Metallocenes for making propylene copolymers

Abstract

The present disclosure relates to a process for producing a propylene copolymer resin comprising polymerizing propylene and at least one comonomer selected from the group consisting of ethylene and C4-C10 alpha olefin comonomers; wherein the process is carried out in the presence of a polymerization catalyst comprising: (i) a metallocene complex of formula (I); (ii) a co-catalyst system comprising a co-catalyst comprising a Group 13 element; and (iii) optionally a carrier. Wherein the metallocene complex of formula (I) is the following formula (I) wherein Mt is Zr or Hf; x is a sigma ligand; r < 1 >, each independently, equal to or different from each other, is a C1-C20 hydrocarbon group, optionally containing up to two heteroatoms of groups 14-16 of the periodic table, or forming together with the Si atom to which they are attached a C4-C8 ring; r2 and R2'are each, independently, equal to or different from each other, CH2-R21 wherein R21 is H, a linear or branched C1-C6-alkyl group, a C3-C8-cycloalkyl group, or a C6-C9-aryl group, with the proviso that R2 and R2 'are not both methyl; r3 and R4 are each independently, equal to or different from each other, H, a linear or branched C1-C6-alkyl group, a C7-C20-arylalkyl group, a C7-C20-alkylaryl group, a C6-C20-aryl group or-OR31 wherein R31 is a C1-C10-hydrocarbyl group wherein at least one R3 of each phenyl group is not H and at least one R4 is not H; r5 and R6, each independently equal to or different from each other, are C1-C10 hydrocarbyl groups, or may form together with the C atom to which they are attached a C5-C7 carbocyclic ring; r51'is a C1-C10-hydrocarbyl group, and R6 'is C (R61) 3, wherein R61 is a linear or branched C1-C6-alkyl group.

Description

Technical Field

[0001] This disclosure relates to novel bisindenyl ligands, their complexes, and catalysts comprising these complexes. This disclosure also relates to the use of novel bisindenyl metallocene catalysts in the production of polypropylene copolymers, particularly copolymers with ethylene and / or butene, especially propylene-ethylene-butene terpolymers, which exhibit high activity levels, high molecular weights, and therefore low molecular weight flow rates (MFRs), and possess ideal melting points and sealing initiation temperatures. Background Technology

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

[0003] Metallocene catalysts are also used to produce propylene-butene copolymers and propylene-ethylene-butene terpolymers. These copolymers and terpolymers are particularly used in membranes, such as blown or cast films, and in the production of sealing layers for multilayer BOPP films. These copolymers and terpolymers must have specific MFR2 values, for example, 0.5 to 3 for blown films, 8-10 for cast films, and the MFR2 must match the MFR2 of the hPP core layer; in the case of sealing layers for multilayer BOPP films, the MFR2 is typically 6 to 8. The main advantage of using metallocene catalysts to produce propylene-butene copolymers and propylene-ethylene-butene terpolymers is that metallocene catalysts exhibit significantly higher reactivity for higher olefins (such as 1-butene and 1-hexene) compared to Ziegler-Natta catalysts. On the other hand, in such copolymerizations using metallocene catalysts, higher olefins tend to decrease the molecular weight of the copolymer, i.e., increase its MFR2. Therefore, it is necessary to reduce the amount of hydrogen used in such methods, but this in turn leads to a decrease in catalyst productivity. For example, solutions to this problem have been described in WO2019215122 and EP20193414, which use a combination of two activators, namely methylaluminoxane and triphenylmethyltetra(pentafluorophenyl)borate.

[0004] WO2019179959 describes a C1 symmetrical diindene complex comprising an indene moiety with 5-methoxy and 6-tert-butyl substituents and an indacenyl moiety with two aryl substituents at positions 4 and 8. The production of propylene-butene copolymers using one of such metallocene catalysts formulated in silica catalysts containing methylaluminoxane and triphenylmethyltetra(pentafluorophenyl)borate activators is also described in WO2023046573 and WO2023046824. With such prior art catalysts, it is sometimes difficult to obtain high molecular weights (e.g., propylene-butene copolymers and propylene-ethylene-butene terpolymers) while maintaining the desired catalyst productivity levels.

[0005] Therefore, the inventors sought to identify new metallocenes capable of providing high molecular weights (e.g., propylene-butene copolymers and propylene-ethylene-butene terpolymers) while maintaining desired catalyst productivity levels, particularly in the case of propylene terpolymerization, especially between propylene, butene, and ethylene. The desired catalysts should also exhibit improved performance in high-temperature polymerization, particularly in loop reactors. Summary of the Invention

[0006] One object of this disclosure is to provide a novel method for producing propylene copolymer resins, comprising reacting propylene with at least one compound selected from ethylene and C4-C4 copolymers. 10 The comonomers of α-olefin comonomers are polymerized, a method that can be used to provide copolymer resins with sufficiently low MFR2 at the desired productivity level.

[0007] The objective of this disclosure is achieved by utilizing a metallocene complex of formula (I), characterized as described in the independent claim. Preferred embodiments of this disclosure are disclosed in the dependent claims.

[0008] Surprisingly, it was found that specific C1-symmetric metallocenes with straight-chain alkyl substituents larger than methyl at one or both 2-positions of the ligand, combined with specific substitutions at other ligand positions, provided the desired properties.

[0009] definition

[0010] The following definitions are used throughout this description:

[0011] The term "C1-C" 20 "-hydrocarbon group" includes C1-C 20 -alkyl, C2-C 20 -Alkenyl, C2-C 20 -Alynyl group, C3-C 20 -Cycloalkyl, C3-C 20 -cycloalkenyl, C6-C 20-Aryl, C7-C 20 -alkylaryl and C7-C 20 -Arylalkyl, or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C1-C1 is preferred. 20 -The hydrocarbon group is C1-C 20 -alkyl, C4-C 20 -Cycloalkyl, C5-C 20 -cycloalkyl-alkyl, C7-C 20 -alkylaryl, C7-C 20 -Arylalkyl and C6-C 20 -Aryl, especially C1-C 10 -alkyl, C6-C 10 -Aryl and C7-C 12 -Arylalkyl, such as C1-C8 alkyl. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0012] The term "C1-C" 10 "-hydrocarbon group" includes C1-C 10 -alkyl, C2-C 10 -Alkenyl, C2-C 10 -Alynyl group, C3-C 10 -Cycloalkyl, C3-C 10 -cycloalkenyl, C6-C 10 -Aryl, C7-C 10 -alkylaryl and C7-C 10 -Arylalkyl, or of course, mixtures of these groups, such as cycloalkyl groups substituted with alkyl groups. Unless otherwise specified, C1-C1 is preferred. 10 -The hydrocarbon group is C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -alkylaryl, C7-C 10 -Arylalkyl and C6-C 10 -Aryl, especially C1-C 10 -alkyl, C6-aryl and C7-C 10 -Arylalkyl, such as C1-C6-alkyl. Most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl and benzyl.

[0013] It should be noted that straight-chain and branched hydrocarbon groups cannot contain cyclic units. Aliphatic hydrocarbon groups cannot contain aryl rings.

[0014] The term “heteroatoms of groups 14-16 of the periodic table” includes, for example, Si, N, O, or S.

[0015] As used in this article, the combination-R 1 The term "C4-C8-ring" in 2Si- refers to a cyclic group containing 4 to 8 carbon atoms and one Si atom, including, for example, silicone diesters, such as silicone butane, silicone pentane, or 9-silicon fluorene.

[0016] When it comes to complex definitions, the term "halogen" includes fluorine, chlorine, bromine, and iodine groups, especially chlorine or fluorine groups.

[0017] 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.

[0018] 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.

[0019] The numbering of these rings will be evident from the structure shown in this article.

[0020] 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.

[0021] The term “molecular weight” as used in this article refers to weight-average molecular weight Mw, unless otherwise stated.

[0022] 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

[0023] polymerization

[0024] This invention relates to a method for producing propylene copolymer resins, comprising reacting propylene with at least one polymer selected from ethylene and C4-C4 polymers in the presence of a polymerization catalyst comprising a specific metallocene catalyst. 10 The comonomers of the α-olefin comonomers, preferably at least two selected from ethylene and C4-C4, are preferred. 10 Different comonomers of α-olefin comonomers, more preferably ethylene and at least one C4-C 10 The α-olefin comonomer is polymerized, and the specific metallocene catalyst comprises, preferably substantially, and more preferably, the following:

[0025] (i) Metallocene complexes of formula (I) as described herein;

[0026] (ii) a catalyst system comprising a catalyst containing a Group 13 element; and

[0027] (iii) Optional carrier.

[0028] Details of the polymerization catalyst are discussed in the section on polymerization catalysts. The polymerization in the method of the present invention can be carried out in one or more steps, such as 1, 2, or 3 steps. Preferably, the same polymerization catalyst is used in each step, and ideally, the polymerization is transferred sequentially from the prepolymerization step to the subsequent polymerization step in a well-known manner.

[0029] Prepolymerization

[0030] The method of the present invention can utilize an online prepolymerization step. The online prepolymerization step is carried out just before the first polymerization step (I) and can be carried out in the presence of hydrogen, although if present, its concentration should be low. The hydrogen concentration can be 0 to 1 mol (hydrogen) / kmol (propylene), preferably 0.001 to 0.1 mol (hydrogen) / kmol (propylene).

[0031] Ideally, the temperature conditions during the prepolymerization step should be kept low, for example, 0 to 50°C, preferably 5 to 40°C, and more preferably 10 to 30°C.

[0032] The prepolymerization stage preferably polymerizes only propylene monomers. The residence time of the prepolymerization reaction stage is short, typically 5 to 30 minutes.

[0033] The prepolymerization stage preferably produces less than 5 wt% of the total polymer formed, for example 3 wt% or less.

[0034] Prepolymerization is preferably carried out in its own dedicated reactor, ideally in a liquid propylene slurry. The prepolymerization catalyst is then transferred to the first polymerization step. However, especially in batch processes, prepolymerization can also be carried out in the same reactor as the first polymerization step.

[0035] Aggregation Steps

[0036] This invention includes the use of propylene and a mixture selected from ethylene and C4-C 10 At least one comonomer of the α-olefin comonomer, preferably selected from ethylene and C4-C 10 Two different comonomers of α-olefin comonomer, more preferably ethylene and at least one C4-C 10 The α-olefin comonomer is polymerized. In one embodiment, propylene is polymerized with ethylene and 1-butene.

[0037] The polymerization process may include one or more polymerization steps, provided that at least one polymerization step includes providing a propylene copolymer portion, preferably a terpolymer portion.

[0038] 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.

[0039] In one embodiment, the method includes the following steps: (I) mixing propylene with at least two compounds selected from ethylene and C4-C 10 Different comonomers of α-olefin comonomers, preferably ethylene and at least one C4-C 10 α-olefin comonomers are polymerized in a slurry reactor to produce propylene terpolymers.

[0040] In the described embodiment, the method is carried out in at least one slurry reactor. When using a slurry polymerization reactor, the method is typically carried out in at least one loop reactor. Ideally, polymerization takes place in bulk, i.e., in a liquid propylene medium. Generally, for slurry reactors, and particularly for bulk reactors, the reaction temperature is typically in the range of 60 to 100°C, preferably 70 to 85°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 0.1 to 5 hours (e.g., 0.3 to 2 hours). Hydrogen is preferably used in the polymerization step. The amount of hydrogen used is typically much larger than that used in the prepolymerization stage.

[0041] Multi-stage aggregation method

[0042] Preferably, propylene copolymer (e.g., propylene terpolymer) resins are produced in a multi-stage process comprising at least two reactors in series. In one example, this method is a multi-stage polymerization method that includes an optional but preferred prepolymerization step, followed by first and second polymerization steps. At least one polymerization step in the multi-stage polymerization method can be carried out in a gas-phase reactor.

[0043] A preferred method configuration is based on Borstar. ® Type cascade.

[0044] Therefore, in another embodiment, the method includes

[0045] (I) Propylene and at least one compound selected from ethylene and C4-C 10 The comonomers of the α-olefin comonomers, preferably at least two selected from ethylene and C4-C4, are preferred. 10Different comonomers of α-olefin comonomers, more preferably ethylene and at least one C4-C 10 The α-olefin comonomer is polymerized in at least one slurry reactor to produce a propylene copolymer comprising 50-99 wt% of the total weight of the final propylene copolymer resin product, and the method further includes the following steps:

[0046] (II) The reaction mixture from step (I) is transferred to a gas-phase reactor for the production of propylene copolymers comprising 1 to 50 wt% of the final propylene copolymer resin product.

[0047] Preferably, the method includes

[0048] (I) Propylene and at least two compounds selected from ethylene and C4-C 10 Different comonomers of α-olefin comonomers, more preferably ethylene and at least one C4-C 10 The α-olefin comonomer is polymerized in at least one slurry reactor to produce a propylene terpolymer comprising 50 to 99 wt% of the total weight of the final propylene terpolymer resin product, and the method further includes the following steps:

[0049] (II) The reaction mixture from step (I) is transferred to a gas-phase reactor for the production of propylene copolymers comprising 1 to 50 wt% of the final propylene copolymer resin product.

[0050] In one example, a) the method of the present invention (multi-stage method) for preparing propylene terpolymer resin includes:

[0051] (I') In the first polymerization step, preferably in at least one slurry reactor, propylene and a mixture selected from ethylene and C4-C are reacted in the presence of a polymerization catalyst. 10 At least one comonomer of an α-olefin comonomer, preferably ethylene, is polymerized to produce a propylene copolymer matrix (A); subsequently

[0052] (II”) In the second polymerization step, preferably in at least one gas-phase reactor, propylene and at least one copolymer selected from ethylene and C4-C are reacted in the presence of a polymerization catalyst and the propylene copolymer matrix (A) from step (I). 10 The comonomers of the α-olefin comonomers, preferably at least two selected from ethylene and C4-C4, are preferred. 10 Different comonomers of α-olefin comonomers, more preferably ethylene and at least one C4-C 10 α-olefin comonomers are polymerized to produce a propylene copolymer (e.g., propylene terpolymer) phase (B) dispersed in a propylene copolymer matrix (A), for example to provide a propylene copolymer, preferably a propylene terpolymer resin.

[0053] Preferably, in the preferred embodiment, a) the propylene copolymer matrix (A) produced in step (I') is produced in an amount less than or equal to 90 wt% of the total weight of the propylene terpolymer resin produced, and b) the propylene terpolymer phase (B) produced in step (II") is produced in an amount greater than or equal to 10 wt% of the total weight of the propylene terpolymer resin produced.

[0054] First polymerization step (I) - Production of propylene copolymer matrix phase

[0055] In one embodiment of the invention, the first polymerization step includes reacting propylene with at least one C4-C 10 The α-olefin comonomer is polymerized. In this embodiment, the comonomer polymerized with propylene can be ethylene or C4-C... 10 α-olefin comonomers, or mixtures of comonomers such as ethylene and C4-C can be used. 10 A mixture of α-olefin comonomers.

[0056] Preferred comonomers for propylene are ethylene, 1-butene, 1-hexene, 1-octene, or any mixture thereof, with ethylene being preferred. When ethylene comonomers are present in the polymer produced in the first polymerization step (I), their content may be up to 5 mol%, or 3.4 wt%, and when butene comonomers are present, their content may be up to 5 mol%, or 6.6 wt%, provided that their combined content relative to the total polymer is up to 5 mol.

[0057] The first polymerization step can be carried out in any suitable reactor or a series of reactors. The first polymerization step can be carried out in a slurry polymerization reactor (e.g., a loop reactor) or a gas-phase polymerization reactor or a combination thereof.

