), 4.47-4.42 (m, 2H), 4.32-4.27(m, 2H), 3.26 (dd, J = 17.3 Hz, J = 7.8 Hz, 1H), 2.70 (dqd, J = 7.8 Hz, J =7.5 Hz, J = 3.8 Hz, 1H), 2.57 (dd, J = 17.3 Hz, J = 3.8 Hz, 1H), 1.30 (d, J =7.5 Hz, 3H). 13 C NMR (CDCl3): δ 207.52, 147.15, 146.65, 144.14, 130.05, 110.79, 108.95, 65.28, 63.60, 41.92, 35.34, 16.36.

[0568] 9-(3,5-dimethylphenyl)-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0569]

[0570] 55.48 g (199.49 mmol) of 9-bromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 37.84 g (252.3 mmol, 1.27 equivalents) of 3,5-dimethylphenyl-boronic acid, and 1.04 g (2.04 mmol, 1 mol.%) of Pd(P t A mixture of Bu3)2, 64.3 g Na2CO3, 330 ml 2-methyltetrahydrofuran, and 295 ml water was refluxed for 2 h. Then, 400 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 400 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a light brown solid. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: dichloromethane, then dichloromethane: ether = 1:10, vol.). The fractions containing the product were combined and evaporated to dryness. The resulting solid was ground with 200 ml n-hexane. The precipitate formed by (G3) was filtered off, washed with 2 × 40 ml n-hexane, and dried under vacuum. The procedure yielded 59.5 g (96.7%) of 9-(3,5-dimethylphenyl)-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one as a white powder. 1H NMR (CDCl3): δ 7.27 (s, 1H), 7.03 (br.s, 1H), 6.95 (br.s, 2H), 4.30-4.23 (m, 4H), 3.10 (dd, J = 17.1 Hz, J= 7.8 Hz, 1H), 2.61 (dqd, J = 7.8 Hz, J = 7.6 Hz, J = 3.9 Hz, 1H), 2.42 (dd,J = 17.1 Hz, J = 3.9 Hz, 1H), 2.38 (s, 6H), 1.24 (d, J = 7.6 Hz, 3H). 13 C NMR(CDCl3): δ 208.42, 146.77, 146.02, 143.90, 137.76, 134.19, 129.42, 129.21,128.28, 127.15, 110.67, 64.72, 63.59, 41.97, 33.93, 21.35, 16.37.

[0571] 5-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin

[0572]

[0573] NaBH4 (11.0 g, 290.8 mmol, 1.5 equivalents) was added to a solution of 9-(3,5-dimethylphenyl)-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (59.5 g, 193.0 mmol) in 550 mL THF cooled to 5 °C. 200 mL of MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 1000 mL of dichloromethane and 1000 mL of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 50 mL of dichloromethane. The combined organic extracts were passed through a silica gel 60 filter (40–63 µm; eluent: dichloromethane) (~30 ml) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a white solid mass, which was dissolved in 800 ml of toluene preheated to approximately 60 °C, and then TsOH (1.0 g) was added. The mixture was refluxed using a Dean-Stark separator for 10 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with a 10% K₂CO₃ aqueous solution to separate the organic layer, and the aqueous layer was extracted with 100 ml of dichloromethane. The combined organic extracts were dried over K₂CO₃, passed through a silica gel 60 filter (40–63 µm), and the resulting eluent was evaporated to dryness. The crude product was milled with 200 ml of n-hexane. The precipitate formed by (G₃) was filtered off, washed with 2 × 20 ml of n-hexane, and dried under vacuum. The procedure yielded 53.08 g (96.7%) of 5-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin as a white powder. 1 H NMR(CDCl3): δ 7.01 (br.s, 2H), 6.98 (br.s, 1H), 6.76 (s, 1H), 6.37 (m, 1H), 4.24-4.21 (m, 2H), 4.21-4.17 (m, 2H), 3.08 (s, 2H), 2.36 (s, 6H), 2.05 (m, 3H). 13 C NMR (CDCl3): δ 145.32, 142.45, 138.59, 137.46, 136.35, 135.27, 128.94,127.26, 127.18, 126.28, 107.50, 64.40, 64.15, 42.18, 21.41, 16.66.

[0574] 5,9-Dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (Method A)

[0575]

[0576] At -50 °C, a solution of 7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (37.0 g, 181.2 mmol, prepared as above) in 50 mL of dichloromethane was added dropwise to a suspension of AlCl3 (60.0 g, 500 mmol, 2.48 equivalents) in 500 mL of dichloromethane over 15 min. The reaction mixture was stirred at this temperature for 5 min, followed by the dropwise addition of bromine (19.0 mL, 59.26 g, 370.82 mmol, 2.05 equivalents) over 15 min. The resulting mixture was stirred at room temperature for 4 h, and then poured into a 2000 cm³ container. 3 In crushed ice. Separate the organic layer and extract the aqueous layer with 300 ml of dichloromethane. Wash the combined organic extracts with an aqueous K2CO3 solution, dry with K2CO3 and pass through a silica gel 60 short pad (40–63 µm), then wash with 200 ml of dichloromethane. Evaporate the combined organic eluent to about 200 ml and add 200 ml of n-hexane. Filter off the white solid (G3) precipitate and dry under vacuum to give 43.75 g (66.7%) of pure 5,9-dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one. 1 H NMR (CDCl3): δ 4.49-4.45 (m, 2H), 4.44-4.39(m, 2H), 3.23 (dd, J = 17.4 Hz, J = 8.1 Hz, 1H), 2.73 (dqd, J = 8.1 Hz, J =7.4 Hz, J = 4.1 Hz, 1H), 2.54 (dd, J = 17.4 Hz, J = 4.1 Hz, 1H), 1.32 (d, J =7.4 Hz, 3H). 13 C NMR (CDCl3): δ 205.34, 148.32, 146.49, 141.37, 127.55, 108.36, 107.25, 65.18, 64.30, 42.64, 34.70, 16.45.

[0577] 5,9-Dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (Method B)

[0578]

[0579] 36.9 g (180.7 mmol) of 7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 110.0 g of NaOAc, and 1.5 g of... n A mixture of Bu4NBr, 300 ml dichloromethane, and 600 ml water was cooled to +5 °C, and then bromine (18.5 ml, 57.7 g, 361.1 mmol, 2.0 mmol) was added dropwise over 20 min at this temperature. The resulting mixture was stirred at this temperature for 1 h, followed by the addition of 55.0 g NaOAc, and then the addition of bromine (9.0 ml, 28.1 g, 175.7 mmol) dropwise over 10 min. The mixture was stirred overnight at room temperature to give a pale orange suspension containing a large amount of precipitate. An aqueous solution of Na2SO3 was added to neutralize the excess bromine, followed by the addition of 500 ml dichloromethane to dissolve the formed precipitate. The organic layer was separated, and the aqueous phase was extracted with 2 × 300 ml dichloromethane. The combined organic extracts were filtered through a silica gel 60 filter (40–63 μm) and washed with 200 ml dichloromethane. The combined organic eluent was evaporated to approximately 200 ml. The pink solid precipitated by (G3) was filtered off and dried under vacuum to give 32.58 g (49.8%) of pure 5,9-dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one. 50 ml of n-hexane was added to the mother liquor, and the resulting mixture was evaporated to approximately 50 ml. The white solid precipitated by (G3) was filtered off, washed with 2 × 10 ml of n-hexane, and dried under vacuum to give 13.69 g of a mixture of 5,9-dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one and 9-bromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one in a 93:7 ratio.

