Diphenylsilane-bridged C1 symmetric catalysts and polymers produced therefrom.

Abstract

Diarylsilane-bridged metallocene catalysts, methods for their preparation, and propylene (co)polymers produced therefrom are disclosed. The resulting silane-bridged metallocene catalysts are highly active in the polymerization of olefins, particularly ethylene and propylene. Diarylsilane-bridged metallocenes can be synthesized by displacing the dichlorocyclopentadienyl fragment with indenyllithium. Direct lithiation / displacement with aryl or alkyllithium reagents provides dilithiated ligands that undergo metallation with Group IV metal precursors.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 370829, filed August 9, 2022, the disclosure of which is incorporated herein by reference. [Background technology]

[0002] BACKGROUND OF THE INVENTION FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to asymmetric metallocene catalyst compounds. More specifically, embodiments of the present disclosure relate to asymmetric bridged metallocenes having substituted indacenyl ligands and propylene polymers made therefrom.

[0003] Description of Related Art Traditional bridged metallocene synthesis relies on replacing the leaving group X with the lithium salt of indene, indacene, or cyclopentadiene. Recently, silane-bridged metallocenes have been discovered and shown to be capable of efficiently producing propylene polymers with desirable physical and mechanical properties.

[0004] Diphenylsilane-bridged metallocenes, in particular, have been studied. However, diphenylsilane-bridged metallocenes remain a rather elusive synthetic target due to the difficulty of their preparation. The challenge with the introduction of the diphenylsilane bridge relates to the increased proton acidity of the key CpHSi(Ph)X (X = Cl, OTf) intermediate, where the addition of a second nucleophile (e.g., indenyllithium or fluorenyllithium) leads to a mixture of products. This added second nucleophile also favors deprotonation of Cp rather than the intended nucleophilic substitution of the Si-X group. This deprotonation substantially complicates the synthesis, requiring numerous tedious purification steps.

[0005] Related literature includes CN101235106, which details the synthesis of 1-indenyl analogues of diphenylsilane, US9,790,240B2, which describes a mixed C2 symmetry system of diphenylsilane derivatives, and "ansa-metallocenes with Ph2Si bridges: HfCl2[Ph2Si(η 5 -C5H4)] and HfCl2[Ph2Si(C 13 H9)(η 5 -C5H4)]2 (Izmer, V. et al., (2001) J. Chem. Soc., Dalton Trans., pp. 1131-1136), WO2001 / 005870A1 and WO2002 / 002575A1, which describe C2-symmetric complexes with arylsilane bridges, and "C1-symmetric metallocene / MAO-catalyzed alternating ethene / propene copolymers" (Heuer, B. et al., (2005) Macromolecules, v.38(8), pp. 3054-3059); EP 0754698 A2; EP 1046642 A2, which describes Cp-fluorenyl analogs with diphenylsilane bridges; US 2019 / 0161559 A1 and WO 2018 / 151904 A1, which describe bis-Cp analogs with diphenylsilane bridges; US 2020 / 043758, WO 2014 / 099303, US 9,266,910 B2, and KR 2020003044.

[0006] There remains a need for new, more reliable methods for synthesizing diphenylsilane-bridged metallocenes for producing propylene polymers. Summary of the Invention

[0007] The present disclosure provides diarylsilane-bridged metallocene catalysts, methods for their preparation, and propylene (co)polymers prepared therefrom. The resulting silane-bridged metallocene catalysts are highly active in the polymerization of olefins, particularly ethylene and, surprisingly, propylene. In at least one embodiment, a catalyst system is provided comprising a metallocene compound as described by formula (I): JPEG2025526711000001.jpg97170In the formula, M is a Group 4 metal, X1 and X2 are each a monovalent anionic ligand, or X1 and X2 are bonded to form a metallocycle ring, and R 1 is hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0008] J 1 and J 2 are independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 aryl. Optionally, J 1 and J 2 may be linked to form a 4-, 5-, or 6-membered ring.