[0058] When using a slurry polymerization reactor, the method is typically carried out in at least one loop reactor. Ideally, polymerization takes place in bulk, i.e., in a liquid propylene medium. Generally, for slurry reactors, and especially for bulk reactors, the reaction temperature is typically in the range of 60 to 100°C, preferably 70 to 85°C. The reactor pressure is typically in the range of 5 to 80 bar (e.g., 20 to 60 bar), and the residence time is typically in the range of 0.1 to 5 hours (e.g., 0.3 to 2 hours). When using a gas-phase reactor, the reaction temperature is typically in the range of 60 to 120°C, preferably 70 to 90°C. The reactor pressure is typically in the range of 10 to 35 bar (e.g., 15 to 30 bar), and the residence time is typically in the range of 0.5 to 5 hours (e.g., 1 to 2 hours).

[0059] In a preferred embodiment, the first polymerization step is carried out in a slurry loop reactor cascaded with the gas-phase reactor. In this case, the polymer produced in the loop reactor is transferred to the first gas-phase reactor.

[0060] It is preferable to use hydrogen in the first polymerization step. The amount of hydrogen used is typically much larger than that used in the prepolymerization stage.

[0061] Second polymerization step (II) - gas phase production

[0062] The second polymerization step (II) of the method of the present invention may be a gas-phase polymerization step, wherein propylene and preferably at least two compounds selected from ethylene and C4-C are used. 10 Different comonomers of the α-olefin comonomer are polymerized in the presence of a polymerization catalyst and the polymer from step (I). This polymerization step is carried out in at least one gas-phase reactor, optionally in the presence of an inert gas (e.g., propane). Therefore, the second polymerization step can be carried out in a single gas-phase reactor or in more than one gas-phase reactor connected in series or parallel.

[0063] One or more C4-C 10 The α-olefin comonomer may be, for example, 1-butene, 1-hexene, 1-octene, or any mixture thereof. Preferably, step (II) comprises the polymerization of propylene, ethylene, and butene.

[0064] In the method of the present invention, the temperature in the gas-phase reactor is typically in the range of 60 to 120°C, preferably in the range of 65 to 110°C, more preferably in the range of 65 to 100°C, and even more preferably in the range of 70 to 90°C. Higher gas-phase reactor temperatures will, for example, benefit higher levels of productivity, and in some embodiments, will benefit the reactivity of the comonomer (e.g., ethylene).

[0065] In the method of the present invention, the reactor pressure is at least 10 bar, preferably at least 15 bar, more preferably at least 16 bar, typically in the range of 10 to 60 bar, preferably in the range of 15 to 50 bar.

[0066] Residence time in any gas-phase reactor is typically 0.5 to 8 hours (e.g., 0.5 to 4 hours). The gas used will be a mixture of monomers, which may optionally be a mixture with a non-reactive gas (e.g., propane).

[0067] The hydrogen content in one or more gas-phase reactors is important for controlling polymer properties, but is independent of the hydrogen added in the prepolymerization and first polymerization steps. Hydrogen remaining in one or more reactors from step I may be partially vented before being transferred to one or more gas-phase reactors from step I, but it may also be transferred to one or more gas-phase reactors from step II along with the polymer / monomer mixture from step I, where more hydrogen may be added to control the molecular weight (Mw) of the copolymer (preferably a terpolymer) to the desired value.

[0068] The production ratio or distribution (by weight) between the first polymerization step and the second polymerization step is ideally 55:45 to 90:10, preferably 55:45 to 87:13, and more preferably 60:40 to 85:15. Note that any small amount of polymer formed in the prepolymerization is considered part of the polymer prepared in the first polymerization step.

[0069] Polymerization catalyst

[0070] The method of the present invention uses a polymerization catalyst, which comprises, preferably substantially, and more preferably comprises:

[0071] (i) Metallocene complexes of formula (I);

[0072] (ii) a catalyst system comprising a catalyst containing a Group 13 element; and

[0073] (iii) Optional carrier.

[0074] Metallocene catalyst complexes

[0075] The metallocene catalyst complexes of the present invention are asymmetric. Asymmetry refers only to the fact that the two ligands forming the metallocene are different, that is, each ligand carries a set of substituents with different chemical properties.

[0076] The metallocene complexes of the present invention are preferably the trans configuration of chiral racemic-bridged bis-indenyl C1-symmetric metallocenes. Although the complexes of the present invention are formally C1-symmetric, they ideally maintain pseudo-C2 symmetry because they maintain C2 symmetry near the metal center, although not around the ligands. In terms of their chemical properties, trans and cis enantiomer pairs are formed during the synthesis of the complexes (in the case of C1-symmetric complexes). For the purposes of the present invention, racemic-trans refers to the two indenyl ligands oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-cis refers to the two indenyl ligands oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the figure below.

[0077]

[0078] Formula (I) and any sub-formulas are intended to cover both cis and trans configurations. Preferred metallocene catalyst complexes are trans-configured.

[0079] The metallocene complexes of the present invention are preferably used in the form of racemic trans isomers. Therefore, ideally, at least 95 mol%, for example at least 98 mol%, and especially at least 99 mol%, of the metallocene catalyst complexes are in the racemic trans isomer form.

[0080] The metallocene catalyst complexes of the present invention require a combination of three significant features of the ligand framework:

[0081] 1: Indene ligands with 4,8-diaryl substitution (preferably indane-based),

[0082] 2: A 5-alkyloxy group (preferably 5-alkoxyindene (preferably methoxyindene)) having a 6-tert-alkyl group (preferably tert-alkyl, most preferably tert-butyl) substituent, and

[0083] 3: At least one alkyl substituent larger than methyl is present at the 2-position of the ligand.

[0084] Therefore, the present invention utilizes the metallocene complex of formula (I).

[0085]

[0086] in

[0087] Mt is either Zr or Hf;

[0088] X is a σ-ligand;

[0089] 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;

[0090] R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, provided that R is present. 2 and R 2’ Not all of them are methyl groups;

[0091] 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;

[0092] R 5 and R 6 Each being independently the same or different from the others is C1-C. 10 Hydrocarbon groups, or they can form C5-C7 carbon rings together with the C atoms they are attached to;

[0093] R 51’ It is C1-C 10 -hydrocarbon group; and

[0094] R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0095] For the metallocene complex of formula (I) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0096] In the complex of formula (I), Mt is preferably Zr or Hf, with Zr being more preferred.

[0097] 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.

[0098] Preferably, R 1 Each being independently the same or different from the others is C1-C. 10 -Hydrocarbon group, more preferably C1-C 10 -alkyl, C4-C 10 -Cycloalkyl, C5-C 10 -cycloalkyl-alkyl, C7-C 10 -Arylalkyl, C6-C 10 -Aryl or C7-C 10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, or even more preferably two Rs 1All are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In one embodiment, each R... 1 Independently identical or different from each other, is arbitrarily determined by C1-C. 10 -alkoxy-substituted C1-C 10 -alkyl or C1-C6-alkyl. Preferably two Rs. 1 The groups are identical. Most preferably, the two R groups are identical. 1 They are all methyl groups.

[0099] Preferably, R 1 Each is independently the same or different from the others, and is a C1-C6 alkyl group, more preferably methyl.

[0100] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C3-C8 cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or cyclohexyl, provided that R is present. 2 and R 2’ Not all are methyl, R is preferred. 21 It is H, a straight-chain C1-C3-alkyl or a branched C3-alkyl, provided that R 2 and R 2’ Not all of them are methyl. R is preferred. 2’ It is not methyl, but preferably CH2-R. 21 , where R 21 It is a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, more preferably R. 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl, R 2 It is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, preferably R. 21 It is H, a straight-chain C1-C6-alkyl group, or a branched C3-alkyl group. R is further preferred. 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2’ It is ethyl or n-propyl.

[0101] Advantageously, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21It is H or a straight-chain or branched C1-C6-alkyl group; preferably H or a straight-chain group, more preferably H or a straight-chain C1-C6-alkyl group, and even more preferably H or a straight-chain C1-C4-alkyl group; preferably H, methyl, or ethyl, provided that R 2 and R 2’ Not all of them are methyl.

[0102] In some implementation schemes, R 2 and R 2’ One of them is a methyl group, and the other has the formula CH2-R. 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0103] In some implementation schemes, R 2 It is methyl, R 2’ Having the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0104] In some implementation schemes, R 2 and R 2’ None of them are methyl groups. For example, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

[0105] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31 , where R 31 It is a C1-C4 hydrocarbon group. Even more preferably, each R... 3 and R 4 Each is independently identical or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4Not H.

[0106] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0107] 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.

[0108] Advantageously, for two phenyl groups, one or two R on each phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 It is the same as 3',5'-dimethyl or 4'-tert-butyl.

[0109] 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.

[0110] In one implementation, each phenyl group has two R groups. 3 It's not H, and the R on both phenyl groups 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and the two R's on the phenyl group are... 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

[0111] Preferred R 5 and R 6 Together form -(R 56 )m-, where each R 56 Independently, it is a -CH2-, -CHR*-, or -C(R*)2- group, wherein R* is a C1-C2-alkyl group, preferably methyl, and m is 3 to 5, preferably 3 to 4; more preferably, it is in the -(R 56 ) m In, each R 56 It is -CH2-, where m is 3 to 5, preferably 3 to 4, and most preferably 3.

[0112] Preferred R 51’It is a straight-chain or branched C1-C6-alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, C7-C 10 -Arylalkyl, C7-C 10 -alkylaryl or C6-C 10 -aryl, more preferably straight-chain C1-C6-alkyl, branched C3-C6-alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0113] Preferred R 6 'Is C(R) 61 )3, where R 61 It is a straight-chain C1-C3-alkyl group; more preferably methyl. Therefore, advantageously, R 6 It is schuding.

[0114] From another perspective, the present invention utilizes the metallocene catalyst complex of formula (Ia).

[0115] (Ia)

[0116] in

[0117] Mt is either Zr or Hf;

[0118] X is a σ-ligand;

[0119] n is 1 to 3, for example 1, 2 or 3, preferably 1;

[0120] 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;

[0121] R 2 and R 2 'Each is independently the same as or different from the others, which is CH2-R' 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl group, provided that R is present. 2 and R 2 Not all of them are methyl;

[0122] 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;

[0123] R 51 'It is C1-C' 10 -hydrocarbon group; and

[0124] R 6 'Is C(R) 61 )3, where R 61 It is a straight-chain or branched C1-C6-alkyl group.

[0125] For the metallocene complex of formula (Ia) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0126] In the complex of formula (Ia), Mt is preferably Zr or Hf, with Zr being more preferred.

[0127] 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.

[0128] 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.

[0129] Preferably, R 1 Each is independently the same or different from the others, and is a C1-C6 alkyl group, more preferably methyl.

[0130] Preferably, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl, a branched C3-C6-alkyl, or a C3-C8 cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or cyclohexyl, provided that R is present. 2 and R 2’ Not all are methyl, R is preferred. 21 It is H, a straight-chain C1-C3-alkyl or a branched C3-alkyl, provided that R 2 and R 2’ Not all of them are methyl. R is preferred. 2’ It is not methyl, but preferably CH2-R. 21 , where R 21 It is a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, more preferably R. 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl, R 2 It is CH2-R 21 , where R 21 It is H, a straight-chain C1-C6-alkyl or a branched C3-C6-alkyl, preferably R. 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group. R is further preferred. 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2’ It is ethyl or n-propyl.

[0131] Advantageously, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group; preferably H or a straight-chain group, more preferably H or a straight-chain C1-C6-alkyl group, and even more preferably H or a straight-chain C1-C4-alkyl group; preferably H, methyl, or ethyl, provided that R 2 and R 2’ Not all of them are methyl.

[0132] In some implementation schemes, R 2 and R 2’ One of them is a methyl group, and the other has the formula CH2-R. 21 , where R21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0133] In some implementation schemes, R 2 It is methyl, R 2’ Having the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0134] In some implementation schemes, R 2 and R 2 None of them are methyl groups. For example, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

[0135] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31 , where R 31 It is a C1-C4 hydrocarbon group. Even more preferably, each R... 3 and R 4 Each is independently identical or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0136] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0137] Therefore, one or two R are preferred. 3 and / or R 4 The group is H. If the two R groups are H, then... 3 and / or R 4 If the group is H, then the remaining R 3 and / or R 4The groups are preferably located at the para position. If an R 3 and / or R 4 If the group is H, then the remaining R 3 and / or R 4 The group is preferably located at the meta position.

[0138] Advantageously, for two phenyl groups, one or two R on each phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 It is the same as 3',5'-dimethyl or 4'-tert-butyl.

[0139] For the indenyl moiety, one or two R on the phenyl group are preferred. 4 Not H, two Rs are preferred. 4 It's not H, the optimal choice is these two Rs. 4 Similar to 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0140] In one implementation, each phenyl group has two R groups. 3 It's not H, and the R on both phenyl groups 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and the two R's on the phenyl group are... 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

[0141] Preferred R 51’ It is a straight-chain or branched C1-C6-alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, C7-C 10 -Arylalkyl, C7-C 10 -alkylaryl or C6-C 10 -aryl, more preferably straight-chain C1-C6-alkyl, branched C3-C6-alkyl or C6-aryl, even more preferably straight-chain C1-C4-alkyl, even more preferably methyl or ethyl, most preferably methyl.

[0142] Preferred R 6’ It is C(R) 61 )3, where R 61 It is a straight-chain C1-C3-alkyl group; more preferably methyl. Therefore, advantageously, R 6’ It is tert-butyl.

[0143] From another perspective, this invention utilizes a metallocene catalyst complex of formula (Ib).

[0144] (Ib)

[0145] in

[0146] Mt is either Zr or Hf;

[0147] X is a σ-ligand;

[0148] 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;

[0149] R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H, a straight-chain or branched C1-C6-alkyl group, provided that R 2 and R 2 Not all of them are methyl;

[0150] 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.

[0151] For the metallocene complexes of formula (Ib) defined above, the following represent preferred embodiments, which can be selected individually or in combination:

[0152] In the complex of formula (Ib), Mt is preferably Zr or Hf, with Zr being more preferred.

[0153] 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.

[0154] 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.

[0155] Preferably, R 1 Each is independently the same or different from the others, and is a C1-C6 alkyl group, more preferably methyl.

[0156] 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, provided that R is present. 2 and R 2’ Not all are methyl; R is preferred. 2’ It is not methyl, but preferably CH2-R. 21 , where R 21 It is a straight-chain C1-C3-alkyl or a branched C3-alkyl, R 2 It is CH2-R 21 , where R 21 It is H, a straight-chain C1-C3-alkyl group, or a branched C3-alkyl group. R is further preferred. 2 It is methyl or ethyl. Most preferably, R 2 It is methyl or ethyl, R 2’ It is ethyl or n-propyl.

[0157] Advantageously, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is H or a straight-chain or branched C1-C6-alkyl group; preferably H or a straight-chain group, more preferably H or a straight-chain C1-C6-alkyl group, and even more preferably H or a straight-chain C1-C4-alkyl group; preferably H, methyl, or ethyl, provided that R2 and R 2’ Not all of them are methyl.

[0158] In some implementation schemes, R 2 and R 2’ One of them is a methyl group, and the other has the formula CH2-R. 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0159] In some implementation schemes, R 2 It is methyl, R 2’ Having the formula CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl group. In such an embodiment, R 21 Preferably, it is a straight-chain or branched C1-C4-alkyl group; more preferably, it is a straight-chain C1-C4-alkyl group, and even more preferably, it is a methyl or ethyl group.