[0580] 5,9-Bis(3,5-dimethylphenyl)-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0581]

[0582] 58.82 g (162.48 mmol) of 5,9-dibromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 54.83 g (365.6 mmol, 2.25 equivalents) of 3,5-dimethylphenylboronic acid, and 1.3 g (2.54 mmol, 1.57 mol.%) of Pd(P t A mixture of Bu3)2, 93.1 g Na2CO3, 600 ml 2-methyltetrahydrofuran, and 420 ml water was refluxed for 5 h. Then, 500 ml water was added, the organic layer was separated, and the aqueous layer was extracted with 400 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a brownish-yellow solid block. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: dichloromethane). This procedure yielded 66.4 g (99.1%) of 5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one as a yellow solid block. 1 H NMR(CDCl3): δ 7.04 (s, 1H), 7.01 (s, 1H), 6.99 (s, 2H), 6.97 (s, 2H), 4.26-4.20(m, 2H), 4.20-4.14 (m, 2H), 3.07 (dd, J = 17.1 Hz, J = 8.0 Hz, 1H), 2.55(dqd, J = 8.0 Hz, J = 7.3 Hz, J = 4.5 Hz, 1H), 2.40 (dd, J = 17.1 Hz, J = 4.5Hz, 1H), 2.39 (s, 6H), 2.36 (s, 6H), 1.16 (d, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ 207.03, 146.02, 145.93, 140.67, 137.73, 136.68, 134.42, 132.71, 129.47,129.33, 128.48, 127.57, 127.26, 127.14, 126.18, 64.47, 63.65, 42.40, 33.37, 21.42, 21.35, 16.06.

[0583] 5,9-Bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin

[0584]

[0585] NaBH4 (9.2 g, 243.2 mmol, 1.51 equivalents) was added to a solution of 5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (66.4 g, 161.0 mmol) in 550 mL THF cooled to 5 °C. 200 mL of MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 1000 mL of dichloromethane and 1000 mL of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 50 mL of dichloromethane. The combined organic extracts were passed through a silica gel 60 filter (40–63 µm; eluent: dichloromethane) (~30 ml) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a white solid mass, which was then dissolved in 700 ml of toluene preheated to approximately 60 °C, followed by the addition of 0.9 g TsOH. The mixture was refluxed using a Dean-Stark separator for 10 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. During the cooling of the resulting mixture to room temperature, a large amount of white precipitate formed. The resulting suspension was washed with a 10% K₂CO₃ aqueous solution, and dichloromethane was added to the resulting suspension until the precipitate was completely dissolved (total volume of organic phase approximately 1200 ml). The organic layer was separated, and the aqueous layer was extracted with 150 ml of dichloromethane. The combined organic extracts were dried over K₂CO₃, passed through a silica gel 60 filter (40–63 µm), and the resulting eluent was evaporated to dryness. The crude product was ground with 200 ml of n-hexane, the precipitate formed by (G3) was filtered off, washed with 2 × 50 ml of n-hexane, and dried under vacuum. This procedure yielded 61.57 g (96.5%) of 5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin as a white powder. 1 H NMR (CDCl3): δ 7.08 (s,2H), 7.06 (s, 2H), 7.00 (s, 2H), 6.29 (m, 1H), 4.23-4.17 (m, 4H), 3.15 (s,2H), 2.38 (2s, sum 12H), 2.01 (m, 3H). 13C NMR (CDCl3): δ 144.89, 139.42,137.70, 137.49, 137.45, 137.31, 136.46, 135.96, 134.69, 128.94, 128.75,128.10, 127.38, 126.35, 125.83, 122.10, 64.20, 42.52, 21.45, 16.72.

[0586] 7-Ethyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0587]

[0588] 2-Ethylacryloyl chloride (27.6 g, 233 mmol) was added dropwise over 15 min to a suspension of AlCl3 (33.0 g, 244 mmol) cooled to -78 °C in 300 mL of dichloromethane, followed by the dropwise addition of benzo-1,4-dioxane (31.7 g, 233 mmol). The reaction mixture was allowed to reach room temperature over 1 h, and then stirred at room temperature for 19 h. The resulting mixture was poured into a 500 cm³ container. 3 On crushed ice. Separate the organic layer and extract the aqueous layer with 2 × 100 ml dichloromethane. Wash the combined organic extracts with an aqueous K₂CO₃ solution, dry with K₂CO₃, and pass through a silica gel 60 short pad (40–63 µm), then wash again with 100 ml dichloromethane. Evaporate the combined organic eluent to dryness. Wash the residue with a mixture of 50 ml n-hexane and about 4 ml dichloromethane, then dry under vacuum to give 31.5 g (62%) of the title substance as a white solid mass. 1 H NMR (CDCl3): δ 7.23 (s, 1H), 6.89 (s, 1H), 4.33-4.31 (m, 2H), 4.27-4.25 (m,2H), 3.18 (dd, J = 16.9 Hz, J = 7.7 Hz, 1H), 2.69 (dd, J = 16.9 Hz, J = 3.7Hz, 1H), 2.57 (m, 1H), 1.99-1.89 (m, 1H), 1.55-1.44 (m, 1H), 0.98 (t, J = 7.4Hz, 3H). 13C NMR (CDCl3): δ 207.50, 149.88, 147.73, 143.53, 130.44, 113.94, 111.54, 64.58, 63.80, 48.98, 31.56, 24.56, 11.49.

[0589] 9-Bromo-7-ethyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0590]

[0591] 15.7 g (72 mmol) of 7-ethyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 23.6 g of NaOAc, and 0.6 g of... n A mixture of Bu4NBr, 75 ml dichloromethane, and 150 ml water was cooled to +5 °C, and then 3.71 ml (72 mmol) of bromine was added dropwise over 20 min at this temperature. The resulting mixture was stirred at this temperature for 1 h, followed by the addition of a solution of 4.9 g NaOAc in 50 ml water, and finally, 0.8 ml (15 mmol) of bromine was added dropwise over 10 min. The mixture was stirred at 5 °C for 1 h, and then washed with an aqueous solution of Na2SO3 to remove excess bromine. The organic layer was separated, and the aqueous layer was extracted again with 2 × 100 ml dichloromethane. The combined organic extracts were filtered through a silica gel 60 filter (40–63 μm) and washed again with 50 ml dichloromethane. The combined organic eluents were evaporated to dryness. The residue was washed twice with 150 ml n-hexane and dried under vacuum to give 17.8 g (83%, approximately 93% purity) of the title substance as a white solid mass. 1 HNMR (CDCl3): δ 7.22 (s, 1H), 4.46-4.44 (m, 2H), 4.30-4.28 (m, 2H), 3.18 (dd,J = 17.1 Hz, J = 7.6 Hz, 1H), 2.68-2.58 (m, 2H), 1.95 (m, 1H), 1.58-1.47 (m,1H), 1.01 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 207.09, 147.59, 146.69, 144.20, 130.77, 110.75, 109.07, 65.35, 63.67, 48.78, 32.86, 24.55, 11.49.