[0009] Each R 2 -R 6 is hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0010] Each R 7 -R 16 is hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 aryl, and optionally R 11 and R 12 may be linked to form a silafluorene moiety.

[0011] Each R 17 , R 18 , R 19 , and R 20are independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0012] So that the above-described features of the present disclosure may be understood in detail, a more particular description of the present disclosure, briefly summarized above, can be made by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and should not be considered as limiting the scope of the present disclosure, which may admit of other equally effective embodiments. [Brief explanation of the drawings]

[0013] [Figure 1] 1H NMR spectrum of the dilithium salt, which was prepared in a single step (“one pot”) according to one or more embodiments described in this disclosure.

[0014] [Figure 2] 1H NMR spectrum of catalyst I2, which was prepared in the experimental section below. DETAILED DESCRIPTION OF THE INVENTION

[0015] (Detailed explanation) According to one or more embodiments provided in the present disclosure, diarylsilane-bridged metallocenes can be synthesized by displacing the dichlorocyclopentadienyl fragment with indenyllithium. In a subsequent step, direct lithiation / displacement with an aryl or alkyllithium reagent provides the dilithiated ligand, which is then metallated with a Group IV metal precursor.

[0016] Surprisingly and unexpectedly, it has been discovered that a significant diversity of silane groups in ansa metallocenes can be produced. It has also been surprisingly and unexpectedly discovered that diphenylsilane-bridged metallocenes can be synthesized in fewer steps than conventional synthetic methods. It has even more surprisingly and unexpectedly been discovered that homopropylene and ethylene-propylene copolymers can be produced from the silane-bridged metallocenes, which have improved molecular weight characteristics and can be produced while maintaining excellent catalytic activity and polymer melting point temperatures.

[0017] The general synthetic method provided in this disclosure avoids and eliminates the electronic effects of the prior art that favor deprotonation rather than nucleophilic substitution. The general synthetic method described in this disclosure also allows for a significant diversification of arylsilane derivatives, particularly diarylsilane derivatives. The general synthetic method for preparing the catalysts can also be applied to mixed asymmetric diaryl or monoaryl derivatives. The resulting silane-bridged metallocene catalysts are highly active in the polymerization of olefins, particularly ethylene and, surprisingly, propylene.

[0018] The conventional preparation of silyl-bridged metallocenes requires four steps as shown below. JPEG2025526711000002.jpg45170

[0019] The reactivity of diphenylsilane analogs has previously been shown to favor deprotonation over substitution, as shown below. JPEG2025526711000003.jpg51168

[0020] We have now surprisingly and unexpectedly discovered that diphenylsilane-bridged metallocenes can be synthesized in just three steps. To do this, a dichlorocyclopentadienyl fragment is first substituted with indenyllithium. Direct lithiation / substitution is then carried out with an aryl or alkyllithium reagent to provide a dilithiated ligand, which is then transmetallated with at least one Group 4 metal salt to provide a metallocene precursor containing a diaryl bridge, as shown in the reaction below. JPEG2025526711000004.jpg52170

[0021] These novel metallocene compounds and novel synthesis techniques, as well as the polymers produced therefrom, are described in further detail below. Each appended claim defines a particular invention, and it is recognized that equivalents to the various elements or limitations set forth in the claims are intended to be infringing objects. Depending on the context, all references below to "the invention" may in some cases refer only to certain specific embodiments. In other cases, it will be recognized that references to "the invention" refer to one or more, but not necessarily all, of the subject matter recited in the claims. Each invention is described in further detail below, including specific embodiments, versions, and examples, but the invention is not limited to these embodiments, versions, or examples, and includes those that will enable one skilled in the art to make and use the invention when the information in this disclosure is combined with known information and techniques.

[0022] The diphenylsilane-bridged metallocenes provided herein may be supported or unsupported and may be represented by formula (I): JPEG2025526711000005.jpg79170In the formula, M is a Group 4 metal.

[0023] X1 and X2 can each be a monovalent anionic ligand, or X1 and X2 can combine to form a metallocycle ring.