[0160] In some implementation schemes, R 2 and R 2’ None of them are methyl groups. For example, R 2 and R 2’ Each being independently the same as or different from the others, is CH2-R 21 , where R 21 It is a straight-chain or branched C1-C6-alkyl, more preferably a straight-chain or branched C1-C4-alkyl, even more preferably methyl or ethyl, and even more preferably methyl.

[0161] Preferably, R 3 and R 4 Each is independently identical or different from the others, and is H, a straight-chain or branched C1-C6-alkyl or C6-C 20 aryl, more preferably H, straight-chain or branched C1-C4-alkyl or -OR 31 , where R 31 It is a C1-C4 hydrocarbon group. Even more preferably, each R... 3 and R 4 Each is independently identical or different from the others, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, wherein each phenyl group has at least one R. 3 Not H and at least one R 4 Not H.

[0162] In addition, each benzene ring may have the same substitution pattern, or the three benzene rings may have different substitution patterns.

[0163] 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.

[0164] Advantageously, for two phenyl groups, one or two R on each phenyl group 3 Not H, but more preferably R on the two phenyl groups. 3 It is the same as 3',5'-dimethyl or 4'-tert-butyl.

[0165] For the indenyl moiety, one or two R on the phenyl group are preferred. 4 Not H, two Rs are preferred. 4 It's not H, the optimal choice is these two Rs. 4 Similar to 3',5'-dimethyl or 3',5'-di-tert-butyl.

[0166] In one implementation, each phenyl group has two R groups. 3 It's not H, and the R on both phenyl groups 3 It is a straight-chain or branched C1-C6-alkyl group, preferably methyl, and the two R's on the phenyl group are... 4 It's not H, and these two Rs 4 It is a straight-chain or branched C1-C6 alkyl group, preferably methyl.

[0167] Preferred metallocene catalyst complexes are MC-I1, MC-I2 and MC-I3, as described in the examples below.

[0168] co-catalyst

[0169] 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. In some instances, organoboron and / or borate compounds are not used.

[0170] According to the present invention, the cocatalyst system comprising an aluminoxane cocatalyst and optionally a boron-containing cocatalyst is advantageously used in combination with the metallocene catalyst complexes defined above.

[0171] Preferably, only aluminum-containing cocatalysts (such as organoaluminum compounds used to activate metallocene catalysts) are used in this invention.

[0172] 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 complexes defined above.

[0173] 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.

[0174] The appropriate amount of catalyst will be well known to those skilled in the art.

[0175] Preferably, the amount of co-catalyst is selected to achieve a molar ratio below the defined range.

[0176] 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.

[0177] When using a boron cocatalyst, the molar ratio of boron (B) to metallocene metal ions (Mt) (preferably zirconium), B / Mt, can be in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, and especially 0.5:1 to 3:1 mol / mol. Even more preferably, the molar ratio of boron (B) to metallocene metal ions (Mt) (preferably zirconium), B / Mt, is 0.5:1 to 2:1.

[0178] Aluminoxane co-catalyst

[0179] Aluminoxane co-catalysts can be one of formula (A):

[0180] (A)

[0181] Where n is typically 6 to 20, and R has the following meanings.

[0182] 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).

[0183] The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used as cocatalysts according to the present invention are prepared by means of their chemical process rather than as pure compounds, the molar concentrations of the aluminoxane solutions mentioned below are based on their aluminum content.

[0184] Boron-containing cocatalyst

[0185] According to the present invention, the aluminoxane cocatalyst can be used in combination with the boron-containing cocatalyst.

[0186] 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.

[0187] 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.

[0188] Meaningful boron-containing cocatalysts include those compounds of formula (B).

[0189] BY3 (B)

[0190] Where Y is the same or different, and is hydrogen, C1-C 10 - Haloalkyl or C6-C 20 - Halogenated aryl groups or fluorine, chlorine, bromine or iodine.

[0191] 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).

[0192] 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).

[0193] 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.

[0194] Tris(pentafluorophenyl)borane is particularly preferred.

[0195] However, borates, i.e., compounds containing borate anions, are preferred. These compounds have the formula (C):

[0196] Z4B–W + (C)

[0197] Wherein Z is a substituted phenyl derivative, and the substituent is a halo-C1-C6-alkyl or halogen; W + It is a cationic counterion.

[0198] Preferably, the substituent of Z is fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0199] 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).

[0200] Preferred ionic compounds that can be used according to the present invention include:

[0201] Tributylammonium tetra(pentafluorophenyl)borate

[0202] Tributylammonium tetra(trifluoromethylphenyl)borate

[0203] Tributylammonium tetra(4-fluorophenyl)borate,

[0204] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid

[0205] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid

[0206] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

[0207] N,N-di(propylammonium) tetra(pentafluorophenyl)borate,

[0208] di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate,

[0209] Triphenylcarbomon tetra(pentafluorophenyl)borate

[0210] Or ferrocene tetra(pentafluorophenyl)borate.

[0211] Preferred is triphenylcarbium tetra(pentafluorophenyl)borate,

[0212] N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)boronic acid or

[0213] N,N-dimethylbenzylammonium tetra(pentafluorophenyl)boronic acid.

[0214] The preferred option is triphenylcarbium tetra(pentafluorophenyl)borate.

[0215] N,N-dimethylaniline tetratetra(pentafluorophenyl)boronic acid,

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

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

[0218] Catalyst manufacturing

[0219] 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.

[0220] Particularly preferred is that the support is a porous material, allowing the complex to be loaded into the pores of the support, for example using methods similar to those described in WO94 / 14856, WO95 / 12622, and WO2006 / 097497. Particle size is not critical, but is preferably in the range of 5 to 200 μm, more preferably 20 to 80 μm. The use of such supports is conventional in the art. Particularly preferred procedures for producing such supported catalysts are those described in WO2020 / 239598 and WO2020 / 239603.

[0221] In another embodiment, no external support is used, but the catalyst still exists in solid particulate form. Therefore, no external support material, such as an inert organic or inorganic support (e.g., silica as described above), is used. Such a catalyst can be prepared as described, for example, in WO2003 / 051934, WO2014 / 060540, and WO2019 / 179959.

[0222] The particulate carrier material used is an inorganic porous carrier, such as silica, alumina, or mixed oxides (e.g., silica-alumina), especially silica.

[0223] Silica carrier is preferred.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] The use of these carriers is common practice in this field.

[0230] 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).

[0231] The polymerization catalyst of the present invention can be produced by, for example, the method described in WO2020 / 239603 or WO2020 / 239598.

[0232] Polymerization catalysts containing such metallocenes can be produced by a method comprising the following steps:

[0233] P1-a) A porous inorganic support is mixed with a first portion of the aluminoxane cocatalyst in a hydrocarbon solvent to obtain an aluminoxane cocatalyst-treated support, which is then optionally heat-treated.

[0234] 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, and the boron-containing cocatalyst (if present) is added in an amount such that the molar ratio of boron to M in the feed is in the range of 0.1:1 to 10:1;

[0235] P1-c) Add the solution obtained in step b) to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0236] P1-d) The supported catalyst system thus obtained is dried.

[0237] 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.

[0238] In a preferred aspect of the invention, the method includes:

[0239] 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.

[0240] P2-b) The metallocene is dissolved in a hydrocarbon solvent, optionally with the addition of a methylaluminoxane cocatalyst, wherein the amount of the methylaluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt% of the total amount of the methylaluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of the methylaluminoxane cocatalyst, to obtain a metallocene solution optionally containing an aluminoxane cocatalyst;

[0241] P2-c) Add the metallocene solution to the support treated with the aluminoxane co-catalyst obtained in step a), and optionally...

[0242] P2-d) The supported catalyst system thus obtained is dried.

[0243] 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%.

[0244] 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).

[0245] polymer

[0246] A feature of this invention is that the claimed method is capable of forming polypropylene with a very high melting point. 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 one 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.

[0247] propylene copolymer

[0248] The method of this invention prepares ethylene or C4-C... 10 propylene copolymers of α-olefin comonomers, preferably containing ethylene and C4-C 10 Propylene terpolymers of α-olefin comonomers, more preferably propylene-ethylene-butene terpolymers, can be prepared with high productivity. The polymerization rate can be at least 13 kg polymer / g catalyst, preferably at least 14 kg polymer / g catalyst, more preferably at least 14.5 kg polymer / g catalyst. The polymerization temperature can be higher than 60°C, preferably higher than 65°C.

[0249] The method of the present invention can be used to produce propylene copolymers, preferably propylene terpolymers, with relatively low MFR2. For example, the MFR2 can be below 15, preferably below 10, and for example below 8. When such copolymers are produced in liquid monomers, the MFR2 can be below 10, preferably below 8.

[0250] The total monomer content of the propylene copolymer can be from 0.5 to 10% by weight, preferably from 1 to 8% by weight, for example, from 2 to 7% by weight. For example, the propylene copolymer can have an ethylene content of 0.5 to 2% by weight and be C4-C4. 10 A terpolymer containing 4 to 8% by weight of α-olefin comonomer. The propylene copolymer may contain 0.8 to 1.8% by weight of ethylene and be C4-C6.10 A terpolymer containing 4.5 to 7% by weight of α-olefin comonomer. The propylene copolymer may contain 0.9 to 1.5% by weight of ethylene and be C4-C6. 10 A terpolymer containing 4.8 to 6.5% by weight of α-olefin comonomer. The propylene copolymer may contain 1.0 to 1.3% by weight of ethylene and be C4-C6. 10 The propylene copolymer is a terpolymer containing 5.0 to 6.0% by weight of α-olefin comonomer. In one embodiment, the propylene copolymer may be a terpolymer containing 0.8 to 1.8% by weight of ethylene and 4.5 to 7% by weight of C4 α-olefin comonomer. The propylene copolymer may be a terpolymer containing 0.9 to 1.5% by weight of ethylene and 4.8 to 6.5% by weight of C4 α-olefin comonomer. The propylene copolymer may be a terpolymer containing 1.0 to 1.3% by weight of ethylene and 5.0 to 6.0% by weight of C4 α-olefin comonomer.

[0251] In some instances, the propylene copolymer has the ethylene content and C4-C content as described above. 10 The terpolymer has an α-olefin comonomer content (e.g., C4 α-olefin comonomer) and its MFR2 can be less than 15, preferably less than 10, for example less than 8. Some embodiments of this disclosure have the advantage that propylene copolymers with such MFR2 properties can be produced at desired productivity levels. Preferably, such propylene copolymers can be produced at relatively high productivity levels, for example, at least 13 kg polymer / gram catalyst, preferably at least 14 kg polymer / gram catalyst, more preferably at least 14.5 kg polymer / gram catalyst.

[0252] 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.

[0253] The invention will now be described with reference to the following non-limiting examples.

[0254] experiment

[0255] Measurement methods

[0256] Determination of Al, B and Zr (ICP method)

[0257] In a glove box, an equal volume (approximately 40 mg) of the catalyst was weighed into a glass weighing boat using an analytical balance. The sample was then exposed to air overnight while being placed in a steel secondary container equipped with an air inlet. The contents of the boat were then rinsed into a 20 mL Xpress microwave oven container with 5 mL of concentrated nitric acid (65%). The sample was then microwave-assisted digested at 150 °C for 35 min using a MARS 6 laboratory microwave apparatus. The digested sample was allowed to cool for at least 4 h and then transferred to a 100 mL glass volumetric flask. A standard solution containing 1000 mg / L LY and Rh (0.4 mL) was added. The flask was then filled with distilled water and shaken thoroughly. The solution was filtered through a 0.45 µm nylon syringe filter and analyzed using a Thermo iCAP 6300 ICP-OES and iTEVA software.

[0258] The instrument was calibrated for Al, B, Hf, Mg, Ti, and Zr using a blank solution (5% HNO3 solution) and six standard solutions (containing 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L of Al, B, Hf, Mg, Ti, and Zr, respectively, in a 5% distilled aqueous solution of HNO3). However, not every calibration point was used for every wavelength. Each calibration solution contained 4 mg / L of LY and Rh standards. Al at 394.401 nm was calibrated using the following calibration points: blank solution, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L. The calibration method for Al 167.079 nm is consistent with that for Al 394.401 nm, but 100 mg / L is excluded, and Zr 339.198 nm is calibrated using blank solution, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L standard solutions. Curve fitting and 1 / concentration weighting are used for the calibration curve.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] Catalyst activity

[0263] Catalyst activity is calculated based on the following formula:

[0264]

[0265] Catalyst productivity is calculated based on the following formula:

[0266]

[0267] Polymer powder bulk density

[0268] Instrument: Electronic balance: measuring range 0.1g-11000g

[0269] Glass graduated cylinder: Volume = Maximum 250 ml

[0270] Plastic medicine spoon: Volume = 125 ml

[0271] Plastic funnel: D=105 mm

[0272] 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.

[0273] Calculation: Polymer mass (g) / Measurement volume (ml)

[0274] XS

[0275] The xylene soluble fraction (XS) defined and described in this invention is determined according to ISO 16152 as follows: 2.5 ± 0.1 g of polymer is dissolved in 250 ml of o-xylene under reflux and continuous stirring in a nitrogen atmosphere. After 30 minutes, the solution is cooled, first at ambient temperature for 15 minutes, and then maintained at a controlled temperature of 25 ± 0.5 °C for 4 hours. The solution is then filtered through filter paper. To determine the xylene soluble content, an equal fraction of the filtrate (100 ml) is taken. This fraction is evaporated in a nitrogen stream, and the residue is vacuum dried at 100 °C until constant weight is achieved.

[0276] The soluble fraction (weight percentage) of xylene can then be determined as follows:

[0277] XS% = (100 xm 1 xv 0 ) / (m 0 xv 1 ),

[0278] 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.

[0279] 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.

[0280] GPC: Average molecular weight, molecular weight distribution, and polydispersity index (Mn, Mw, Mw / Mn)

[0281] 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).

[0282] 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 a dual light scattering detector with 15° and 90° angles (PL-LS 15 / 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 injection concentration of the polymer solution at 160 °C (c...) is... 160℃ ) Determine in the following manner.

[0283]

[0284] Where: w 25 (Polymer weight) and V 25 (Volume of TCB at 25℃).

[0285] 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:

[0286] K PS = 19 x 10 -5 ml / g, α PS = 0.655

[0287] K PP = 39 x 10 -5 ml / g, α PP= 0.725

[0288] Third-order polynomial fitting was used to fit the calibration data.

[0289] 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.

[0290] 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).

[0291] (1)

[0292] (2)

[0293] (3)

[0294] (4)

[0295] DSC

[0296] 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. SIT is calculated from the DSC curve as described in US2021309774.

[0297] melt flow rate

[0298] 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)).

[0299] NMR

[0300] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the comonomer content of polymers.

[0301] Using a Bruker Avance III 500 NMR spectrometer, the NMR spectra were observed at 500.13 and 125.76 MHz. 1 H and 13 C was used for the operation, and a quantitative record was made in the molten state. 13 C{ 1 H NMR spectroscopy. All spectra were performed using H NMR spectroscopy. 13Recordings were performed using a C-optimized 7 mm magic angle rotation (MAS) probe tip at 180 °C, with nitrogen used for all pneumatic devices. Approximately 200 mg of material was loaded into a 7 mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This device was chosen primarily for the high sensitivity required for rapid identification and accurate quantification {as described in Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol.Chem.Phys.2006;207:382; Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol.Chem.Phys.2007;208:2128; Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373}. Standard single-pulse excitation was employed, utilizing a NOE with a short cyclic delay of 3 s (as described in Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004;37:813; Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol.Chem.Phys.2006;207:382), and an RS-HEPT decoupling scheme was used {Filip, X., Tripon, C., Filip, C., J. Mag.Resn.2005, 176, 239, Griffin, JM, Tripon, C., Samoson, A., Filip, C., and Brown, SP, Mag.Res. In Chem. 2007, 45, S1, S198. A total of 16384 (16k) transients were obtained for each spectrum.