[0592] 9-(3,5-dimethylphenyl)-7-ethyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0593]

[0594] 17.28 g (58 mmol) of 9-bromo-7-ethyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 11.05 g (73.6 mmol, 1.27 equivalents) of 3,5-dimethylphenylboronic acid, and 0.3 g (0.58 mmol, 1 mol.%) of Pd(P t A mixture of Bu3)2, 18.7 g Na2CO3, 100 ml 2-methyltetrahydrofuran, and 90 ml water was refluxed for 5 h. Then 200 ml water was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 100 ml dichloromethane. The combined organic extracts were dried with K2CO3 and then evaporated to dryness. The crude product was dissolved in 50 ml dichloromethane, and 75 ml hexane was added. Most of the dichloromethane was evaporated, the (G3) precipitate of the title product was filtered off, and dried under vacuum to give 14.7 g (78.5%) white solid mass.

[0595] 1 H NMR (CDCl3): δ 7.27 (s, 1H), 7.04 (br.s, 1H), 6.96 (br.s, 2H), 4.29-4.24 (m, 4H), 3.02 (dd, J = 17.6 Hz, J = 8.1 Hz, 1H), 2.55-2.46 (m, 2H), 2.38 (s, 6H), 1.97-1.87 (m, 1H), 1.52-1.41 (m, 1H), 0.94 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 207.91, 146.78, 146.38, 143.90, 137.84, 134.31, 129.91,129.48, 128.36, 127.20, 110.58, 64.77, 63.64, 48.84, 31.36, 24.55, 21.40,11.61.

[0596] 5-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin

[0597]

[0598] NaBH4 (2.58 g, 68.3 mmol, 1.5 equivalents) was added to a solution of 9-(3,5-dimethylphenyl)-7-ethyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (14.7 g, 45.5 mmol) in 190 ml THF cooled to 5 °C. 70 ml MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 150 ml dichloromethane and 300 ml water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 2 × 50 ml dichloromethane. The combined organic extracts were evaporated to dryness to give a white solid mass. The block was dissolved in 300 ml of toluene and heated to approximately 60 °C, then 0.5 g of TsOH was added. The mixture was refluxed using a Dean-Stark separator for 10 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with 10% K₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 100 ml of dichloromethane. The combined organic extracts were dried over K₂CO₃, passed through a silica gel 60 filter (40–63 µm), and then evaporated to dryness. The crude product was ground with 40 ml of n-pentane, the (G₃) precipitate was filtered off, and the product was dried under vacuum. This procedure yielded 11.88 g (85.2%) of the title product as a white powder. 1 H NMR (CDCl3): δ 7.02 (br.s,2H), 6.98 (br.s, 1H), 6.78 (s, 1H), 6.38 (m, 1H), 4.23-4.21 (m, 2H), 4.19-4.17 (m, 2H), 3.10 (s, 2H), 2.40 (m, 2H), 2.36 (s, 6H), 1.14 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 151.76, 142.47, 138.40, 137.52, 137.46, 136.38, 135.01,128.93, 127.27, 124.36, 107.66, 64.39, 64.14, 40.42, 24.24, 21.40, 13.27.

[0599] 7-Isopropyl-2,3,7,8-Tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0600]

[0601] 2-Isopropylacrylyl chloride (78.0 g, 588 mmol) was added dropwise over 15 min to a suspension of 82.3 g (617 mmol) AlCl3 cooled to -78 °C in 500 mL dichloromethane, followed by the dropwise addition of benzo-1,4-dioxane (80.05 g, 588 mmol). The reaction mixture was allowed to reach room temperature over 1 h, and then stirred at room temperature for 19 h. The resulting mixture was poured into a 1500 cm³ container. 3 Place on crushed ice. Separate the organic layer and extract the aqueous layer with 2 × 200 ml dichloromethane. Wash the combined organic extracts with aqueous K₂CO₃ solution, dry with K₂CO₃ and pass through a silica gel 60 short pad (40–63 µm), then wash with 200 ml dichloromethane. Evaporate the combined organic eluent to dryness. Wash the residue with 300 ml n-hexane and dry under vacuum to give 105.4 g (77.1%) of the title substance as a white solid mass. 1 H NMR (CDCl3): δ 7.22(s, 1H), 6.90 (s, 1H), 4.33-4.31 (m, 2H), 4.27-4.25 (m, 2H), 3.00 (dd, J =17.1 Hz, J = 8.0 Hz, 1H), 2.79 (dd, J = 17.1 Hz, J = 3.8 Hz, 1H), 2.64-2.60(m, 1H), 2.42-2.32 (m, 1H), 1.03 (d, J = 6.9 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). 13 C NMR (CDCl3): δ 207.40, 149.83, 148.14, 143.50, 131.19, 113.89, 111.37, 64.60, 63.82, 53.31, 29.04, 27.39, 20.86, 17.02.

[0602] 9-Bromo-7-isopropyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0603]

[0604] 51.1 g (220 mmol) of 7-isopropyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 67.0 g of NaOAc, and 1.8 g of... n A mixture of Bu4NBr, 200 ml dichloromethane, and 400 ml water was cooled to +5 °C, and bromine (11.3 ml, 35.15 g, 220 mmol) was added dropwise over 20 min at this temperature. The resulting mixture was stirred at this temperature for 1 h, followed by the addition of a solution of 16.4 g NaOAc in 100 ml water, and finally, bromine (2.6 ml, 8.0 g, 50 mmol) over 10 min. The mixture was stirred at 5 °C for 1 h, and then washed with an aqueous solution of Na2SO3 to remove excess bromine. The organic layer was separated, and the aqueous layer was extracted again with 2 × 200 ml dichloromethane. The combined organic extracts were filtered through a silica gel 60 filter (40–63 μm) and washed again with 200 ml dichloromethane. The combined organic eluent was evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 1000 mm, eluent: dichloromethane). The yield was 37.2 g (54.3%). 1 H NMR (CDCl3): δ 7.20 (s, 1H), 4.46-4.44 (m, 2H), 4.30-4.28 (m, 2H), 3.00 (dd, J = 17.5 Hz, J = 8.0 Hz, 1H), 2.75 (dd, J = 17.5Hz, J = 3.8 Hz, 1H), 2.66 (m, 1H), 2.39 (m, 1H), 1.05 (d, J = 6.9 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). 13 C NMR (CDCl3): δ 206.84, 147.82, 146.57, 144.09, 131.34, 110.44, 108.98, 65.29, 63.61, 53.07, 29.05, 28.79, 20.73, 17.06.