[0024] R 1 is hydrogen, unsubstituted C1-C 40Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0025] J 1 and J 2 is hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 aryl. Optionally, J 1 and J 2 may be linked to form a 4-, 5-, or 6-membered ring.

[0026] Each R 2 -R 6 is hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0027] Each R 7 -R 16 is hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, where each R' is hydrogen, halogen, or C1-C 10 Alkyl, or C6-C 10 aryl. Optionally, R 11 and R 12 can be combined.

[0028] Each R 17 , R 18 , R 19 , and R 20 are independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R″-SiR′ 3 wherein R″ is C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0029] For purposes of nomenclature, the following numbering scheme is used for indenyl: Note that indenyl can be thought of as a cyclopentadienyl fused to a benzene ring. The structure is depicted below and named as the anion: JPEG2025526711000006.jpg51165

[0030] Also, for clarity, the ring structures below are substituted indenyls, where the substitutions at the 5 and 6 positions above form the ring structure. For purposes of specific compound naming, these ligands are described below. Similar numbering and naming schemes are used for these types of substituted indenyls, including indacenyl, cyclopenta[b]naphthalenyl, heterocyclopentanaphthyl, heterocyclopentaindenyl, etc., and are shown below. Each structure is drawn and named as an anion.

[0031] Non-limiting examples of indacenyl and cyclopenta[b]naphthalenyl include: JPEG2025526711000007.jpg150170

[0032] The synthetic route provided in this disclosure allows for significant diversification of C1 symmetric catalysts through bridge modifications. For example, the following complexes are accessible using the synthetic route provided in this disclosure: JPEG2025526711000008.jpg86170 JPEG2025526711000009.jpg221170 JPEG2025526711000010.jpg221170 JPEG2025526711000011.jpg87170

[0033] (activator) The bridged metallocene compounds can be activated for polymerization catalysis in any manner sufficient to permit coordination or cationic polymerization. In the case of coordination polymerization, this can be achieved by abstracting one ligand and allowing another to insert an unsaturated monomer, or by similarly abstracting and replacing it with yet another ligand that allows for the insertion of an unsaturated monomer (a labile ligand), such as an alkyl, silyl, or hydride. Traditional activators for coordination polymerization techniques are suitable, including Lewis acids such as aluminoxane compounds, and ionizing anion precursor compounds that abstract one ligand to ionize the bridged metallocene metal center to a cation and provide a counterbalancing non-coordinating anion.

[0034] For example, a suitable activator may include a cationic moiety. In any embodiment, the cationic moiety has the formula [R 1 R 2 R 3 AH] + where A is nitrogen and R 1 and R 2 are both —(CH)— groups, where a is 3, 4, 5, or 6, and together with the nitrogen atom form a 4-, 5-, 6-, or 7-membered non-aromatic ring to which one or more aromatic or heteroaromatic rings may optionally be fused via adjacent ring carbon atoms; R 3 is C1, C2, C3, C4, or C5 alkyl, or N-methylpyrrolidinium or N-methylpiperidinium. Alternatively, in any embodiment, the cation moiety has the formula [R n AH4_ n ] +where A is nitrogen, n is 2 or 3, and all R are the same and are C1-C3 alkyl groups, such as trimethylammonium, trimethylanilinium, triethylammonium, dimethylanilinium, and dimethylammonium.

[0035] Suitable activators may be or include an anionic component [Y]. The anionic component may be a non-coordinating anion (NCA) and may have the formula [B(R 4 )4] - wherein R 4 is an aryl group or a substituted aryl group, the one or more substituents of which may be the same or different and are selected from the group consisting of alkyl, aryl, halogen atoms, halogenated aryl, and haloalkylaryl groups. The substituents may be perhalogenated aryl groups or perfluorinated aryl groups, including perfluorophenyl, perfluoronaphthyl, and perfluorobiphenyl.

[0036] Suitable activators may also be or include non-coordinating anions (NCAs) and have the formula (Z)d + (Ad - ), wherein Z is (LH) or a reducible Lewis acid, L is a Lewis base, and H is hydrogen; (LH) + is a Brønsted acid, and Ad - is the charge d - where d is an integer of 1 to 3.