[0302] Quantitative 13 C{ 1 The ¹H NMR spectra were processed, integrated, and the quantitative properties were determined by integration. All chemical shifts were internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

[0303] The characteristic signal corresponding to the introduction of 1-butene {AJBrandolini, DDHills, “NMRspectra of polymers and polymer additives”, Marcel Deker Inc., 2000} was observed and the content of comonomers was quantified.

[0304] The amount of isolated 1-butene introduced into the PBP sequence was quantified using the integral of the αB2 site at 43.6 ppm combined with the number of reporter sites for each comonomer:

[0305] B = I αB2 / 2

[0306] The amount of 1-butene sequentially introduced into the PBBP sequence was quantified using the integral of the ααB2B2 site at 40.5 ppm combined with the number of reporter sites for each comonomer:

[0307] BB = 2 * I ααB2B2

[0308] In the presence of BB, the B value is corrected for the influence of the αB2 site generated by BB:

[0309] B = (I αB2 / 2) – BB / 2

[0310] The total 1-butene content is calculated based on the sum of isolated and continuously introduced 1-butene:

[0311] B 总计 = B + BB

[0312] The characteristic signal corresponding to the introduction of ethylene {AJBrandolini, DDHills, “NMRspectra of polymers and polymer additives”, Marcel Deker Inc., 2000} was observed and the content of comonomers was quantified.

[0313] The amount of isolated ethylene introduced into the PEP sequence was quantified using the integral of the Sββ site at 24.3 ppm combined with the number of reporter sites for each comonomer:

[0314] E = I Sββ

[0315] If a characteristic signal corresponding to ethylene in a continuously introduced PEE sequence is observed, the Sβδ site at 27.0 ppm is used for quantification:

[0316] EE = I Sβδ

[0317] Characteristic signals corresponding to regional defects were observed. The presence of isolated 2,1-erythro-type regional defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm, a methylene site at 42.4 ppm, and confirmed by other characteristic sites. The presence of 2,1-regional defects adjacent to ethylene units was indicated by two inequivalent Sαβ signals at 34.8 ppm and 34.4 ppm, and a Tγγ signal at 33.7 ppm, respectively.

[0318] Isolated 2,1-Erythian region defects (P 21e孤立 The amount was calculated using the integral of the methylene site at 42.4 ppm (I). e9 To quantify:

[0319] P 21e孤立 = I e9

[0320] If present, the 2,1 region defect (P) adjacent to ethylene E21 The amount was calculated using the integral of the methine site at 33.7 ppm (I). Tγγ Quantitative:

[0321] P E21 = I Tγγ

[0322] The total ethylene content is then calculated based on the sum of ethylene from isolated, continuously introduced, and neighboring defects in region 2,1:

[0323] E 总计 = E + EE + P E21

[0324] The amount of propylene was quantified based on the Sαα methylene site at 46.7 ppm, which includes all additional propylene units not covered by Sαα, such as the factor 3*P. 21e孤立 Corresponding to three missing propylene units from isolated 2,1-erythroid region defects:

[0325] P 总计 = I Sαα + 3*P 21e孤立 + B + 0.5*BB + E + 0.5*EE + 2*P E21

[0326] The total mole fractions of 1-butene and ethylene in the polymer are then calculated as follows:

[0327] fB =B总计 / (E) 总计 + P 总计 + B 总计 )

[0328] fE =E 总计 / (E) 总计 + P 总计 + B 总计 )

[0329] The molar percentage introduced by the comonomer is calculated from the mole fraction:

[0330] B [mol%] = 100 * fB

[0331] E [mol%] = 100 * fE

[0332] The weight percentage of comonomers introduced is calculated as a mole fraction:

[0333] B [wt%] = 100 * ( fB * 56.11 ) / ( (fE * 28.05) + (fB * 56.11) + ((1-(fE+fB)) * 42.08) )

[0334] E [wt%] = 100 * ( fE * 28.05 ) / ( (fE * 28.05) + (fB * 56.11) + ((1-(fE+fB)) * 42.08) )

[0335] Mole percentage of isolated 2,1-erythroide region defects relative to all propylene:

[0336] [21e] mol% = 100 * P 21e孤立 / P 总计

[0337] The molar percentage of defects in the 2,1 region adjacent to ethylene relative to all propylene:

[0338] [E21] mol% = 100 *P E21 / P 总计

[0339] The total number of defects in 2.1 is quantified as follows:

[0340]

[21] mol% = [21e] + [E21]

[0341] No characteristic signals corresponding to other types of regional defects (2,1-Soviet type, 3,1 insertion) were observed {Resconi,L., Cavallo, L., Fait, A., Piemontesi, F., Chem.Rev. 2000, 100, 1253}.

[0342] Metallocene synthesis

[0343] Synthesis of MC-C1

[0344] The synthesis of this metallocene has been carried out as described in WO2019179959, MC-2.

[0345] Synthesis of MC-C2

[0346] Isopropylmalonic acid

[0347]

[0348] 125 g of potassium hydroxide was placed in a solution at 1000 cm. 3 The aqueous solution was added to a solution of 110.0 g (544 mmol) diethyl isopropyl 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. Isopropylmalonic acid was extracted with 4 × 500 ml diethyl ether. The combined extracts were evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 76.4 g (96.1%) of isopropylmalonic acid as a white solid.

[0349] 1 H NMR (CDCl3): δ 9.72 (br.s, 2H), 3.24 (d, J = 8.3 Hz, 1H), 2.48-2.34(m, 1H), 1.07 (d, J = 6.8 Hz, 6H).

[0350] 2-Isopropylacrylic acid

[0351]

[0352] Diethylamine (62.4 ml, 44.3 g, 0.606 mol) was added dropwise to a solution of isopropylmalonic acid (76.4 g, 523 mmol) in 750 ml of ethyl acetate at 5 °C. Paraform (22.1 g, 0.736 mol) was added to the resulting suspension. The resulting mixture was refluxed for 5 h, then cooled to 5 °C, and 350 ml of diethyl ether and 1000 cm⁻¹ were added. 3 2M HCl. After mixing, the organic layer was separated, and the aqueous layer was extracted again with 2 × 500 ml diethyl ether. The combined organic phases were dried over Na₂SO₄ and then evaporated to dryness. The residue was purified by vacuum distillation to give 2-isopropylacrylic acid, bp 65℃ / 4 mm Hg. 57.0 g (95.5%) of colorless liquid was obtained.

[0353] 1 H NMR (CDCl3): δ 12.45 (br.s, 1H), 6.30 (s, 1H), 5.65 (t, 1H), 2.81 (septd, J = 6.9 Hz, J = 0.9 Hz, 1H), 1.11 (d, J = 6.9 Hz, 6H). 13C NMR (CDCl3): δ 173.30, 146.47, 124.31, 28.94, 21.76.

[0354] 6-tert-butyl-5-methoxy-2-isopropylindan-1-one

[0355]

[0356] At 50°C, 114.1 g (1.0 mol) of 2-isopropylacrylic acid was added to a mixture of 220 g P4O 10 The mixture was prepared with Eaton's reagent obtained from 1120 mL of MeSO3H. 131.2 g (0.8 mol) of 1-tert-butyl-2-methoxybenzene was added dropwise to the mixture while vigorously stirring at 50–53 °C (water bath temperature) for about 1 h. The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 1.5 L of cold water and 3 kg of ice. The crude product was extracted with 3 × 600 mL of dichloromethane. The combined organic phases were washed with an aqueous K2CO3 solution, dried over K2CO3, filtered through a silica gel 60 short pad (40–63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 193.8 g (93.0%, approximately 95% purity) of 6-tert-butyl-5-methoxy-2-isopropylindan-1-one as a pale yellow oil (bp 150–190 °C / 4 mm Hg).

[0357] 1 H NMR (CDCl3): δ 7.66 (s, 1H), 6.89 (s, 1H), 3.93 (s, 3H), 3.04 (dd,J = 17.4 Hz, J = 8.0 Hz, 1H), 2.84 (dd,J = 17.4 Hz, J = 3.8 Hz, 1H), 2.67-2.60 (m, 1H), 2.48-2.34 (m, 1H), 1.37 (s, 9H), 1.05 (d, J = 6.9 Hz, 3H), 0.77(d, J = 6.9 Hz, 3H). 13 C NMR (CDCl3): δ 207.45, 164.44, 155.10, 138.54, 130.07,121.69, 107.64, 55.14, 53.20, 35.00, 29.54, 28.87, 27.65, 20.96, 17.00.

[0358] 4-Bromo-6-tert-butyl-2-isopropyl-5-methoxyindan-1-one

[0359]

[0360] Bromine (20.8 ml, 64.9 g, 405.9 mmol) was added dropwise over 5 min to 97.0 g (0.372 mol) of 6-tert-butyl-2-isopropyl-5-methoxyindan-1-one, 113.2 g of sodium acetate, and 3.0 g of other compounds. n A mixture of Bu4NI, 310 ml dichloromethane, and 645 ml water was stirred vigorously at 5 °C. The mixture was stirred at 5 °C for 2 h, then a solution of 52.2 g sodium acetate in 290 ml water was added, followed by 10.8 ml (33.7 g, 210.8 mmol) bromine. The resulting mixture was stirred at this temperature for another 1 h, then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 3 × 250 ml dichloromethane. The combined organic extracts were dried over K2CO3, evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 124.84 g (98.9%, approximately 95% purity) of a pale yellow oil, which was ready for use without further purification.

[0361] 1H NMR (CDCl3): δ 7.68 (s, 1H), 4.04 (s, 3H), 3.04 (dd, J = 17.9 Hz, J= 8.1 Hz, 1H), 2.80 (dd, J = 17.9 Hz, J = 3.9 Hz, 1H), 2.71-2.64 (m, 1H), 2.49-2.35 (m, 1H), 1.40 (s, 9H), 1.08 (d, J = 6.9 Hz, 3H), 0.80 (d, J = 6.8Hz, 3H). 13 C NMR (CDCl3): δ 207.21, 162.59, 154.47, 145.24, 133.82, 121.03,116.56, 61.54, 53.32, 35.56, 30.54, 29.41, 28.94, 20.78, 17.17.

[0362] 6-tert-butyl-2-isopropyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0363]

[0364] 124.84 g (368.0 mmol) of 4-bromo-6-tert-butyl-2-isopropyl-5-methoxyindan-1-one, 69.7 g (464.7 mmol, 1.26 equivalents) of 3,5-Me2C6H3B(OH)2, and 1.9 g (3.72 mmol, 1 mol%) of Pd (P t A mixture of Bu3)2, 118.3 g Na2CO3, 600 ml 2-methyltetrahydrofuran, and 540 ml water was refluxed for 6 h. Then, 500 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 300 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a pale yellow solid. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane-dichloromethane = 1:1, then 1:5, vol.). 121.55 g (90.6%, approximately 95% purity) of pale yellow crystalline material was obtained.

[0365] 1H NMR (CDCl3): δ 7.71 (s, 1H), 7.04 (s, 1H), 7.03 (s, 2H), 3.31 (s,3H), 2.87 (dd, J = 18.5 Hz, J = 8.8 Hz, 1H), 2.65-2.54 (dd and m, 2H), 2.43-2.34 (s and m, 7H), 1.42 (s, 9H), 0.99 (d, J = 6.9 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). 13 C NMR (CDCl3): δ 208.19, 163.34, 153.44, 143.11, 138.08, 136.33, 132.64,132.12, 129.08, 127.20, 120.93, 77.00, 60.46, 53.37, 35.33, 30.50, 28.88,27.38, 21.39, 20.90, 17.25.

[0366] 5-tert-butyl-2-isopropyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0367]

[0368] NaBH4 (18.9 g, 0.5 mol, 1.5 equivalents) was added to a solution of 121.55 g (333.45 mmol) of 6-tert-butyl-2-isopropyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 600 mL of THF cooled to 5 °C. MeOH (300 mL) was added dropwise to the mixture at 5 °C over approximately 5 h, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 1000 mL of dichloromethane and 1000 mL of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 100 mL of dichloromethane. The combined organic phases were passed through a silica gel 60 mat (40–63 µm; eluent: dichloromethane) (~30 mL) to remove most of the palladium black. The resulting eluent was evaporated to dryness to give a gray solid block. 1.0 g of TsOH was added to this block in 1000 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 300 ml of dichloromethane. The combined organic phases were dried with K₂CO₃ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, hexane-dichloromethane = 5:1), followed by recrystallization from n-hexane (heat → -30 °C). This procedure yielded 96.93 g (83.4%) of pure 5-tert-butyl-7-(3,5-dimethylphenyl)-2-isopropyl-6-methoxy-1H-indene.

[0369] 1 H NMR (CDCl3): δ 7.24 (s, 1H), 7.09 (s, 2H), 6.99 (s, 1H), 6.46 (m,1H), 3.24 (s, 3H), 3.15 (m, 2H), 2.68 (sept, J = 6.8 Hz, 1H), 2.37 (s, 6H), 1.43 (s, 9H), 1.14 (d, J = 6.8 Hz, 6H). 13 C NMR (CDCl3): δ 156.43, 154.33,141.34, 140.95, 140.23, 138.29, 137.69, 131.99, 128.49, 127.22, 123.86,117.32, 60.67, 39.15, 35.13, 31.00, 30.04, 22.64, 21.44.

[0370] [6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane

[0371]

[0372] Will n A hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 mmol) was added in a single batch to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-isopropyl-6-methoxy-1H-indene (6.97 g, 20.0 mmol) in 200 ml of diethyl ether, cooled to -50 °C. The mixture was stirred overnight at room temperature, and the resulting yellow suspension was then cooled to -50 °C. Dichlorodimethylsilane (12.1 ml, 12.95 g, 100.3 mmol, 5.02 equivalents) was added in a single batch, followed by 5 ml of THF. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit (G3) funnel. The filter cake was washed with 2 × 50 ml of toluene. The combined filtrates were evaporated to dryness to obtain [6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane, a pale yellow viscous oil that can be used without further purification.

[0373] 1 H NMR (CDCl3): δ 7.40 (s, 1H), 7.10 (br.s, 2H), 7.00 (m, 1H), 6.44(s, 1H), 3.76 (s, 1H), 3.23 (s, 3H), 2.89 (sept.d, J = 6.8 Hz, J = 1.3 Hz,1H), 2.39 (s, 6H), 1.43 (s, 9H), 1.20 (d, J = 6.7 Hz, 3H), 1.12 (d, J = 6.9Hz, 3H), 0.43 (s, 3H), 0.12 (s, 3H). 13 C NMR (CDCl3): δ 157.53, 155.85, 143.40,137.91, 137.60, 136.43, 128.33, 127.92, 127.89, 122.52, 121.06, 60.45, 47.72,35.16, 31.16, 29.45, 24.43, 21.45, 21.17, 1.35, -0.77.

[0374] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-isopropyl-1H-indene-1-yl]dimethylsilane

[0375] Will n A hexane solution of BuLi (2.5 M, 8.0 ml, 20.0 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 (7.57 g, 20.0 mmol) in a mixture of 120 ml diethyl ether and 25 ml THF cooled to -50 °C. The resulting mixture was stirred overnight at room temperature, and the resulting pale orange solution containing a large amount of orange precipitate was then cooled to -50 °C, and 200 mg CuCN was added. The resulting mixture was stirred at -25 °C for 0.5 h, and then approximately 20.0 mmol of a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-isopropyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane (prepared above) in 200 ml Et2O was added in a single addition. The mixture was stirred overnight at room temperature, then filtered through a silica gel 60 liner (40–63 µm) and washed with 2 × 50 ml Et₂O. The combined organic eluents were evaporated to dryness, and the residue was dried under vacuum at high temperature to give 15.58 g (99.5%, approximately 85% purity) of the title product (a mixture of approximately 63:37 stereoisomers) as a pale yellow, glassy solid, which was ready for use without further purification.