[0605] 9-(3,5-dimethylphenyl)-7-isopropyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one

[0606]

[0607] 37.2 g (119.6 mmol) of 9-bromo-7-isopropyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one, 22.78 g (151.9 mmol, 1.27 equivalents) of 3,5-dimethylphenylboronic acid, and 0.61 g (1.2 mmol, 1 mol.%) of Pd(P t A mixture of Bu3)2, 38.5 g Na2CO3, 200 ml 2-methyltetrahydrofuran, and 180 ml water was refluxed for 2 h. Then, 400 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 200 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, d 50 mm, l 500 mm, eluent: dichloromethane, then dichloromethane: ether = 1:10, vol.). This procedure yielded 37.4 g (93%) of the title product as a white powder. 1 H NMR (CDCl3): δ 7.26 (s, 1H), 7.05 (br.s, 1H), 6.96 (br.s,2H), 4.30-4.23 (m, 4H), 2.85 (dd, J = 18.1 Hz, J = 8.6 Hz, 1H), 2.60-2.54 (m,2H), 2.39 (s, 6H), 2.39-2.32 (m, 1H), 0.97 (d, J = 6.9 Hz, 3H), 0.75 (d, J =6.8 Hz, 3H). 13 C NMR (CDCl3): δ 207.75, 146.72, 143.83, 137.83, 134.36, 130.59,129.46, 128.30, 127.19, 110.35, 64.74, 63.61, 53.12, 29.02, 27.09, 21.39,20.83, 17.15.

[0608] 5-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin

[0609]

[0610] NaBH4 (6.35 g, 168.0 mmol, 1.5 equivalents) was added to a solution of 9-(3,5-dimethylphenyl)-7-isopropyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one (37.4 g, 111.2 mmol) in 380 mL THF cooled to 5 °C. 140 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 500 mL of dichloromethane and 1000 mL of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 2 × 50 mL of dichloromethane. The combined organic extracts were evaporated to dryness to give a white solid mass, which was dissolved in 500 ml of toluene preheated to approximately 60 °C, and then 1.0 g of TsOH was added. The mixture was refluxed using a Dean-Stark separator for 10 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with 10% K₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 100 ml of dichloromethane. The combined organic extracts were dried over K₂CO₃, passed through a silica gel 60 filter bed (40–63 µm), and then evaporated to dryness. The crude product was ground with 50 ml of n-hexane, the (G₃) precipitate was filtered off, the filter cake was washed with 20 ml of n-hexane, and dried under vacuum. This procedure yielded 31.8 g (89%) of the title product as a white powder. 1 H NMR (CDCl3): δ 7.02 (br.s, 2H), 6.99 (br.s, 1H), 6.79 (s, 1H), 6.38 (m, 1H), 4.22-4.20 (m,2H), 4.18-4.16 (m, 2H), 3.11 (s, 2H), 2.66 (sep, J = 6.8 Hz, 1H), 2.36 (s, 6H), 1.14 (d, J = 6.9 Hz, 6H). 13 C NMR (CDCl3): δ 156.37, 142.49, 138.21,137.57, 137.48, 136.38, 134.87, 128.95, 127.31, 127.27, 123.28, 107.78,64.39, 64.12, 38.59, 30.01, 22.52, 21.41.

[0611] This invention relates to metallocene 1 (IM1).

[0612] Bis[9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane

[0613]

[0614] At -50℃, n A hexane solution of BuLi (2.5 M, 16.0 ml, 40.0 mmol) was added in a single dose to 11.7 g (40.0 mmol) of 5-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin in a solution of 200 ml diethyl ether and 10 ml THF.

[0615] The mixture was stirred overnight at room temperature, and the resulting yellow solution was then cooled to -50°C and 150 mg CuCN was added. The resulting mixture was stirred at -20°C for 15 min, and then 2.58 g (20.0 mmol) of dichlorodimethylsilane was added in a single batch. The mixture was stirred at room temperature for 4 h, and then filtered through a silica gel 60 filter (40–63 µm), followed by washing with 2 × 40 mL of diethyl ether. The combined pale yellow organic eluent was evaporated to dryness, and the residue was dried under vacuum at high temperature to give 12.66 g (approximately 98.8%, approximately 75% purity) of the title product (a mixture of approximately 55:45 stereoisomers) as a pale yellow glassy substance, which was ready for use without further purification.

[0616] trans-dimethylsilanediyl-bis[9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride

[0617]

[0618] At room temperature, nA hexane solution of BuLi (2.5 M, 14.0 mL, 35.0 mmol) was added in a single batch to a solution of 11.18 g (17.45 mmol) of bis[9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane in 110 mL of di-n-butyl ether. The mixture was stirred at room temperature for 4.5 h, and the resulting red solution was cooled to 0 °C in an ice bath, followed by the addition of ZrCl4 (4.07 g, 17.47 mmol). The reaction mixture was stirred at room temperature for 24 h to obtain a red suspension. The suspension was evaporated to dryness, and the resulting solid was extracted with 150 mL of boiling toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of approximately 64:36 racemic and meso-zirconia dichloroethylene. The filter cake contained meso-zirconia dichloroethylene. The latter precipitate was extracted with 4 × 50 ml boiling toluene. The resulting extract was evaporated to approximately 20 ml, and 20 ml of hexane was added. The red crystalline solid precipitated from this solution at room temperature was collected and then dried under vacuum. This procedure yielded 1.2 g (8.5%) racemic zirconium dichloroethylene. The toluene solution obtained above (after the first filtration) was evaporated to approximately 80 ml. The orange solid precipitated from this hot solution was collected and dried under vacuum. This procedure yielded 1.72 g racemic zirconium dichloroethylene, with 0.8 mol of toluene per mol of complex.

[0619] Meso dichlorozirconium: C 42 H 42 Analytical values ​​of Cl2O4SiZr: C, 62.98; H, 5.29. Measured values: C, 63.25; H, 5.52. 1 H NMR (CDCl3): δ 7.14 (br.s, 4H), 7.05 (s, 2H), 6.94 (s,2H), 6.39 (s, 2H), 4.25-4.17 (m, 4H), 4.14-4.06 (m, 4H), 2.33 (s, 12H), 2.32 (s, 6H), 1.35 (s, 3H), 1.16 (s, 3H). 13 C10 NMR (CDCl3): δ 144.25, 142.74, 137.35, 135.15, 134.66, 132.69, 129.22, 127.69, 122.88, 121.54, 118.88, 110.74, 80.90, 64.56, 64.06, 21.46, 18.78, 2.71, 2.37. Racemic zirconium dichloroethylene: ...42 H 42 Analytical calculation values ​​for Cl2O4SiZr*0.8C7H8: C, 65.36; H, 5.58. Measured values: C, 65.30; H, 5.76. 1 H NMR (CDCl3): δ 7.23 (br.s, 4H), 7.00 (s, 2H), 6.96 (s, 2H), 6.58 (s, 2H), 4.30-4.17 (m,8H), 2.33 (s, 12H), 2.21 (s, 6H), 1.22 (s, 6H). 13 C NMR (CDCl3): δ 145.21,143.58, 137.47, 134.45, 134.27, 130.22, 129.26, 127.73, 122.46, 121.43,120.89, 108.68, 79.31, 64.55, 64.31, 21.38, 18.51, 2.39.

[0620] This invention relates to metallocene 2 (IM2).