[0037] Suitable activators may also be or include non-coordinating anions (NCAs) and have the formula (Z)d + (Ad - ) in which Ad - is the charge d - where d is an integer from 1 to 3, and Z is a non-coordinating anion having the formula (ArC + ), wherein Ar is an aryl or heteroatom-substituted aryl, C1-C 40 or substituted C-C hydrocarbyl40 is a hydrocarbyl of the formula:

[0038] The ratio of activator to catalytic metal center can be at least 1:100, or at least 1:250, or at least 1:1500.

[0039] The cationic and anionic components of the catalyst system of the present disclosure together form an activator compound. In any embodiment, the activator can be N,N-dimethylanilinium-tetra(perfluorophenyl)borate, N,N-dimethylanilinium-tetra(perfluoronaphthyl)borate, N,N-dimethylanilinium-tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium-tetra(perfluorophenyl)borate, triphenylcarbenium-tetra(perfluoronaphthyl)borate, triphenylcarbenium-tetrakis(perfluorobiphenyl)borate, or triphenylcarbenium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0040] See also International Publication Nos. WO2021 / 162748, WO2013 / 134038, and WO2000 / 024793, which are incorporated herein by reference, for detailed descriptions of suitable catalyst systems.

[0041] (Support material) The silane-bridged metallocenes can be supported or unsupported. If supported, any suitable support material can be used. Suitable support materials can include, but are not limited to, Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon oxide / clay, or mixtures thereof. Silica is preferred.

[0042] (Polymerization reaction) Any conventional solution polymerization, slurry polymerization, or gas phase polymerization process can be used to produce ethylene copolymers using the diphenylsilane-bridged metallocene catalyst provided in the present disclosure. Preferably, a solution polymerization or gas phase polymerization process is used. Any conventional solution polymerization, slurry polymerization, or gas phase polymerization process can be used to produce propylene homopolymers or ethylene-propylene random copolymers using the diphenylsilane-bridged metallocene catalyst provided in the present disclosure. Preferably, a solution polymerization or slurry polymerization process is used.

[0043] Solution polymerization is a bulk polymerization process that uses the monomers and / or comonomers to be polymerized as solvents or diluents, with little or no inert solvent used as a liquid or diluent, a small amount of which may be used as a carrier for catalysts and scavengers.

[0044] The term "solution polymerization" refers to a polymerization process in which the polymer is dissolved in a liquid polymerization solvent, such as an inert solvent, monomer, or a mixture thereof. Solution polymerization is typically homogeneous and refers to a polymerization process in which the polymer product is dissolved in the polymerization solvent. It has been described that such systems are preferably non-turbid (Oliveira, J. et al., (2000, Ind. Eng. Chem. Res., v. 29, pg. 4627). A homogeneous polymerization process is typically one in which at least 90% by weight of the product is soluble in the reaction solvent.

[0045] The term "slurry polymerization" refers to a polymerization process in which a supported catalyst is used and monomer is polymerized on particles of the supported catalyst, and at least 95% by weight of the supported catalyst-derived polymer product is in granular form as solid particles (not dissolved in a diluent).

[0046] When the polymerization is carried out as a slurry (suspension) polymerization or a solution polymerization, an inert solvent or diluent may be used. Suitable diluents / solvents include non-coordinating inert liquids. Examples include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as commercially available (ISOPAR®); perhalogenated hydrocarbons such as perfluorinated C 4-10 Examples of suitable diluents / solvents include alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable diluents / solvents also include liquid olefins that can serve as monomers or comonomers, such as ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; and cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the diluent / solvent is not aromatic, and the content of aromatic compounds in the diluent / solvent is preferably less than 1 wt. %, preferably less than 0.5 wt. %, and preferably less than 0 wt. %, based on the weight of the diluent / solvent. As a solvent, mineral spirits or hydrogenated diesel oil fractions can also be used. Toluene can also be used. The polymerization is preferably carried out in the liquid monomer. When an inert solvent is used, the monomer is typically metered in gaseous or liquid form.