[0376] trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-isopropyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (MC-C2)

[0377]

[0378] At room temperature n BuLi's hexane solution (2.5 M, 14.8 ml, 37.0 mmol) was added in a single addition to [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-isopropyl-1H-indene-1-yl]dimethylsilane (14.46 g, approx. 18.46 mmol) in 95 ml nThe mixture was stirred overnight at room temperature in a pale yellow solution of Bu₂O. The resulting red solution was then cooled to 0°C in an ice bath, and ZrCl₄ (4.3 g, 18.45 mmol) was added. The reaction mixture was stirred at room temperature for 24 h to give an orange-red solution with a LiCl precipitate. The mixture was evaporated to dryness (to a red foamy state), and the residue was treated with 100 ml of warm toluene. The resulting suspension was filtered through a glass frosted funnel (G4), and the filter cake was washed with 2 × 20 ml of warm toluene. The filtrate was evaporated to approximately 20 ml, and then 30 ml of n-hexane was added to the solution. The yellow solid precipitated overnight at room temperature was collected and dried under vacuum. This procedure yielded 3.3 g of the reverse complex. The mother liquor was evaporated to an oily state, and the residue was dissolved in 30 ml of n-hexane. The yellow powder precipitated overnight at room temperature was collected and dried under vacuum. This procedure yielded 3.4 g of the reverse complex. The mother liquor was evaporated to dryness, and the residue was dissolved in 30 ml of n-hexane. The yellow powder precipitated overnight from the solution at -25°C was collected and dried under vacuum. This procedure yielded 1.55 g of the reverse complex. The mother liquor was evaporated again to dryness, and the residue was dissolved in 20 ml of n-pentane. The yellow powder precipitated overnight from the solution at -25°C was collected and dried under vacuum. This procedure yielded 0.85 g of the reverse complex. Therefore, the total yield of trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-isopropyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride isolated in this synthesis was 9.1 g (52.3%).

[0379] For C 56 H 64 Cl2OSiZr, calculated values: C, 71.30; H, 6.84. Measured values: C, 71.38; H, 7.00.

[0380] 1¹H NMR (CDCl₃): δ 7.42 (s, 1H), 7.11 (s, 1H), 6.99 (s, 2H), 6.97 (s, 1H), 6.93 (s, 1H), 6.88 (s, 1H), 6.61 (s, 1H), 7.8–6.7 (very broad singlet (br.s), 4H), 3.36 (s, 3H), 3.21–3.04 (m, 2H), 3.04–2.84 (m, 2H), 2.54–2.40 (m, 1H), 2.43, 2.36, 2.35 and 2.28 (4s, total 21H), 2.05–1.92 (m, 1H), 1.80–1.64 (m, 1H), 1.34 (s, 9H), 1.16 (s, 3H), 1.08 (d, J = 6.4 Hz, 3H), 0.84 (d, J = 6.6 Hz, 3H), -0.14 (s, 3H). 13 C NMR (CDCl3): δ 159.89, 146.50, 144.76, 144.43, 142.85,141.58, 138.34, 138.15, 137.32, 136.84, 135.47, 132.74, 132.31, 132.19,131.26, 129.38, 129.16, 128.97, 128.81, 128.74, 127.60, 126.90, 125.09,121.69, 121.25, 116.29, 83.13, 81.42, 62.40, 35.67, 33.93, 32.61, 30.43, 29.57, 28.91, 26.04, 21.52, 21.41, 21.25, 20.41, 20.05, 4.07, 3.05.

[0381] Synthesis of MC-I1

[0382] Ethylmalonic acid

[0383]

[0384] 196.4 g (3.5 mol) of potassium hydroxide was heated at 1000 cm⁻¹ 3 The aqueous solution was added to a solution of 188.2 g (1.0 mol) diethyl malonate in 500 ml of methanol. The resulting mixture was refluxed for 5 h, and then the ethanol and methanol were distilled off. Then 1000 cm⁻¹ of the aqueous solution was added. 3The resulting mixture was acidified to pH 1.0 with 12 M HCl. Ethylmalonic acid was extracted with 5 × 300 ml 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.

[0385] 1 ¹H NMR (DMSO-d6): δ 4.28 (broad singlet (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): δ171.12, 53.36, 22.01, 11.95.

[0386] 2-Ethylacrylic acid

[0387]

[0388] 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.

[0389] 1 1H NMR (CDCl3): δ 12.55 (broad singlet (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).

[0390] 6-tert-butyl-5-methoxy-2-ethylindan-1-one

[0391]

[0392] 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).

[0393] 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.

[0394] 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one

[0395]

[0396] 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.

[0397] 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.

[0398] 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0399]

[0400] 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 tA mixture of Bu3)2, 63.4 g Na2CO3, 325 ml 2-methyltetrahydrofuran, and 290 ml water was refluxed for 6 h. Then 500 ml 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.

[0401] 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.

[0402] 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0403]

[0404] 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).

[0405] 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.

[0406] [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane

[0407]

[0408] Will n A hexane solution of BuLi (2.5 M, 10.9 mL, 27.25 mmol) was added in a single dose to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene (9.05 g, 27.06 mmol) cooled to -50 °C in 200 mL of diethyl ether. The mixture was stirred overnight at room temperature, and the resulting orange-yellow solution was then cooled to -50 °C, to which dichlorodimethylsilane (16.3 mL, 17.44 g, 135.1 mmol, 5.0 equivalents) was added in a single dose. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3), and the filter cake was washed with 2 × 50 mL of toluene. The combined filtrates were evaporated to dryness to give the title compound as a pale yellow viscous oil, which was ready for use without further purification.

[0409] 1 H NMR (CDCl3): δ 7.39 (s, 1H), 7.09 (s, 2H), 6.99 (s, 1H), 6.45 (s,1H), 3.65 (s, 1H), 3.24 (s, 3H), 2.67-2.46 (m, 2H), 2.38 (s, 6H), 1.43 (s,9H), 1.15 (t,J = 7.5 Hz, 3H), 0.43 (s, 3H), 0.15 (s, 3H). 13 C NMR (CDCl3): δ155.83, 152.58, 143.55, 137.96, 137.58, 137.55, 136.53, 128.33, 127.90,127.74, 124.52, 121.00, 60.46, 48.34, 35.16, 31.17, 24.71, 21.44, 13.76,1.21, -0.66.

[0410] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane

[0411]

[0412] 2.47 ml (6.17 mmol) 2.5 M n A hexane solution of BuLi was added in one step to a suspension of 2.33 g (6.15 mmol) of 4,8-bis(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indane in 27 ml of diethyl ether and 8 ml of THF, cooled to -50 °C. The resulting mixture was stirred overnight at room temperature, and then the resulting pale orange solution containing a large amount of orange precipitate was cooled to -50 °C, and 45 mg of CuCN was added. Over approximately 0.5 h, the temperature of the reaction mixture was raised to -17 °C, and then a solution of 2.65 g (6.2 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]chlorodimethylsilane in 45 ml of diethyl ether was added in one step to the suspension. The mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was dissolved in a mixture of 90 ml hexane and 10 ml dichloromethane. The resulting solution was filtered through a silica gel 60 filter (40–63 µm, 15 ml) (and then washed with a mixture of 2 × 25 ml hexane and dichloromethane (10:1)). The eluent was evaporated to dryness, and the residue was dried under vacuum to give 5.0 g of the title product (a mixture of approximately 60:40 stereoisomers) as a white powder that was ready for use without further purification.

[0413] trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (MC-I1)

[0414]

[0415] 5.0 ml (12.5 mmol) 2.5 M n BuLi's hexane solution was added in a single step at 0°C to 5.0 g (approximately 6.2 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane in 32 ml of [[6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-indene-1-yl]dimethylsilane]. nThe mixture was stirred overnight at room temperature in a pale yellow solution of Bu₂O. The resulting red turbid solution was then cooled to 0°C in an ice bath, and 1.45 g (6.2 mmol) of ZrCl₄ was added. The reaction mixture was stirred at room temperature for 24 h to give an orange-red suspension. This suspension was evaporated to dryness (to an orange powder state). 40 mL of pentane was added to the solid. The yellow precipitate that fell from the mixture at room temperature was collected and dried under vacuum. This procedure yielded 4.2 g of a 99:1 mixture of trans-zirconium chloride and cis-zirconium chloride, along with approximately 0.52 g of LiCl impurities. Thus, the title complex was obtained in approximately 63% yield.

[0416] Synthesis of MC-I2

[0417] Synthesis of 2-n-propyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0418] Method 1

[0419] 2-Bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxyindan-1-ol

[0420]

[0421] Water (20 ml) was added to a solution of 61.29 g (0.2 mol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene in a mixture of 550 ml DMSO and 300 ml THF. Then, 37.38 g (210 mmol, 1.05 equivalent) of N-bromosuccinimide was added in portions over 90 min. The resulting mixture was then stirred overnight at room temperature. Next, 1200 ml of water and 600 ml of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted again with 2 × 150 ml of dichloromethane. The combined organic extracts were washed with 6 × 1000 ml of water, dried over Na₂SO₄, and evaporated to dryness. The residue was dissolved in 300 ml of hexane and allowed to crystallize at 5 °C for 30 min. The resulting white crystals (G3) were filtered off, washed with n-hexane, and dried under vacuum. The procedure yielded 64.89 g of the title product. The combined filtrate was evaporated to dryness, and the residue was recrystallized from 35 ml of n-hexane in the same manner. This procedure yielded an additional 8.07 g of the title product. Therefore, the total yield of 2-bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxyindan-1-ol isolated in this synthesis was 72.96 g (90.4%).

[0422] 1H NMR (CDCl3): δ 7.34 (s, 1H), 6.99-6.94 (2s, 3H total), 5.29 (dd, J =6.2 Hz, J = 6.0 Hz, 1H), 4.17 (ddd, J = 7.7 Hz, J = 7.4 Hz, J = 6.0 Hz, 1H), 3.30 (dd, J = 16.4 Hz, J = 7.4 Hz, 1H), 3.24 (s, 3H), 3.06 (dd, J = 16.4 Hz,J = 7.7 Hz, 1H), 2.40 (d, J = 6.2 Hz, 1H), 2.35 (s, 6H), 1.42 (s, 9H). 13 C NMR(CDCl3): δ 158.21, 142.68, 137.99, 137.83, 136.83, 135.68, 131.99, 128.82,127.14, 121.07, 83.74, 60.37, 54.83, 39.88, 35.30, 30.73, 21.38.

[0423] 2-Bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene

[0424]

[0425] TsOH (2.0 g) was added to a solution of 2-bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-1H-indene (72.96 g, 180.88 mmol) preheated to approximately 60 °C in 600 mL of toluene. The mixture was refluxed using a Dean-Stark separatory for 7 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 200 mL of dichloromethane. The combined organic extracts were dried over K₂CO₃ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, hexane-dichloromethane = 2:1) to give 70.51 g (approximately 100%) of 2-bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene as a pale yellow glassy solid.

[0426] 1H NMR (CDCl3): δ 7.24 (s, 1H), 7.05 (s, 2H), 6.99 (s, 1H), 6.87 (t, J= 1.6 Hz, 1H), 3.41 (d, J = 1.6 Hz, 2H), 3.26 (s, 3H), 2.36 (s, 6H), 1.43 (s,9H). 13 C NMR (CDCl3): δ 155.18, 141.55, 141.19, 138.79, 137.91, 137.46, 132.79,131.78, 128.82, 126.95, 123.25, 117.55, 60.65, 45.50, 35.19, 30.88, 21.40.

[0427] 5 / 6-tert-butyl-7 / 4-(3,5-dimethylphenyl)-6 / 5-methoxy-2-propyl-1H-indene

[0428]

[0429] [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](triphenylphosphine)nickel(II) dichloride (NiCl2(IPr)PPh3, 0.45 g, 0.57 mmol, 2.5 mol%) was added to 2-bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene (8.1 g, 21 mmol) and nA mixture of PrMgBr and THF (1.0 M, 105 mL, 5 equivalents) was added. The solution was refluxed for 30 min. The resulting dark solution was poured into a mixture of 200 g ice and 200 mL water. Then, 50 mL of 1.0 M hydrochloric acid was added. The organic layer was separated. The aqueous layer was extracted with 4 × 100 mL dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, eluent: hexane-dichloromethane = 10:1, vol.). 7.0 g of a pale yellow oil was obtained. This product was a mixture of two isomers of indene and approximately 9% debromination byproduct impurities. To reduce the content of debromination byproducts, the crude product (7.0 g) was refluxed for 30 min with a mixture of 0.25 g TsOH in 100 mL toluene. After cooling the solution to room temperature, 200 ml of K2CO3 aqueous solution was added to separate the organic layer. The aqueous layer was extracted with 2 × 40 ml of toluene. The combined organic extracts were dried with K2CO3 and then evaporated to dryness. The resulting substance was distilled under reduced pressure to give 5.5 g (75%, purity approximately 97%) of a mixture of approximately 2:3 isomers as a colorless oil, bp 160-210℃ / 3 mm Hg.

[0430] Minor isomers: 1 ¹H NMR (CDCl₃): δ 7.34 (s, 1H), 7.10 (s, 2H), 6.98 (broad singlet (br.s), 1H), 6.34 (s, 1H), 3.30 (s, 2H), 3.25 (s, 3H), 2.38–2.34 (m, 8H), 1.59–1.50 (m, 2H), 1.44 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ156.08, 151.14, 144.16, 137.87, 137.72, 137.53, 137.43, 131.86 128.28,127.84, 125.40, 120.81, 60.44, 41.13, 35.04, 33.52, 31.11, 22.44, 21.42,14.01.

[0431] Major isomers: 1¹H NMR (CDCl₃): δ 7.23 (s, 1H), 7.09 (s, 2H), 6.98 (broad singlet (br.s), 1H), 6.45 (m, 1H), 3.25 (s, 3H), 3.12 (s, 2H), 2.38–2.34 (m, 8H), 1.59–1.50 (m, 2H), 1.44 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ154.24, 149.97, 141.56, 140.85, 140.44, 138.30, 137.65, 131.87, 128.46,127.20, 126.05, 117.13, 60.65, 41.04, 35.12, 33.29, 31.00, 22.29, 21.42,13.94.

[0432] [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl]chlorodimethylsilane

[0433]

[0434] Will n A hexane solution of BuLi (2.5 M, 6.3 mL, 16.0 mmol) was added in a single dose to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-propyl-1H-indene (5.5 g, 15.78 mmol) cooled to -50 °C in a mixture of 120 mL diethyl ether and 10 mL THF. The mixture was stirred overnight at room temperature, and the resulting yellow solution was then cooled to -50 °C, and dichlorodimethylsilane (9.5 mL, 10.07 g, 78.0 mmol, 5.0 equivalents) was added in a single dose. The resulting mixture was stirred overnight at room temperature and then filtered through a glass frit funnel (G3), and the filter cake was washed with 2 × 50 mL toluene. The combined filtrates were evaporated to dryness to give the title product, which was ready for use without further purification.