[0621] bis[9-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane

[0622]

[0623] At -50°C, 15.2 ml (38.18 mmol) of 2.5 M dioxin was added at once to a suspension of 11.7 g (38.18 mmol) of 5-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin in a mixture of 200 ml diethyl ether and 50 ml THF. nBuLi was dissolved in hexane. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was cooled to -50°C and 200 mg CuCN was added. The resulting mixture was stirred at -20°C for 15 min, and then 2.46 g (19.09 mmol) of dichlorodimethylsilane was added in a single batch. The mixture was stirred overnight at room temperature and then evaporated to dryness. The crude product was dissolved in a mixture of 50 ml dichloromethane and 50 ml hexane and filtered through a silica gel 60 filter (40-63 μm), and then washed with 2 × 40 ml dichloromethane. The combined organic eluents were evaporated to dryness, and the residue was dried under vacuum at high temperature to give 12.9 g (considered yield, approximately 91% purity) of the title product (a mixture of approximately 55:45 stereoisomers) as a white powder, which could be used without further purification.

[0624] Racemic-dimethylsilanediyl-bis[η] 5 -9-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride

[0625]

[0626] At -20°C, 15.3 ml (38.2 mmol) of 2.5 M dibutyl ether was added in a single batch to a solution of 12.9 g (approximately 19.09 mmol) of bis[9-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl](dimethyl)silane in 110 ml of di-n-butyl ether. nA hexane solution of BuLi was prepared. The mixture was stirred at room temperature for 4.5 h, and the resulting yellow suspension was cooled to 0 °C and 4.45 g (19.09 mmol) of ZrCl4 was added. The reaction mixture was stirred at room temperature for 24 h to give an orange suspension. The suspension was evaporated to dryness, and the solid formed was extracted with 400 ml of boiling toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of racemic zirconium dichlorocerocene and meso zirconium dichlorocerocene in a ratio of approximately 55:45. The filter cake (approximately 1.9 g) contained meso zirconium dichlorocerocene. The red precipitate that precipitated overnight from the mother liquor obtained above at room temperature was collected and dried under vacuum. This procedure yielded 3.5 g of meso zirconium dichlorocerocene, with 1 mol of toluene per mol of complex. The mother liquor was evaporated to approximately 120 ml. The orange crystalline precipitate that precipitated from this solution at room temperature was collected and dried under vacuum. This procedure yielded 0.56 g of racemic zirconium dichlorocerocerocene, with 1 mol of toluene per mol of complex. Evaporate the mother liquor to approximately 50 ml. Collect the orange crystalline precipitate that forms from this solution at room temperature. This procedure yields 4.3 g of a mixture of approximately 92:8 racemic and meso-zirconia dichloroethylene, which is recrystallized from 50 ml of toluene. Collect the orange crystalline solid that forms from this solution at room temperature and dry it under vacuum. This procedure yields 3.35 g of racemic zirconia dichloroethylene, with each mol of complex corresponding to 1 mol of toluene.

[0627] Meso dichlorozirconium: C 44 H 46 Analytical values ​​of Cl2O4SiZr*C7H8: C, 66.50; H, 5.91. Measured values: C, 66.71; H, 6.18. 1 H NMR (CDCl3): δ 7.16 (br.s, 4H), 7.07 (s, 2H), 6.94 (s,2H), 6.42 (s, 2H), 4.25-4.17 (m, 4H), 4.12-4.06 (m, 4H), 2.62 (m, 4H), 2.33 (s, 12H), 1.37 (s, 3H), 1.17-1.13 (m, 9H). 13 C NMR (CDCl3): δ 144.34, 142.78,142.27, 137.33, 134.68, 132.74, 129.17, 127.74, 123.09, 121.62, 116.99,110.82, 79.55, 64.57, 64.07, 26.27, 21.46, 17.69, 2.76, 2.70.

[0628] Racemic dichlorozirconium: C 44 H 46 Analytical values ​​of Cl2O4SiZr*C7H8: C, 66.50; H, 5.91. Measured values: C, 66.63; H, 6.06. 1 H NMR (CDCl3): δ 7.25 (br.s, 4H), 6.98 (s, 2H), 6.96 (s,2H), 6.62 (s, 2H), 4.29-4.15 (m, 8H), 2.69 (m, 2H), 2.41 (m, 2H), 2.33 (s,12H), 1.22 (s, 6H), 1.07 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 145.28,143.51, 141.58, 137.43 (br. s), 134.47, 130.23, 129.20, 127.80, 122.51,121.54, 118.86, 108.78, 78.00, 64.53, 64.29, 25.91, 21.37, 17.46, 2.73.

[0629] This invention relates to metallocene 3 (IM3).

[0630] [5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]chlorodimethylsilane

[0631]

[0632] Will nA hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 mmol) was added in a single addition to a suspension of 5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin (7.93 g, 20.0 mmol) in 180 ml diethyl ether and 12 ml THF, cooled to -50 °C. The mixture was stirred at room temperature for 20 h, and the resulting orange suspension was then cooled to -50 °C, and dichlorodimethylsilane (12.1 ml, 12.95 g, 100.3 mmol, 5.0 equivalent) was added in a single addition. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G4), and the filter cake was washed with 100 ml of hot toluene. The combined filtrates were evaporated to dryness to give [5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]chlorodimethylsilane, a white solid that can be used without further purification.

[0633] 1 H NMR (CDCl3): δ 7.16 (s, 2H), 7.05 (s, 2H), 7.00 (s, 1H), 6.98 (s,1H), 6.38 (m, 1H), 4.29-4.25 (m, 1H), 4.23-4.21 (m, 2H), 4.12-4.07 (m, 1H), 3.99 (s, 1H), 2.38 (s, 6H), 2.37 (s, 6H), 2.21 (m, 3H), -0.17 (s, 3H), -0.19 (s, 3H). 13 C NMR (CDCl3): δ 145.72, 139.32, 137.95, 137.44, 137.33, 136.26, 136.02, 134.34, 129.13, 128.83, 128.12, 125.97, 125.43, 122.07, 64.16, 64.14,49.58, 21.47, 21.42, 18.04, 3.64, -1.48.

[0634] [5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane

[0635]

[0636] At -50℃, n A hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 mmol) was added in a single addition to a solution of 5-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin (5.85 g, 20.01 mmol) in a mixture of 100 ml diethyl ether and 5 ml THF. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C and 150 mg CuCN was added. The resulting mixture was stirred at -20 °C for 15 min, and then a solution of [5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]chlorodimethylsilane (9.78 g, 20.0 mmol) in a mixture of 100 ml diethyl ether and 100 ml THF was added in a single addition. The mixture was stirred overnight at room temperature, then filtered through a silica gel 60 filter (40–63 µm) and washed with 2 × 40 mL of diethyl ether. The combined pale yellow organic eluent was evaporated to dryness, and the residue was dried under vacuum at high temperature to give 14.5 g (approximately 97.3%, approximately 65% ​​pure) of the title product (a mixture of approximately 55:45 stereoisomers) as a yellow, glassy solid, which was ready for use without further purification.

[0637] trans-dimethylsilanediyl[5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydroindo[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydroindo[5,6-b][1,4]dioxin-6-yl]zirconium dichloride

[0638]

[0639] At room temperature, nA hexane solution of BuLi (2.5 M, 13.85 mL, 34.6 mmol) was added in a single batch to a solution of [5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane (12.92 g, 17.35 mmol) in 110 mL of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to 0 °C in an ice bath, and ZrCl4 (4.05 g, 17.35 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give an orange suspension. The suspension was evaporated to dryness. The solid formed was extracted with 150 mL of boiling toluene. Based on NMR spectral evidence, the obtained extract contained a mixture of approximately 75:25 trans-IM3 and cis-IM3, as well as polymer byproduct impurities. The mother liquor was evaporated to approximately 50 ml. The orange solid precipitated from this solution at room temperature was collected and dried under vacuum. This procedure yielded 1.15 g of trans-IM3.