[0047] (comonomer) The at least one other comonomer may be any one or more of C4-C 20 The above C4-C olefins may be included. 20The comonomers may be linear, branched, or cyclic. 20 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. The C2 concentration in the reactor may range from 0.1 to 40.0 wt%, 1 to 40.0 wt%, 1 to 35 wt%, 2 to 20 wt%, 3 to 10 wt%, or 0.1 to 10 wt%. The C4-C2 concentration in the reactor may range from 0.1 to 40.0 wt%, 1 to 40.0 wt%, 1 to 35 wt%, 2 to 20 wt%, 3 to 10 wt%, or 0.1 to 10 wt%. 20 The comonomer concentration can range from 0.1 to 50% by weight, from 1 to 35% by weight, from 2 to 20% by weight, or from 3 to 10% by weight.

[0048] Specific examples of the comonomer include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof. Preferred are hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and homologs and derivatives thereof. Preferred are norbornene, norbornadiene, and dicyclopentadiene.

[0049] In preferred embodiments, one or more dienes (diolefin comonomers) are added to the polymerization process. The diene is present in the polymer produced according to the present disclosure in an amount of up to 10 wt %, preferably 0.00001-8.0 wt %, preferably 0.002-8.0 wt %, and more preferably 0.003-8.0 wt %, based on the total weight of the composition. In some embodiments, 500 ppm or less, preferably 400 ppm or less, and preferably 300 ppm or less of diene is added to the polymerization process. In other embodiments, at least 50 ppm, or 100 ppm or more, or 150 ppm or more of diene is added to the polymerization process.

[0050] Suitable diolefin comonomers are any hydrocarbon structure, preferably C4-C 30and has at least two unsaturated bonds, at least one of which is readily incorporated into a growing polymer chain. It is further preferred that the diolefin comonomer be selected from alpha, omega-diene monomers (i.e., divinyl monomers). More preferably, the diolefin comonomer is a linear divinyl monomer, most preferably containing from 4 to 30 carbon atoms. Specific examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, and pentacosadiene. Included are dienes such as hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, and triacontadiene; particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g / mol). Preferred cyclic dienes include cyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, 5-ethylidene-2-norbornene, divinylbenzene, and dicyclopentadiene, or higher ring-containing diolefins, with or without substituents at various ring positions.

[0051] (polymer) In some embodiments, the polymers produced from the diphenylsilane-bridged metallocenes provided herein may be homopolymers of propylene or copolymers of propylene, which may contain from about 0.1% to about 50% (e.g., 1% to 20%) by weight of one or more C2 or C4-C6 olefins, based on the total weight of the polymer. 20 olefin comonomer, for example from about 0.5 wt. % to about 18 wt. %, for example from about 1 wt. % to about 15 wt. %, for example from about 3 wt. % to about 10 wt. %, based on the total amount of the propylene copolymer, of one or more C2 or C4-C 20of olefin comonomers (e.g., ethylene or C4-C 12 α-olefins such as ethylene, butene, hexene, octene, decene, dodecene, e.g., ethylene, butene, hexene, octene, or C4-C 14 and α,ω-dienes such as butadiene, 1,5-hexadiene, 1,4-heptadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene.

[0052] The propylene homopolymers or propylene copolymers produced in this disclosure may have some degree of isotacticity and may be isotactic or highly isotactic. 13 "Highly isotactic" as used in this disclosure is defined as having at least 10% isotactic pentads according to analysis by C NMR, and is as described in US 2008 / 0045638 at paragraph

[0613] et seq. 13 Atactic polypropylene is defined as having at least 60% isotactic pentads according to analysis by C NMR. In at least one embodiment of the present disclosure, a propylene homopolymer having at least about 85% isotacticity, such as at least about 90% isotacticity, can be produced. In another embodiment, the propylene polymer produced can be atactic. Atactic polypropylene is: 13 It is defined as having less than 10% isotactic or syndiotactic pentads according to analysis by C NMR.