[0435] 1H NMR (CDCl3): δ 7.39 (s, 1H), 7.09 (br. s, 2H), 6.99 (s, 1H), 6.45(s, 1H), 3.64 (s, 1H), 3.25 (s, 3H), 2.54-2.49 (m, 2H), 2.38 (s, 6H), 1.68-1.48 (m, 2H), 1.43 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H), 0.42 (s, 3H), 0.15 (s,3H). 13 C NMR (CDCl3): δ 155.79, 150.92, 143.54, 137.95, 137.56, 137.49, 136.54,128.31, 127.89, 127.65, 125.43, 120.99, 60.46, 48.22, 35.16, 33.72, 31.16,22.75, 21.44, 14.06, 1.19, -0.64.

[0436] Method 2

[0437] n-propylmalonic acid

[0438]

[0439] 99.7 g (1.78 mol) of potassium hydroxide was heated at 500 cm⁻¹ 3 The aqueous solution was added to a solution of 101.1 g (0.5 mol) diethyl n-propylmalonate in 100 mL of methanol. The resulting mixture was refluxed for 5 h, and then the ethanol and methanol were distilled off. Then 500 cm⁻¹ of the aqueous solution was added. 3 The resulting mixture was acidified to pH 1.0 with 12 M HCl. Propylmalonic acid was extracted with 4 × 400 ml diethyl ether. The combined extracts were evaporated to dryness, and the residue was dried under vacuum. This procedure yielded 76.4 g (approximately 100%) of n-propylmalonic acid, which was ready for use without further purification.

[0440] 2-n-Propylacrylic acid

[0441]

[0442] Diethylamine (42.4 g, 0.58 mol) was added dropwise to a solution of approximately 0.5 mol of n-propylmalonic acid in 650 mL of ethyl acetate at 5 °C. 21.3 g (0.71 mol) of paraformaldehyde was added to the resulting suspension. The mixture was refluxed for 5 h, then cooled to 5 °C, and 350 mL of diethyl ether and 1000 cm⁻¹ of ethyl acetate were added. 3 2M HCl. After mixing, separate the organic layer, and extract the aqueous layer again with 2 × 500 ml diethyl ether. Dry the combined organic extracts with Na₂SO₄, and then evaporate to dryness. Purify the residue by vacuum distillation to give 2-n-propylacrylic acid, bp 67-70℃ / 4 mm Hg. 46.1 g (80%) of colorless liquid is obtained.

[0443] 1 H NMR (CDCl3): δ 12.54 (br.s, 1H), 6.30 (m, 1H), 5.65 (m, 1H), 2.29(t,J = 7.3 Hz, 2H), 1.52 (sext, J = 7.4 Hz, 2H), 0.94 (t, J = 7.4 Hz, 3H). 13 CNMR (CDCl3): δ 173.24, 140.02, 127.04, 33.44, 21.48, 13.58.

[0444] 6-tert-butyl-5-methoxy-2-n-propylindan-1-one

[0445]

[0446] At 50°C, 46.1 g (0.4 mol) of 2-n-propylacrylic acid was added to a mixture of 55 g P4O3 and 4-propylacrylic acid. 10 The mixture was added dropwise to Eaton's reagent obtained from 280 ml MeSO3H. 52.5 g (0.32 mol) of 1-tert-butyl-2-methoxybenzene was added dropwise to this mixture while vigorously stirring at 50–53 °C for about 1 h. The resulting mixture was stirred at this temperature for 1 h, then cooled to room temperature and poured into a mixture of 0.5 L cold water and 1 kg ice. The crude product was extracted with 3 × 300 ml dichloromethane. The combined organic extracts were washed with an aqueous K2CO3 solution, dried over K2CO3, filtered through a silica gel 60 short pad (40–63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 62.6 g (75%) of 6-tert-butyl-5-methoxy-2-n-propylindan-1-one as a pale yellow oil (bp 155–170 °C / 4 mm Hg).

[0447] 1 H NMR (CDCl3): δ 7.67 (s, 1H), 6.87 (s, 1H), 3.93 (s, 3H), 3.23 (dd,J= 17.1 Hz, J = 7.6 Hz, 1H), 2.71 (dd,J = 17.1 Hz, J = 3.5 Hz, 1H), 2.66-2.60(m, 1H), 1.94-1.88 (m, 1H), 1.51-1.39 (m, 3H), 1.37 (s, 9H), 0.95 (t, J = 7.4Hz, 3H). 13 C NMR (CDCl3): δ 207.76, 164.51, 154.70, 138.64, 129.18, 121.89,107.70, 55.15, 47.41, 34.99, 33.83, 32.47, 29.53, 20.63, 14.05.

[0448] 4-Bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one

[0449]

[0450] At 5°C, bromine (6.2 ml, 19.2 g, 120 mmol) was added dropwise over 15 min to 31.3 g (0.120 mol) of 6-tert-butyl-2-n-propyl-5-methoxyindan-1-one, 39.45 g of sodium acetate, and 1.0 g of sodium acetate. n A mixture of Bu4NI, 100 ml dichloromethane, and 200 ml water was stirred vigorously. The mixture was stirred at 5 °C for 1 h, then a solution of 20 g sodium acetate in 100 ml water was added, followed by 3.1 ml (60 mmol) bromine. The resulting mixture was stirred at this temperature for another 1 h, then washed with an aqueous solution of Na2SO3 to remove excess bromine. The crude product was extracted with 3 × 100 ml dichloromethane. The combined organic extracts were dried over K2CO3, filtered through a silica gel 60 filter (40–63 µm), and evaporated to dryness. The residue was crystallized from about 50 ml n-pentane at -15 °C to give 33.2 g of the title product (81.6%).

[0451] 1H NMR (CDCl3): δ 7.69 (s, 1H), 4.03 (s, 3H), 3.22 (dd,J = 18.3 Hz, J= 8.4 Hz, 1H), 2.72-2.65 (m, 2H), 1.97-1.88 (m, 1H), 1.54-1.43 (m, 3H), 1.40(s, 9H), 0.97 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ 207.70, 162.75, 154.24,145.43, 133.15, 121.38, 116.66, 61.64, 47.52, 35.66, 34.04, 33.64, 30.62,20.59, 14.03.

[0452] 6-tert-butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one

[0453]

[0454] 16.6 g (48.9 mmol) of 4-bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one, 9.45 g (63.0 mmol, 1.28 equivalents) of 3,5-Me2C6H3B(OH)2, and 0.26 g (0.5 mmol, 1 mol%) of Pd (P t A mixture of Bu3)2, 15.8 g Na2CO3, 80 ml 2-methyltetrahydrofuran, and 75 ml water was refluxed for 6 h. Then, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 50 ml dichloromethane. The combined organic extracts were dried with K2CO3 and then evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: dichloromethane-hexane = 2:1, vol.). The combined eluents were evaporated to dryness, and the residue was washed with 30 ml n-pentane and dried under vacuum. This procedure yielded 15.7 g (88.0%) of the title product.

[0455] 1H NMR (CDCl3): δ 7.73 (s, 1H), 7.03 (s, 1H), 7.02 (s, 2H), 3.31 (s,3H), 3.06 (dd,J = 17.3 Hz, J = 7.6 Hz, 1H), 2.58 (m, 1H), 2.49 (dd, J = 17.3Hz, J = 3.8 Hz, 1H), 2.39 (s, 6H), 1.94-1.84 (m, 1H), 1.42 (s, 9H), 1.40-1.34(m, 3H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (CDCl3): δ 208.45, 163.41, 153.09,143.21, 138.06, 136.28, 132.67, 131.33, 129.07, 127.17, 121.14, 60.48, 47.51,35.33, 33.67, 32.20, 30.50, 21.37, 20.62, 14.02.

[0456] 5-tert-butyl-2-n-propyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

[0457]

[0458] NaBH4 (2.44 g, 64.6 mmol) was added to a solution of 6-tert-butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one (15.7 g, 43 mmol) in 180 mL THF cooled to 5 °C. 70 mL of MeOH was added dropwise to the mixture over approximately 5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. The mixture was then evaporated to dryness, and 200 mL of dichloromethane and 200 mL of water were added to the residue. The resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 2 × 50 mL of dichloromethane. The combined organic extracts were evaporated to dryness. TsOH (300 mg) was added to a solution of the residue in 300 mL of toluene. The mixture was refluxed using a Dean-Stark separator for 10 min and then cooled to room temperature using a water bath. The solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 2 × 50 ml dichloromethane. The combined organic extracts were dried with K₂CO₃ and then evaporated to dryness. The product was purified by rapid chromatography on silica gel 60 (40–63 µm, eluent: dichloromethane-hexane = 1:1, vol.), and dried under vacuum to give 14.0 g (93.4%) of pure product, a mixture of two isomers of indene.

[0459] 1 ¹H NMR (CDCl₃): δ 7.34 (s), 7.23 (s), 7.10 (s), 7.09 (s), 6.98 (s), 6.45 (m), 6.34 (s), 3.30 (s), 3.25 (s), 3.12 (s), 2.38–2.34 (m), 1.55 (sextile, J = 7.4 Hz), 1.44 (s), 0.91 (t, J = 7.3 Hz). 13C NMR (CDCl3): δ 156.08,154.24, 151.14, 149.97, 144.16, 141.56, 140.85, 140.44, 138.30, 137.87,137.72, 137.65, 137.53, 137.43, 131.87, 128.46, 128.28, 127.84, 127.20,126.05, 125.40, 120.81, 117.13, 60.65, 60.44, 41.13, 41.04, 35.12, 35.04,33.52, 33.29, 31.11, 31.00, 22.44, 22.29, 21.42, 14.01, 13.94.

[0460] [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-indene-1-yl]dimethylsilane

[0461]

[0462] Will n A hexane solution of BuLi (2.5 M, 3.17 ml, 7.92 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 (3.0 g, 7.92 mmol) in a mixture of 40 ml diethyl ether and 35 ml THF cooled to -50 °C. The resulting mixture was stirred overnight at room temperature, and the resulting pale orange solution containing a large amount of orange precipitate was then cooled to -50 °C, and 75 mg CuCN was added. The resulting mixture was stirred at -25 °C for 0.5 h, and then a single addition of a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-propyl-5-methoxy-1H-inden-1-yl]chlorodimethylsilane (3.5 g, 7.93 mmol) in 50 ml THF was added. The mixture was stirred overnight at room temperature, then filtered through a silica gel 60 filter bed (40–63 µm) and washed with 2 × 50 mL of diethyl ether. The combined organic eluents were evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, 600 mL, eluent: hexane-dichloromethane = 5:1, vol.). This procedure yielded 4.7 g (76%, approximately 98% purity) of the title product (a mixture of two stereoisomers in approximately 2:3 ratio) as a colorless, glassy solid.

[0463] trans-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl][2-propyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride (MC-I2)

[0464]

[0465] At room temperature n A hexane solution of BuLi (2.5 M, 4.8 mL, 12.0 mmol) was added in a single batch to a solution of 4.7 g (6.0 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-indene-1-yl]dimethylsilane in 50 mL of di-n-butyl ether. The mixture was stirred overnight at room temperature, and the resulting red solution was then cooled to 0 °C in an ice bath, followed by the addition of 1.4 g (6.0 mmol) of ZrCl4. The reaction mixture was stirred at room temperature for 24 h to give an orange-red suspension. The mixture was evaporated to dryness. The solid was extracted with 50 mL of hot toluene. Based on NMR spectral evidence, the resulting extract contained a mixture of trans- and cis-zirconium dichlorodichloroethylene in a ratio of approximately 4:1. The extract was evaporated to dryness, and 30 ml of hexane was added. The yellow precipitate that formed from the resulting solution at room temperature was collected and dried under vacuum. This procedure yielded 3.1 g of trans-zirconium chloride and di-n-butyl ether impurities, which were further recrystallized from a mixture of about 5 ml toluene and 15 ml hexane to give 1.45 g of yellow trans-zirconium chloride powder containing 0.5 mol of toluene per mol of the complex. Therefore, the adjusted net weight of the isolated trans-complex was 1.38 g (24%). For C 56 H 64 Cl2OSiZr*0.5(C7H8), calculated values: C, 72.23; H, 6.93. Measured values: C, 72.15; H, 7.21. 1¹H NMR (CDCl₃): δ 7.42 (s, 1H), 7.25 (very broad singlet (br.s), 4H), 7.14 (s, 1H), 7.03 (s, 1H), 6.99 (s, 1H), 6.96 (s, 1H), 6.94 (s, 1H), 6.81 (s, 1H), 6.59 (s, 1H), 3.39 (s, 3H), 3.13–3.03 (m, 2H), 2.97–2.90 (m, 1H), 2.57–2.43 (m, 2H), 2.41 (s, 3H), 2.37 (s, 3H), 2.34 (12H), 2.29 (s, 3H), 2.18–2.11 (m, 1H), 2.05-1.97 (m, 1H), 1.81-1.70 (m, 1H), 1.35 (s, 9H), 1.30-1.18 (m, 2H), 1.14 (s, 3H), 0.82 (t, J = 7.3 Hz, 3H), -0.13 (s, 3H). 13 C NMR(CDCl3): δ 159.90, 144.63, 144.17, 143.25, 141.39, 139.87, 138.39, 138.06,137.74 (br. s), 137.22, 136.84, 134.70, 134.44, 132.03, 131.99, 131.72,130.56, 129.02, 128.81, 128.69, 127.90, 127.52, 126.91, 123.55, 123.38,121.17, 120.33, 81.89, 81.61, 62.65, 35.68, 34.06, 33.94, 32.39, 30.40, 26.97, 26.04, 21.56, 21.47, 21.41, 21.25, 19.86, 13.87, 3.83, 2.31.

[0466] Synthesis of MC-I3

[0467] Synthesis of the second indene proligand: 4,8-bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indane

[0468] 2-Ethylacryloyl chloride

[0469]

[0470] One drop of DMF was added to a solution of 77.1 g (0.77 mol) 2-ethylacrylic acid in 600 mL of dichloromethane, cooled in an ice bath. Then, 108 g (0.85 mol) oxaloyl chloride was added dropwise to the resulting solution over 1 h, and the reaction mixture was stirred overnight at room temperature. The resulting mixture was concentrated, and the residue was distilled under vacuum to give 65 g (71.2%) 2-ethylacrylyl chloride as a colorless liquid, bp 55-75 °C / 100 mbar.

[0471] 1 H NMR (CDCl3): δ 6.55 (s, 1H), 6.02 (s, 1H), 2.39 (q, J = 7.4 Hz, 2H), 1.12 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 168.73, 146.60, 132.03, 25.33, 12.55.

[0472] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one, Method A

[0473] 2-Ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0474]

[0475] Over 15 min, a mixture of 65.0 g (548 mmol) of 2-ethylacrylyl chloride and 65.0 g (548 mmol) of indane was added dropwise to a suspension of 182 g (1.37 mol) of AlCl3 in 1000 mL of dichloromethane cooled to 0 °C. The cooling bath was then removed, and the solution was stirred overnight at room temperature. The reaction mixture was poured into 2 kg of crushed ice, the organic phase was separated, and the aqueous phase was extracted with 3 × 200 mL of dichloromethane. The combined organic extracts were washed with an aqueous K₂CO₃ solution, dried over K₂CO₃, and passed through a silica gel 60 short pad (40–63 µm). The eluent was evaporated to dryness. The resulting oil was vacuum distilled to give 80.92 g (approximately 74%, purity approximately 70%) of a pale yellow oil, bp 130–145 °C / 3 mm Hg. The 2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one thus obtained can be used without further purification.