[0640] C 50 H 50 Analytical values ​​of Cl2O4SiZr: C, 66.35; H, 5.57. Measured values: C, 66.52; H, 5.80. 1 H NMR (CDCl3): δ 7.32 (very br.s, 2H), 7.24 (very br.s, 2H), 7.22 (s,1H), 7.02 (s, 1H), 7.00 (s, 1H), 6.96 (s, 2H), 6.94 (s, 1H), 6.69 (s, 1H),6.62 (s, 1H), 4.28-4.09 (m, 8H), 2.39 (s, 3H), 2.36 (s, 3H), 2.33 (s, 6H),2.33 (s, 6H), 2.31 (s, 3H), 2.03 (s, 3H), 1.08 (s, 3H), -0.20 (s, 3H). 13C NMR(CDCl3): δ 145.28, 143.59, 143.50, 142.76, 138.04, 137.44 (br.s), 137.14,136.96, 134.97, 134.54, 134.51, 133.21, 131.08, 129.74, 129.45, 129.22,129.18, 129.10, 127.94, 127.78, 127.69, 126.85, 123.24, 122.14, 122.01,121.80, 121.05, 108.85, 80.01, 79.92, 64.53, 64.44, 64.29, 64.12, 21.52, 21.36, 21.30, 21.23, 19.85, 18.72, 3.54, 1.53.

[0641] Compared to metallocene (CM4)

[0642] Chloro[9-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane

[0643]

[0644] Will n A hexane solution of BuLi (2.5 M, 5.0 mL, 12.5 mmol) was added in a single dose to a solution of 5-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin (4.0 g, 12.5 mmol) cooled to -50 °C in a mixture of 100 mL diethyl ether and 10 mL THF. The mixture was stirred at room temperature for 20 h, and the resulting orange suspension was then cooled to -50 °C, and dichlorodimethylsilane (7.5 mL, 7.95 g, 61.6 mmol, approximately 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 (G4), and the filter cake was washed with 50 mL of hot toluene. The combined filtrates were evaporated to dryness to give the title substance, which was ready for use without further purification. 1HNMR (CDCl3): δ 7.04 (br.s, 2H), 7.00 (s, 1H), 6.99 (s, 1H), 6.38 (br.s, 1H), 4.27-4.20 (m, 4H), 3.70 (s, 1H), 2.90-2.83 (m, 1H), 2.38 (s, 6H), 1.19 (d, J = 6.6 Hz, 3H), 1.11 (d, J = 6.9 Hz, 3H), 0.42 (s, 3H), 0.16 (s, 3H). 13 C NMR(CDCl3): δ 155.84, 140.39, 139.06, 137.84, 137.35, 135.86, 134.80, 128.83,128.09, 123.04, 122.30, 111.85, 64.41, 64.13, 47.15, 29.36, 24.35, 21.46,21.21, 1.07, -0.68.

[0645] [9-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane

[0646]

[0647] At -50℃, nA hexane solution of BuLi (2.5 M, 5.0 ml, 12.5 mmol) was added in a single dose to a solution of 5-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin (3.65 g, 12.5 mmol) in a mixture of 50 ml diethyl ether and 50 ml THF. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C and 100 mg CuCN was added. The resulting mixture was stirred at -20 °C for 15 min, and then approximately 12.5 mmol of a solution of chloro[9-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane in 100 ml diethyl ether was added in a single dose. The mixture was stirred overnight at room temperature, then filtered through a silica gel 60 filter (40–63 µm) and washed with 2 × 40 mL of diethyl ether. The combined pale yellow eluent was evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, 600 mL, eluent: hexane: dichloromethane = 1:3, vol.). This procedure yielded 7.10 g (84.9%, approximately 97% purity) of the title product (a mixture of approximately 63:37 stereoisomers) as a white solid. This product was ready for use without further purification.

[0648] trans-dimethylsilanediyl[9-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride

[0649]

[0650] At room temperature, nA hexane solution of BuLi (2.5 M, 8.5 mL, 21.25 mmol) was added in a single batch to a solution of [9-(3,5-dimethylphenyl)-7-isopropyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-6H-indeno[5,6-b][1,4]dioxin-6-yl]dimethylsilane (7.10 g, 10.6 mmol) in 110 mL of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to 0 °C and ZrCl4 (2.47 g, 10.6 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give an orange suspension. The suspension was evaporated to dryness. The solid formed was extracted with 50 mL of boiling toluene. Based on NMR spectral evidence, the obtained extract contained a mixture of approximately 1:1 trans and cis isomers of CM4, as well as polymer byproduct impurities. The extract was evaporated to approximately 30 ml, and 15 ml of hexane was added. The red solid precipitated from this solution within 15 min was collected and dried under vacuum. This procedure yielded 2.2 g of the cis isomer as a solvate with approximately 0.45 molecules of toluene and 0.2 molecules of hexane. 7 ml of hexane was then added to the mother liquor. The orange solid precipitated from this solution overnight was collected and dried under vacuum. This procedure yielded 2.3 g of a mixture of approximately 4:1 trans and cis isomers. This isomer mixture was crystallized from a mixture of 10 ml toluene and 3 ml hexane to give 250 mg of a mixture of approximately 3:1 cis and trans isomers. The mother liquor was evaporated to approximately 7 ml, and 5 ml of hexane was added. The orange solid precipitated from this solution at room temperature was collected and dried under vacuum. The procedure yielded 1.2 g of a mixture of trans and cis isomers in a ratio of approximately 93:7. Crystallization of this mixture from a mixture of 5 ml toluene and 3 ml hexane gave 420 mg of the pure trans isomer.

[0651] cis isomers:

[0652] C 44 H 46 Analytical values ​​of Cl2O4SiZr: C, 63.74; H, 5.59. Measured values: C, 63.98; H, 5.75.

[0653] 1H NMR (CDCl3): δ 7.18 (br.s, 4H), 7.05 (s, 1H), 7.03 (s, 1H), 6.96(s, 1H), 6.94 (s, 1H), 6.47 (s, 1H), 6.43 (s, 1H), 4.23-4.16 (m, 4H), 4.11-4.05 (m, 4H), 3.03 (sep, J = 6.6 Hz, 1H), 2.34 (s, 6H), 2.33 (s, 6H), 2.24(s, 3H), 1.36 (s, 3H), 1.33 (d, J = 6.6 Hz, 3H), 1.17 (s, 3H), 1.15 (d, J =6.8 Hz, 3H).

[0654] 13 C NMR (CDCl3): δ 148.02, 144.70, 144.65, 142.94, 142.76, 137.38,137.35, 134.69, 133.09, 131.80, 131.30, 129.16, 127.69, 123.90, 123.15,122.18, 121.50, 120.57, 112.99, 110.62, 110.30, 80.80, 79.62, 64.58, 64.10,30.36, 29.50, 21.45, 21.41, 20.02, 17.99, 3.43, 2.69.