[0476] 1H NMR (CDCl3): δ 7.52 (s, 1H), 7.24 (s, 1H), 3.20 (dd, J1 = 7.8 Hz, J2 = 17.1 Hz, 1H), 2.94-2.86 (m, 4H), 2.71 (dd, J1 = 3.6 Hz, J2 = 17.0 Hz,1H), 2.59-2.54 (m, 1H), 2.13-2.05 (m, 2H), 1.96-1.90 (m, 1H), 1.56-1.45 (m,1H), 0.98 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 208.05, 152.68, 152.60, 143.74, 135.46, 121.77, 118.67, 48.89, 32.79, 31.74, 25.52, 24.31, 11.30.

[0477] 4,8-Dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0478]

[0479] At -10 °C, 80.9 g (approximately 404 mmol) of 2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one (prepared as above, approximately 70% purity) was added dropwise over 15 min to a suspension of 134.7 g (1.01 mol, 2.5 equivalents) of AlCl3 in 400 mL of dichloromethane. The reaction mixture was stirred at this temperature for 10 min, followed by the dropwise addition of 41.7 mL (129.4 g, 809 mmol, 2.0 equivalents) of bromine over 1 h. The resulting mixture was stirred overnight at room temperature and then poured into a 1000 cm³ container. 3 In crushed ice. The organic layer was separated, and the aqueous layer was extracted again with 3 × 300 ml dichloromethane. The combined organic extracts were washed with aqueous K₂CO₃ solution, dried with K₂CO₃, and the eluent was evaporated to dryness through a silica gel 60 short pad (40–63 µm). The crude product was crudely purified by crystallization from 500 ml n-hexane to give 89.5 g of crude product. The crude product was then crystallized from 500 ml n-hexane to give an analytically pure product. The mother liquor from the last crystallization was evaporated to about 200 ml, giving a white suspension in hexane. The suspension was heated to boiling point (~65–70 °C) and then filtered (while hot) through a glass frit funnel (G3). The precipitate thus obtained was dried under vacuum to give another batch of the title product. The total yield was 59.9 g (41%).1 H NMR(CDCl3): δ 3.17-3.05 (m, 5H), 2.70-2.60 (m, 2H), 2.17 (quin, J = 7.7 Hz, 2H), 2.03-1.93 (m, 1H), 1.59-1.48 (m, 1H), 1.02 (t, J = 7.4 Hz, 3H). 13 C NMR(CDCl3): δ 204.94, 154.85, 152.52, 146.90, 134.22, 117.80, 115.17, 49.83, 35.64, 34.60, 32.30, 24.53, 23.18, 11.47.

[0480] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0481]

[0482] 59.9 g (167 mmol) of 4,8-dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one, 56.4 g (376 mmol, 2.25 equivalents) of 3,5-dimethylphenylboronic acid, and 1.34 g of Pd(P t A mixture of Bu3)2, 95.8 g Na2CO3, 600 ml 2-methyltetrahydrofuran, and 420 ml water was refluxed for 7 h. Then, 600 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 300 ml dichloromethane. The combined organic extracts were dried over K2CO3 and then evaporated to dryness to give a brown solid mass. The product was separated by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 400 mm, eluent: hexane-dichloromethane = 1:3, vol.). The eluent was evaporated to dryness, and the residue was then ground with 300 ml n-hexane. The resulting suspension was filtered through a glass frit funnel (G3), and the resulting white precipitate was washed with 2 × 30 ml n-hexane and then dried under vacuum. The yield was 61.47 g (90%). 1H NMR (CDCl3): δ 7.03 (s, 1H), 6.99 (s, 1H), 6.95(s, 2H), 6.92 (s, 2H), 3.08 (dd, J1 = 8.7 Hz, J2 = 18.0 Hz, 1H), 2.88-2.68(m, 4H), 2.57-2.49(m, 2H), 2.39 (s, 6H), 2.36 (s, 6H), 2.04-1.84 (m, 3H), 1.47-1.36 (m, 1H), 0.91 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl3): δ 207.37, 151.81,149.90, 143.55, 138.22, 137.93, 137.23, 136.88, 135.89, 135.43, 132.40,128.93, 126.74, 126.49, 49.72, 33.03, 31.96, 31.06, 25.64, 24.30, 21.46,21.41, 11.66.

[0483] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one, Method B

[0484] 2-Ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0485]

[0486] At 50°C, 4.76 g (47.5 mmol, 1.27 equivalents) of 2-ethylacrylic acid was added to a mixture of 8.28 g of P4O 10Add 4.43 g (37.5 mmol) of indane (~95% purity) to the rapidly stirred mixture at 48–50 °C over approximately 45 min. Stir the resulting mixture at this temperature for 1 h, then cool to room temperature and pour into a mixture of 0.4 L cold water and 0.1 kg ice. Extract the crude product with 3 × 50 mL of dichloromethane, adding 75 mL of hexane. Filter the combined organic extracts through a silica gel 60 filter (40–63 μm, 20 mL) and wash with 2 × 40 mL of a 1:2 mixture of hexane and dichloromethane. Evaporate the eluent to dryness. The crude product was dissolved in 100 ml of dichloromethane; the resulting solution was washed with an aqueous K2CO3 solution, dried with K2CO3, and then evaporated to dryness to give 7.15 g (95%, about 60% purity) of 2-ethyl-3,5,6,7-tetrahydro-s-indane-1(2H)-one as a yellow oil.

[0487] 4,8-Dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0488]

[0489] At -10 °C, a solution of 7.0 g (approximately 35 mmol) of 2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one (prepared as above, approximately 60% purity) in 10 mL of dichloromethane was added dropwise to a suspension of 11.6 g (87 mmol) of AlCl3 in 40 mL of dichloromethane over 15 min. The reaction mixture was stirred at this temperature for 10 min, and then 4.0 mL (12.4 g, 77.5 mmol, 2.2 equivalents) of bromine was added dropwise over 1 h at -10 °C. The resulting mixture was stirred overnight at room temperature and then poured into a 100 cm³ container. 3In crushed ice. Separate the organic layer and extract the aqueous layer with 3 × 30 ml dichloromethane. Pass the combined organic extracts through a silica gel 60 short pad (40–63 µm, 40 ml), wash the silica gel layer with 2 × 30 ml dichloromethane, and evaporate the resulting eluent to dryness. Dissolve the resulting oily substance in 50 ml hexane. After 5 min, filter off the black precipitate that forms. Crystallize the filtrate overnight at -15 °C to give 6.4 g of crude solid product. Dissolve the crude product under reflux in a mixture of 25 ml n-hexane and 6 ml toluene. Then crystallize (from boiling point to RT) to give 4 g of the desired product and trace amounts of polymerization byproduct impurities. Evaporate the mother liquor from the last crystallization to dryness. Crystallize the residue from a mixture of 10 ml hexane and 1 ml toluene to give another batch (0.9 g) of product. The 4.9 g solid product thus obtained was dissolved in 20 ml of a 1:1 mixture of hexane and dichloromethane, and the solution was passed through a silica gel 60 short-shield layer (40–63 µm, 15 ml). The silica gel layer was then washed with 2 × 20 ml of a 1:1 mixture of hexane and dichloromethane. The combined eluents were evaporated to dryness to give 4.6 g (37%) of the title product as a pale yellow solid.

[0490] 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0491]

[0492] 4.3 g (12 mmol) of 4,8-dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one, 4.14 g (27.6 mmol, 2.3 equivalents) of 3,5-dimethylphenylboronic acid, and 0.1 g of Pd(P tA mixture of Bu3)2, 6.9 g Na2CO3, 43 ml 2-methyltetrahydrofuran, and 30 ml water was refluxed for 7 h. Then 50 ml dichloromethane was added, the organic layer was separated, and the aqueous layer was extracted with 2 × 30 ml dichloromethane. The combined organic extracts were dried with K2CO3 and then evaporated to dryness. The solid mass was dissolved in 30 ml of a 2:3 mixture of hexane and dichloromethane, and the resulting solution was passed through a silica gel 60 short-shield layer (40–63 µm, 20 ml). The silica gel layer was washed with 3 × 20 ml of a 1:1 mixture of hexane and dichloromethane, and the resulting eluent was evaporated to dryness. The solid residue was treated with 20 ml pentane, and the resulting suspension was filtered through a glass frit funnel (G3). The precipitate was dried under vacuum to give 3.8 g of the title product. The mother liquor filtrate was evaporated to about 10 ml to form a suspension, which was then filtered through a glass frit funnel (G3). The residue was vacuum dried to obtain another batch (0.95 g) of the title product. The total yield was 4.75 g (97%, 98% purity).

[0493] 4,8-Bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indah.

[0494]

[0495] Methanol (100 ml) was added dropwise over 5 h at 0–5 °C to a mixture of 20.0 g (49 mmol) of 4,8-bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one and 4.28 g (109 mmol) of NaBH4 in 300 ml of THF. The resulting mixture was stirred overnight at room temperature and then evaporated to dryness. 400 ml of dichloromethane and 1000 ml of water were added to the residue, and the resulting mixture was acidified to pH ~6.5 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted again with 2 × 200 ml of dichloromethane. The combined organic extracts were dried over Na2SO4 and evaporated to dryness to give a white solid block. TsOH (1.0 g) was added to a solution of this solid block in 350 ml of toluene preheated to approximately 60 °C. The mixture was refluxed using a Dean-Stark separatory for 12 min. The reaction mixture was then rapidly cooled to room temperature using an ice-water bath. The resulting solution was washed with 10% Na₂CO₃ to separate the organic layer, and the aqueous layer was extracted with 100 mL of dichloromethane. The combined organic extracts were dried over K₂CO₃ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, d 50 mm, l 30 mm, hexane-dichloromethane = 10:1, vol.). This procedure yielded 19.4 g (100%) of the title product as a white solid. 1H NMR (CDCl3): δ 7.05 (s, 2H), 7.03 (s, 2H), 6.98 (s, 2H), 6.44 (m,1H), 3.25 (s, 2H), 2.89 (t, J =7.3 Hz, 2H), 2.83 (t, J =7.3 Hz, 2H), 2.42-2.33 (m, 14H), 1.98 (quin, J =7.3 Hz, 2H), 1.10 (t, J =7.4 Hz, 3H). 13 C NMR(CDCl3): δ 151.79, 142.60, 140.88, 140.24, 140.19, 139.83, 138.42, 137.55,137.39, 133.53, 129.79, 128.39, 128.18, 127.32, 126.60, 124.41, 40.59, 32.78,32.51, 26.09, 24.45, 21.42, 13.44.

[0496] [4,8-Bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]dimethylsilane

[0497]

[0498] At -50℃, n A hexane solution of BuLi (2.5 M, 3.84 mL, 9.6 mmol) was added in a single addition to a solution of 4,8-bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indane (3.77 g, 9.6 mmol) in a mixture of 40 mL diethyl ether and 40 mL THF. The mixture was stirred overnight at room temperature, and the resulting greenish-yellow suspension was cooled to -50 °C, and 100 mg CuCN was added. The resulting mixture was stirred at -20 °C for 0.5 h, and then a single addition of 4.1 g (9.6 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl](chloro)dimethylsilane in 50 mL THF was added. The resulting mixture was stirred at room temperature for 12 h, then filtered through a silica gel 60 filter (40–63 μm) and washed with 2 × 50 mL diethyl ether. The combined organic eluents were evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 µm, 600 mL, eluent: hexane-dichloromethane = 5:1, vol.). This procedure yielded 5.10 g (6.5 mmol, yield approximately 67.8%, purity approximately 98%) of the title product (a mixture of approximately 40:60 stereoisomers) as a glassy solid.

[0499] trans-dimethylsilanediyl[η5-4,8-bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][η5-6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxyindene-1-yl]zirconium dichloride (MC-I3)

[0500]

[0501] A hexane solution of nBuLi (2.5 M, 5.1 mL, 12.75 mmol) was added in a single step to a solution of [4,8-bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-indene-1-yl]dimethylsilane (5.00 g, 6.38 mmol) in 50 mL of di-n-butyl ether. The mixture was stirred at room temperature for 5 h, and then the resulting solution was cooled to 0 °C in an ice bath, and ZrCl4 (1.49 g, 6.39 mmol) was added. The resulting mixture was stirred at room temperature for 24 h to give a yellow suspension. The suspension was evaporated to dryness, and the residue was extracted with 50 mL of warm toluene. The precipitate (G4) was filtered off. Based on NMR spectral evidence, the resulting filtrate contained approximately 95 / 5 of a mixture of trans- and cis-zirconium dichloroethylene. The filtrate was evaporated to dryness, and 30 mL of hexane was added. The orange precipitate (G3) that fell from the solution overnight at room temperature was filtered off, washed with 10 mL of n-hexane, and then dried under vacuum. This procedure yielded 4.8 g of trans-zirconium dichloroethylene (and approximately 0.6% cis isomer impurities) containing 0.02 mol ether / mol Zr and 0.08 mol n-hexane / mol Zr, thus the adjusted net weight of the isolated complex was approximately 4.75 g (yield approximately 79%).

[0502] For C 56 H 64 Cl2OSiZr., Analytical values: C, 71.30; H, 6.84. Measured values: C, 71.45; H, 7.02. 1 ¹H NMR (CDCl₃): δ 7.65–6.7 (very broad singlet (br.s), 4H), 7.38 (s, 1H), 7.09 (s, 1H), 7.02 (s, 1H), 6.99 (s, 1H), 6.96 (s, 1H), 6.95 (s, 1H), 6.86 (s, 1H), 6.60 (s, 1H), 3.40 (s, 3H), 3.11–2.86 (m, 4H), 2.60–2.25 (m, 22H), 1.99 (m, 1H), 1.82–1.70 (m, 1H), 1.35 (s, 9H), 1.14–1.10 (m, 6H), 0.90 (t, J = 7.4). Hz, 3H), -0.16 (s, 3H). 13C NMR (CDCl3): δ 159.82, 144.81, 144.09, 143.11, 141.75,141.49, 141.12, 138.40, 138.16, 137.77 (br.s), 137.38, 136.92, 134.52,132.25, 132.12, 131.74, 130.93, 128.96, 128.85, 128.79, 128.70, 127.89,127.50 (br.s), 126.85, 122.95, 121.18, 120.77, 119.34, 81.54, 80.54, 62.68, 35.63, 33.91, 32.38, 30.39, 26.52, 26.07, 25.86, 21.46, 21.41, 21.27, 17.00, 16.59, 4.20, 2.38.

[0503] Catalyst synthesis, the chemicals used

[0504] The 30 wt% MAO Axion CA1330 toluene solution was purchased from Chemtura / Lanxess and was ready to use upon receipt, and should be stored at -20°C for no more than 6 months.

[0505] 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.

[0506] All catalysts were prepared using Sunspera AGC DM-L-303 silica calcined at 600°C.

[0507] Catalyst preparation

[0508] These catalysts were prepared using a two-step method. The first step was the preparation of SiO2 / MAO (activated support), followed by a second step in which a toluene solution of the metallocene complex was impregnated onto the dried support from the first step. Only when the solubility of the metallocene in toluene was insufficient was a second portion of MAO added to the metallocene / toluene slurry to promote complete dissolution of the metallocene.

[0509] Preparation of SiO2 / MAO Activated Support

[0510] 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).

[0511] Synthesis of SiO2 / MAO / MC-C1 = Comparative Catalyst 1 (CC1)

[0512] In a nitrogen-filled glove box, 2.1 ml of dry toluene was added to 41.9 mg of metallocene MC-C1 in a diaphragm flask. 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 red, free-flowing powder.

[0513] Synthesis of SiO2 / MAO / MC-C2 = Comparative catalyst 2 (CC2)

[0514] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 29.0 mg of metallocene MC-C2 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes. Next, 2,000 g of SiO2 / MAO was placed in the diaphragm flask. The toluene solution of the metallocene was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting powder was allowed to stand for 1 hour, then transferred to a Schlenk flask and dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a light red, free-flowing powder.