[0655] trans isomer:

[0656] C 44 H 46 Analytical values ​​of Cl2O4SiZr: C, 63.74; H, 5.59. Measured values: C, 63.90; H, 5.76.

[0657] 1H NMR (CDCl3): δ 7.27 (br.s, 4H), 7.02 (s, 1H), 6.97 (s, 1H), 6.95(s, 2H), 6.59 (s, 1H), 6.57 (s, 1H), 4.28-4.15 (m, 8H), 3.22 (sep, J = 6.7Hz, 1H), 2.34 (s, 12H), 2.21 (s, 3H), 1.23 (s, 3H), 1.22 (s, 3H), 1.07 (d, J= 6.7 Hz, 3H), 1.05 (d, J = 6.7 Hz, 3H).

[0658] 13 C NMR (CDCl3): δ 147.65, 145.69, 145.18, 143.68, 143.15, 137.56 (br.s), 137.40, 135.09, 134.53, 134.50, 131.06, 129.28, 129.22, 128.60, 127.89,127.79, 123.20, 123.07, 122.63, 119.92, 119.56, 114.87, 108.89, 108.08,79.76, 77.87, 64.60, 64.56, 64.38, 64.23, 30.65, 29.19, 21.43, 21.37, 19.49, 18.87, 3.16, 2.77.

[0659] Catalyst synthesis, the chemicals used

[0660] 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.

[0661] All catalysts were prepared using Sunspera AGC DM-L-303 silica calcined at 600°C. MAOAxion CA1330 was ready to use upon receipt and should be stored at -20°C for no more than 6 months.

[0662] Catalyst preparation

[0663] 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 equal amount of MAO added to the metallocene / toluene slurry to promote complete dissolution of the metallocene.

[0664] Preparation of SiO2 / MAO Activated Support

[0665] 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).

[0666] SiO2 / MAO / CM1 catalyst = Synthesis of contrast catalyst 1 (CC1)

[0667] In a nitrogen-filled glove box, 2.5 mL of dry toluene was added to 27 mg of metallocene racemic dimethylsilanediylbis(2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconia. The solution was stirred at room temperature for 30 minutes. Next, 2.0 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 red, free-flowing powder.

[0668] SiO2 / MAO / CM2 catalyst = Synthesis of contrast catalyst 2 (CC2)

[0669] In a nitrogen-filled glove box, 2.3 mL of dry toluene was added to 40.4 mg of metallocene CM2, followed by 0.2 mL of a 30 wt% MAO toluene solution (Axion CA1330), and the mixture was stirred at room temperature for 60 min. 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 then vacuum dried at 60 °C for 1 hour to obtain the catalyst as a red, free-flowing powder.

[0670] SiO2 / MAO / CM3 catalyst = Synthesis of contrast catalyst 3 (CC3)

[0671] In a nitrogen-filled glove box, 2.5 mL of dry toluene was added to 27.3 mg of metallocene CM3. 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.

[0672] SiO2 / MAO / CM4 catalyst = Synthesis of contrast catalyst 4 (CC4)

[0673] In a nitrogen-filled glove box, 2.5 mL of dry toluene was added to 25.0 mg of metallocene CM4. 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 yellow, free-flowing powder.

[0674] SiO2 / MAO / CM5 catalyst = Synthesis of contrast catalyst 5 (CC5)

[0675] In a nitrogen-filled glove box, 2.5 mL of dry toluene was added to 26.3 mg of metallocene racemic dimethylsilanediylbis[2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (metallocene CC5) placed in a diaphragm flask. The mixture was stirred at room temperature for 30 minutes. Next, 2.0 g of SiO2 / MAO batch V410 was placed in a diaphragm flask. The toluene solution of the metallocene was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting powder was allowed to stand for 1 hour, then transferred to a Schlenk flask and dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a salmon-red free-flowing powder.

[0676] SiO2 / IM1 catalyst = Synthesis of catalyst 1 (IC1) of the present invention

[0677] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 24.0 mg of metallocene IM1. The mixture was stirred at room temperature for 30 min, and then, to promote metallocene dissolution, 0.1 mL of a 30 wt% MAO toluene solution (Axion CA1330) was added, and stirring was continued at room temperature for another 30 min. 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 min, 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.

[0678] SiO2 / MAO / IM2 catalyst = Synthesis of catalyst 2 (IC2) of the present invention

[0679] In a nitrogen-filled glove box, 2.7 mL of dry toluene was added to 24.9 mg of metallocene IM2. The mixture was stirred at room temperature for 30 min, and then, to promote metallocene dissolution, 0.1 mL of a 30 wt% MAO toluene solution (Axion CA1330) was added, and stirring was continued at room temperature for another 30 min. 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 min, while gently mixing. The resulting mixture was shaken to homogenize and allowed to stand for 1 hour. The resulting solid was vacuum dried at 60 °C for 1 hour to obtain the catalyst as a pinkish-brown free-flowing powder.

[0680] SiO2 / MAO / IM3 catalyst = Synthesis of catalyst 3 (IC3) of the present invention

[0681] In a nitrogen-filled glove box, 2.5 mL of dry toluene was added to 27.2 mg of metallocene IM3. 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 yellow, free-flowing powder.

[0682] The metallocene content in each catalyst was calculated using mass balance. These values ​​are listed in Table 1:

[0683] Table 1: Catalysts tested and their metallocene content

[0684]

[0685] Aggregate Examples

[0686] monomers and gases

[0687] 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 column packing PolyMax301 T-4427B (60°C; Cu / CuO), MS13X-APG 1 / 16 molecular sieve, and SelexsorbCOS 1 / 8.

[0688] Propylene homopolymerization process (bulk, 20-L reactor)

[0689] An additional 3.95 kg of propylene was added 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. Triethylaluminum (0.8 ml of 0.62 mol / L n-heptane solution) was added using a 250 g propylene feed stream, followed by 0.5 NL H₂ over one minute via a mass flow controller. The reactor temperature was stabilized at 25 °C (HB-Therm), and the solution was stirred at 250 rpm for at least 20 min. The catalyst was then injected as described below.

[0690] Load the required amount of solid catalyst into a 5 ml stainless steel vial. Install this feed system on the port of the autoclave lid. Then purge the catalyst into the reactor with 350 g of propylene. Maintain the stirring speed at 250 rpm and prepolymerize at 25°C or 30°C for 10 minutes. Then, at the end of the prepolymerization step, add a second equal amount of H2 over 1 minute at 30°C. Then raise the polymerization temperature to 75°C. Keep the reactor temperature constant throughout the polymerization process. Start measuring the polymerization time when the temperature is 2°C lower than the set polymerization temperature. When the set polymerization time has elapsed, stop the reaction by injecting 5 ml of ethanol, cooling the reactor, and simultaneously flash-evaporating the volatile components. After purging the reactor three times with N2 and performing one vacuum / N2 cycle, open the reactor, remove the polymer powder, and dry it overnight in a fume hood. Add 0.5 wt% Irganox B225 (dissolved in acetone) to 100 g of polymer, then dry it overnight in a fume hood and for an additional 1 hour in a vacuum drying oven at 60°C.

[0691] Results of propylene polymerization (liquid propylene)

[0692] The aggregation results are shown in Table 2.

[0693] Table 2

[0694]

[0695] Figure 1 Catalysts IC1, IC2, and IC3 are shown to be more active than catalysts CC2, CC3, and CC4.

[0696] Figure 2 The results show that MAO-activated metallocenes IM1, IM2, and IM3 (catalysts IC1, IC2, and IC3) produce hPP with higher melting points than CM1, CM2, and CM3 (catalysts CC1, CC2, and CC3) (i.e., more isoselective in propylene polymerization).

[0697] Furthermore, although CC4 has relatively high isoselectivity, its activity is very low and its MFR response to H2 is too strong; therefore, it is not suitable for producing hPP at acceptable productivity across the entire desired MFR range.

[0698] Compared to IC3 (IE10), CC3 (CE5) produces T m Lower hPP.

[0699] A second essential requirement for metallocene catalysts is their ability to introduce ethylene (C2) into the copolymer chain in a random manner, particularly in the production of propylene / ethylene random copolymers in liquid-phase or gas-phase copolymerization, whereby ethylene activates the catalyst productivity without reducing the molecular weight of the copolymer. In other words, the addition of ethylene to the polymerization system should not significantly increase the polymer's molecular weight ratio (MFR). This latter limitation is a common drawback of most metallocene catalysts and needs to be overcome.

[0700] Tables 3, 4, and 5 compare the results of C3 / C2 random copolymerization at ~2 wt% C2 using catalysts IC1, IC2, CC1, CC2, and CC5 with those of hPP. Ethylene exhibits very strong activating effects on both catalysts IE1 and IE2, as well as a positive effect on reducing the polymer MFR, while the opposite was observed for all comparative examples.

[0701] Table 3. Comparison of hPP and rPP results: Polymerization conditions

[0702]

[0703] Table 4. Comparison of hPP and rPP results: Aggregation results

[0704]

[0705] Table 5. FTIR and NMR data of rPP copolymers and corresponding hPPs

[0706]

[0707] The third essential requirement for metallocene catalysts is their ability to produce high-melting-point hPP matrices in gas-phase or liquid-phase propylene polymerization and to produce high-molecular-weight amorphous ethylene / propylene copolymers in the gas phase in the production of impact copolymers.

[0708] As shown in Tables 6, 7 and 8, the performance of IC1 and IC2 is compared with that of CC1, CC2, CC3 and CC5: Clearly, compared with CC2, IC1 and IC2 not only have higher activity than the comparative catalysts, but also produce a matrix with a higher melting point and a higher molecular weight rubber.

[0709] Table 6. Multiphase copolymers: Experimental conditions

[0710]

[0711] Table 7. Multiphase copolymers: Results and polymer analysis of the whole material

[0712]

[0713] Table 8. Analysis of the soluble portion of multiphase copolymers

[0714]

Claims

1. Metallocene complexes of formula (I) (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 or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group; n are independent of each other, either identical or different, and are integers from 1 to 5; 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H; R 5 and R 6 Each is independently C1-C 10 -The hydrocarbon group or the adjacent oxygen atom together form -O(R) 61 ) m -O-, where R 61 It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 2 to 4; R 5’ and R 6’ Each is independently C1-C 10 -The hydrocarbon group or the adjacent oxygen atom together form -O(R) 61’ ) m -O-, where R 61’ It is independently a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group and m is an integer from 1 to 4; R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

2. The metallocene complex of formula (I) according to claim 1, 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 - A hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group; 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H; m are independent of each other, either identical or different, and are integers from 2 to 4; Each R 61 They may be independently identical or different from each other, and are -CH2-, -CHR*-, or -C(R*)2- groups, wherein R* is a C1-C2-alkyl group; R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

3. The metallocene complex of formula (I) according to any one of claims 1 to 2, having formula (Ic) (I-c) 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 - A hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group; 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 at least one R 3 Not H and at least one R 4 Not H; m are independent of each other, either identical or different, and are integers from 2 to 4; Each R 61 They are independently identical or different from each other, and are -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group.

4. The metallocene complex of formula (I) according to any one of claims 1 to 2, having formula (Id) (I-d) 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 - A hydrocarbon group, which optionally contains up to two heteroatoms of groups 14-16 of the periodic table, or forms a C4-C8 ring together with the Si atoms to which they are attached; R 2 and R 2’ Each being independently the same or different from the others is C6-C. 10 -Aryl, heteroaryl or CH2-R 21 , where R 21 Is it H or C1-C? 10 -Hydrocarbon group; 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; m are independent of each other, either identical or different, and are integers from 2 to 4; Each R 61 They are independently identical or different from each other, and are -CH2-, -CHR*-, or -C(R*)2-, where R* is a C1-C2-alkyl group.

5. The metallocene complex of formula (I) according to any one of claims 1, 2 and 4, having formula (Ie) (Ie) 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 - A 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; 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 present phenyl group has at least one R 3 Not H and at least one R 4 Not H; R 7 Is it H, Me, OMe, or C6-C? 20 -Aryl, where C6-C 20 -Aryl is R 3 Substitution 1 to 5 times, wherein at least one R of each aryl group 3 Not H.

6. The metallocene complex of formula (I) according to any one of claims 1 to 3 and 5, having formula (If) (I-f) 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 - A 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; 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 at least one R 3 Not H and at least one R 4 Not H.

7. The metallocene complex of formula (I) according to any one of claims 1, 2, 4 and 5, having formula (Ig) (I-g) 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 - A 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; 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.

8. The metallocene complex according to any one of claims 1 to 6, wherein Two Rs for each phenyl group present 3 Not H and R 3 Same, and The two R's on the phenyl group 4 It's not H, and these two Rs 4 same.

9. The metallocene complex according to any one of claims 1 to 7, wherein the complex is: Dimethylsilanediyl-bis[9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride; Dimethylsilanediyl-bis[η5-9-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-indeno[5,6-b][1,4]dioxin-6-yl]zirconium dichloride; or Dimethylsilanediyl[5,9-bis(3,5-dimethylphenyl)-7-methyl-2,3-dihydroindo[5,6-b][1,4]dioxin-6-yl][9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydroindo[5,6-b][1,4]dioxin-6-yl]zirconium dichloride.

10. A polymerization catalyst, comprising, preferably substantially, the following: (i) the metallocene complex of formula (I) according to any one of claims 1 to 9; (ii) a catalyst system comprising a catalyst containing a Group 13 element; and (iii) Optional carrier.

11. The polymerization catalyst according to claim 10, wherein the co-catalyst (ii) is an aluminoxane co-catalyst, preferably without any other co-catalyst.

12. The polymerization catalyst according to claim 10 or 11, wherein it is supported on silica.

13. A method for polymerizing propylene, comprising reacting propylene and optionally at least one of ethylene and C4-C4 polymers in the presence of a metallocene catalyst according to any one of claims 10 to 12. 10 The comonomers of α-olefin comonomers are polymerized.

14. A method for preparing a multiphase polypropylene copolymer, comprising: (I) Propylene is bulk polymerized in the presence of the polymerization catalyst according to claims 10 to 12 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.

15. 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 9 to 11 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 matrix and the polymerization catalyst and in the gas phase, propylene and ethylene are polymerized to form a multiphase polypropylene copolymer comprising a homopolymer matrix and ethylene propylene rubber (EPR).

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