[0515] SiO2 / MAO / MC-I1 = Synthesis of Catalyst 1 (IC1) of the Invention

[0516] In a nitrogen-filled glove box, 5 ml of dry toluene was added to 60.2 mg of metallocene MC-I1 in a diaphragm flask. The solution was stirred at room temperature for 30 min. Next, 0.2 ml of a 30 wt% toluene solution of methylaluminoxane (MAO) (Axion CA1330) was added, and the solution was stirred again for 30 min. Then, the toluene solution of metallocene and MAO was added dropwise over 10 min to 4.003 g of SiO2 / MAO support in the diaphragm flask using a syringe, while gently mixing. The resulting powder was allowed to stand for 1 hour, then transferred to a Schlenk flask and dried under vacuum at 60 °C for 1 hour and 45 min to obtain the catalyst as a light red free-flowing powder.

[0517] Synthesis of SiO2 / MAO / MC-I2 = Catalyst 2 (IC2) of the present invention

[0518] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 28.4 mg of metallocene MC-I2 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes. Next, 2,000 g of SiO2 / MAO was placed in the diaphragm flask. The toluene solution of the metallocene was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting powder was allowed to stand for 1 hour, then transferred to a Schlenk flask and dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a red, free-flowing powder.

[0519] Synthesis of SiO2 / MAO / MC-I3 = Catalyst 3 (IC3) of the present invention

[0520] In a nitrogen-filled glove box, 2.5 ml of dry toluene was added to 28.4 mg of metallocene MC-I3 in a diaphragm flask. The solution was stirred at room temperature for 30 minutes. Next, 2,000 g of SiO2 / MAO was placed in the diaphragm flask. The toluene solution of the metallocene was added dropwise to the SiO2 / MAO support using a syringe over 5 minutes, while gently mixing. The resulting powder was allowed to stand for 1 hour, then transferred to a Schlenk flask and dried under vacuum at 60 °C for 1 hour to obtain the catalyst as a light red, free-flowing powder.

[0521] The metallocene content in each catalyst was calculated using mass balance. These values ​​are listed in Table 1:

[0522] Table 1: Catalysts tested and their metallocene content

[0523]

[0524] * MC = Metallocene; the metallocene content in the dried catalyst is calculated using mass balance.

[0525] Aggregate Examples

[0526] monomers and gases

[0527] Hydrogen (6.0g by mass) was supplied by Air Liquide and was ready for use upon receipt. Propylene (2.3g by mass), butene, and ethylene were purified by chromatographic column packed with PolyMax301 T-4427B (60°C; Cu / CuO), MS13X-APG 1 / 16 molecular sieve, and Selexsorb COS 1 / 8.

[0528] Ternary polymerization process of propylene / butene / ethylene (20-L reactor, liquid monomer)

[0529] Polymerization in liquid monomers

[0530] An additional 4.45 kg of propylene was added using a balance to a stainless steel reactor with a ribbon agitator containing 0.2 bar-g of propylene, with a total volume of 21.2 dm³.

[0531] Add triethylaluminum (0.8 ml of 0.62 mol / L n-heptane solution) to a 250 g propylene feed stream. Then add the selected amount of H2 over one minute using a mass flow controller. Stabilize the reactor temperature to the desired prepolymerization step temperature using an HB thermostat. Stir the solution at 250 rpm for at least 20 min. Then inject the catalyst as described below. Load the required amount of catalyst (solid or slurry form) into a stainless steel vial in the glove box. Then attach the catalyst vial to the port on the reactor lid. Feed the catalyst into the reactor by rinsing 250 g propylene from a balance through the catalyst vial. Maintain the stirring speed at 250 rpm, and proceed with prepolymerization at the set time and temperature. Then increase the polymerization temperature to the target value. At the specified temperature, add ethylene, butene, and a second amount of H2 (if needed) over ~1-2 min using an MFC. Afterward, keep the reactor temperature constant throughout the polymerization process. When the temperature is 2°C lower than the set polymerization temperature, begin measuring the polymerization time. When the set time has elapsed, the reaction is stopped 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, the reactor is opened; the polymer powder is removed and dried overnight in a fume hood. 100 g of polymer is then added to 0.5 wt% Irganox B225 (dissolved in acetone), dried overnight in a fume hood, and then dried for another hour in a vacuum drying oven at 60°C.

[0532] Gas phase polymerization

[0533] After the bulk step is completed, the agitator speed is reduced to 50 rpm and the pressure is reduced to 0.4 bar-g by discharging the monomer. Then, the agitator speed is set to 180 rpm, the reactor temperature is set to 70°C, and a given batch of ethylene is added, achieving the desired comonomer ratio and a pressure of 21 bar-g by feeding a C3 / C2 gas mixture as defined below:

[0534]

[0535] C2 / C3 is the weight ratio of the two monomers, and R is their reactivity ratio, which were determined experimentally. In this experiment, R = 0.4.

[0536] When the pressure reaches 20 °C bar-g, hydrogen is added over 1 minute via a flow controller. The temperature is maintained constant via a thermostat, and the pressure of 21 bar-g is maintained constant by feeding a C2 / C3 and C4 / C3 gas mixture corresponding to the target polymer composition via a mass flow controller until the set duration of this step has elapsed.

[0537] The reactor was then cooled to approximately 30°C, and volatile components were flash-evaporated. After purging the reactor twice with N2 and performing one vacuum / N2 cycle, the product was removed and dried overnight in a fume hood. 0.5 wt% Irganox B225 (acetone solution) was added to 100 g of polymer, and the mixture was dried overnight in a fume hood, followed by drying in a vacuum drying oven at 60°C for 1 hour.

[0538] Aggregation results

[0539] We have found that, compared with comparative methods CE1 to CE6 using comparative catalysts CC1 and CC2, polymerization methods IE1 to IE8 according to the invention using catalysts IC1 to IC3 can produce terpolymers with improved MFR / productivity balance.

[0540] The polymerization results are listed in Tables 2 and 3 (polymerization in liquid monomer) and Tables 4 and 5 (two-step polymerization in liquid monomer and gas phase).

[0541] As can be seen from Tables 2 to 5, the methods according to embodiments of the present invention produce terpolymers with relatively high molecular weight / low MFR2 at relatively high catalyst productivity. Although the catalyst productivity of CE1 and CE2 is 13.8 and 15.0 kg / gcat, respectively, the produced terpolymers have relatively low molecular weight / relatively high MFR2. Similarly, although CE4 and CE5 provide terpolymers with higher molecular weight / lower MFR2, this comes at the cost of productivity. The methods according to embodiments IE1 to IE8 of the present invention provide a balance between improved MFR2 and productivity.

[0542] Table 2. Polymerization in liquid monomers: Conditions

[0543]

[0544] Table 3. Polymerization in liquid monomers: Results

[0545]

[0546] Table 4. Liquid monomer polymerization and gas-phase polymerization: conditions

[0547]

[0548] Table 5. Liquid monomer polymerization and gas-phase polymerization: Results

[0549]

Claims

1. A process for producing a propylene copolymer resin comprising polymerizing propylene and at least one comonomer selected from the group consisting of ethylene and C4-C12 alpha olefin comonomers; and 10 C4-C12 alpha olefin comonomers; and wherein the process is carried out in the presence of a polymerization catalyst comprising: (i) a metallocene complex of formula (I); (ii) a cocatalyst system comprising a cocatalyst comprising a Group 13 element; and (iii) optionally a support, wherein the metallocene complex of formula (I) is (I) wherein Mt is Zr or Hf; X is a sigma ligand; R 1 each independently of one another or of the other occurrences, is C1-C 20 hydrocarbyl, optionally containing up to two heteroatoms of groups 14-16 of the periodic table, or together with the Si atom to which they are attached form a C4-C8-ring; R 2 and R 2’ each independently of one another are CH2-R 21 wherein R 21 is H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl or C6-C9-aryl, with the proviso that R 2 and R 2’ are not both methyl; R 3 and R 4 each independently of one another are H, linear or branched C1-C6-alkyl, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl, C6-C 20 aryl or -OR 31 wherein R 31 is C1-C 10 -hydrocarbyl, wherein at least one R 3 is not H and at least one R 4 is not H; R 5 and R 6 each independently of one another are C1-C 10 hydrocarbyl, or can form, together with the C atom to which they are attached, a C5-C7-carbocyclic ring; R 51’ is C1-C 10 -hydrocarbyl; and R 6’ is C(R 61 )3, wherein R 61 is linear or branched C1-C6-alkyl.

2. The process according to claim 1 which is a process for producing a propylene terpolymer resin comprising: propylene and at least two comonomers selected from ethylene and C4-C 10 different comonomers of the α-olefin comonomers are polymerized; Preferably the process comprises polymerising propylene, ethylene and a comonomer selected from C4-C 10 comonomer of the α-olefin comonomer; more preferably comprising polymerizing propylene, ethylene and butene.

3. The process according to any one of the preceding claims, wherein the metallocene complex of formula (I) is of formula (I-a) (I-a) wherein Mt is Zr or Hf; X is a sigma ligand; n is 1 to 3, for example 1, 2 or 3, preferably 1 ; R 1 each independently of one another or of the other, is C1-C 20 hydrocarbyl, optionally containing up to two heteroatoms of groups 14-16 of the periodic table, or together with the Si atom to which they are attached form a C4-C8-ring; R 2 and R 2’ each independently of one another are CH2-R 21 wherein R 21 is H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl or C6-C9-aryl, with the proviso that R 2 and R 2’ are not both methyl; R 3 and R 4 each independently of one another are H, linear or branched C1-C6-alkyl, C7- 20 -arylalkyl, C7- 20 -alkylaryl, C6- 20 -aryl or -OR 31 wherein R 31 is C1-C 10 -hydrocarbyl, wherein at least one R 3 is not H and at least one R 4 is not H; R 51’ is C1-C 10 -hydrocarbyl; and R 6’ is C(R 61 )3, wherein R 61 is linear or branched C1-C6-alkyl.

4. The process according to any one of the preceding claims, wherein the metallocene complex of formula (I) is of formula (I-b) (I-b) wherein Mt is Zr or Hf; X is a sigma ligand; R 1 each independently of one another or of the other occurrences, is C1-C 20 hydrocarbyl, optionally containing up to two heteroatoms of groups 14-16 of the periodic table, or together with the Si atom to which they are attached form a C4-C8-ring; R 2 and R 2’ each independently of one another are CH2-R 21 wherein R 21 is H, linear or branched C1-C6-alkyl, with the proviso that R 2 and R 2’ are not both methyl; R 3 and R 4 each independently of one another are H, linear or branched C1-C6-alkyl, C7- 20 -arylalkyl, C7- 20 -alkylaryl, C6- 20 -aryl or -OR 31 wherein R 31 is C1-C 10 -hydrocarbyl, wherein at least one R 3 is not H and at least one R 4 is not H.

5. The process according to any one of the preceding claims, wherein one or two R on each phenyl 3 is not H, and on both phenyls, R 3 are the same, and two R on the phenyl group 4 are not H, and the two R 4 are the same; or, wherein each phenyl group has two R 3 is not H, and on both phenyl groups, R 3 is linear or branched C1-C6-alkyl, preferably methyl, and two R on the phenyl group 4 are not H, and the two R 4 are linear or branched C1-C6 alkyl, preferably methyl.

6. The method according to any one of the preceding claims, wherein R 2 and R 2’ are each independently of the other or of the other occurrences the same or different CH2-R 21 wherein R 21 is H or a linear Ci-C6-alkyl group; preferably H or a linear Ci-C4-alkyl group, more preferably H, methyl or ethyl, with the proviso that R 2 and R 2’ are not both methyl.

7. The method according to any one of claims 1 to 5, wherein R 2 and one of R 2’ is methyl and the other has the formula CH2-R 21 wherein R 21 is linear or branched C1-C6-alkyl; preferably linear or branched C1-C4-alkyl; more preferably methyl or ethyl.

8. The method according to any one of claims 1 to 5, wherein R 2 and R 2’ are not both methyl; preferably, wherein R 2 and R 2’ are each independently of the other the same or different CH2-R 21 wherein R 21 is linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4-alkyl, even more preferably methyl or ethyl, yet more preferably methyl.

9. The method according to any one of the preceding claims, wherein R 1 each independently of the other or of the others is C1-C6 alkyl, preferably methyl.

10. The process according to any one of the preceding claims, wherein cocatalyst (ii) is an aluminoxane cocatalyst, preferably in the absence of any other cocatalyst; and / or wherein the polymerization catalyst is supported on silica.

11. The process according to any one of the preceding claims, wherein the process comprises the steps of: (I) in a first polymerization step, preferably in at least one slurry reactor, propylene and at least one comonomer selected from the group consisting of ethylene and C4-C12 α-olefin comonomers, preferably ethylene, are polymerized in the presence of the polymerization catalyst to produce a propylene copolymer matrix (A); followed by 10 (I) in a first polymerization step, preferably in at least one slurry reactor, propylene and at least one comonomer selected from the group consisting of ethylene and C4-C12 α-olefin comonomers, preferably ethylene, are polymerized in the presence of the polymerization catalyst to produce a propylene copolymer matrix (A); followed by (II) In the second polymerization step, preferably in at least one gas reactor, in the presence of the polymerization catalyst and the propylene copolymer matrix (A) from step (I), propylene and at least one compound selected from ethylene and C4-C 10 The comonomers of the α-olefin comonomers, preferably at least two selected from ethylene and C4-C4, are preferred. 10 Different comonomers of α-olefin comonomers, more preferably ethylene and at least one C4-C 10 The α-olefin comonomer is polymerized to produce a propylene copolymer phase (B) dispersed in the propylene copolymer matrix (A).

12. The method of claim 11, wherein, In step (II), propylene and at least two different comonomers selected from ethylene and C4-C 10 αolefin comonomers, preferably ethylene and at least one C4-C 10 αolefin comonomers, are polymerized in the presence of the polymerization catalyst and the propylene copolymer matrix (A) from step (I) to produce a propylene terpolymer phase (B) dispersed in the propylene copolymer matrix (A); and preferably wherein: a) the propylene copolymer matrix (A) produced in step (I) is produced in an amount of less than or equal to 90 wt% of the total weight of the propylene terpolymer resin produced, and b) the propylene terpolymer phase (B) produced in step (II) is produced in an amount of greater than or equal to 10 wt% of the total weight of the propylene terpolymer resin produced.

13. The process according to any one of claims 1 to 10, wherein the process is carried out in at least one slurry reactor comprising the steps of: (I) polymerizing propylene and at least one comonomer selected from the group consisting of ethylene and C4-C 10 different comonomers of alpha olefin comonomers, more preferably ethylene and at least one C4-C 10 different comonomers of alpha olefin comonomers, more preferably ethylene and at least one C4-C 10 to produce a propylene terpolymer. Preferably, (I) polymerizing propylene and at least two comonomers selected from the group consisting of ethylene and C4-C 10 different comonomers of alpha olefin comonomers, more preferably ethylene and at least one C4-C 10 to produce a propylene terpolymer. Preferably, (I) polymerizing propylene and at least two comonomers selected from the group consisting of ethylene and C4-C 14. The process according to claim 13, wherein 50 to 99 wt% of the total weight of the propylene terpolymer resin final product is produced at the end of slurry step (I), and the process further comprises the steps of: (II) transferring the reaction mixture of step (I) to a gas phase reactor for the production of propylene terpolymer accounting for 1 to 50 wt% of the propylene terpolymer resin final product.

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