[0053] Unless otherwise indicated, molecular weight distributions and moments (Mw, Mn, Mz, Mw / Mn, etc.), the comonomer content, and branching index (g') were measured using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band filter-based infrared detector ensemble IR5, and a wavelength of approximately 2,700 cm. -1 ~Approx. 3,000cm -1The system covers the band region (corresponding to saturated CH stretching vibrations) and is equipped with an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Reagent-grade 1,2,4-trichlorobenzene (TCB) (Sigma-Aldrich) containing approximately 300 ppm of the antioxidant BHT can be used as the mobile phase at a nominal flow rate of approximately 1.0 mL / min and a nominal injection volume of approximately 200 μL. The entire system, including the transfer line, column, and detector, can be housed in an oven maintained at approximately 145 °C. A predetermined amount of sample is weighed, and approximately 10 μL of flow marker (heptane) is added and sealed in a standard vial. After loading the vial into an autosampler, the oligomer or polymer can be automatically dissolved within the instrument by adding approximately 8 mL of TCB solvent while continuously shaking at approximately 160 °C. The concentration of the sample solution can be about 0.2 to about 2.0 mg / ml, with lower concentrations used for high molecular weight samples. The concentration c at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal I using the formula c = αI, where α is a mass constant determined using polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatograph to the elution volume and the injected mass, which is equal to the predetermined concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) is determined by combining a universal calibration correlation with column calibration, which is performed using monodisperse polystyrene (PS) standards ranging from 700 to 10 mg / mol. The MW at each elution volume is calculated using the following formula: In the formula, variables with the subscript "PS" refer to polystyrene, and variables without a subscript refer to the test sample. PS =0.67 and K PS= 0.000175, and α and K for other materials are calculated as described in the literature (e.g., Sun, T. et al. (2001) Macromolecules, v. 34, pg. 6812), but for purposes of this disclosure and claims thereof, α = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α = 0.695 and K = 0.000579 for linear ethylene polymers, α = 0.705 and K = 0.0002288 for linear propylene polymers, and α = 0.695 and K = 0.000181 for linear butene polymers. Concentrations are in g / cm 3 Molecular weights are expressed in g / mol, and intrinsic viscosity (K in the Mark-Houwink equation) is expressed in dL / g unless otherwise stated.

[0054] The comonomer composition is determined by the ratio of the intensities of the IR5 detector corresponding to the CH2 and CH3 channels, calibrated with PE and PP homo / copolymer standards, the nominal values of which are previously determined by NMR or FTIR. Specifically, this provides the methyl groups per 1,000 total carbons (CH3 / 1000TC) as a function of molecular weight. Next, when calculating the short-chain branching (SCB / 1000TC) content per 1,000TC as a function of molecular weight, an end-group correction is applied to the CH3 / 1000TC function, assuming each chain is linear and terminated at each end with a methyl group. The weight percent of comonomer is then obtained from the following formula, where f is 0.3, 0.4, 0.6, 0.8, etc. for C3, C4, C6, C8, etc. comonomers, respectively: JPEG2025526711000013.jpg12170

[0055] From the GPC-IR and GPC-4D analyses, the bulk composition of the polymer is obtained by considering all signals in the CH3 and CH2 channels within the integration range of the concentration chromatogram. First, the following ratios are obtained: JPEG2025526711000014.jpg17167

[0056] The same calibration of the CH3 and CH2 signal ratios is then applied as mentioned above to obtain CH3 / 1000TC as a function of molecular weight to obtain bulk CH3 / 1000TC. The bulk methyl chain ends per 1,000TC (bulk CH3end / 1000TC) are obtained by weight averaging the end group corrections over the molecular weight range. JPEG2025526711000015.jpg19170Next, convert bulk SCB / 1000TC to bulk w2 using the same method as above.

[0057] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model of static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972). JPEG2025526711000016.jpg1342

[0058] where ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis above, A2 is the second virial coefficient, P(θ) is the monodisperse random coil form factor, and K0 is an optical constant of the system. JPEG2025526711000017.jpg1441In formula, N A is Avogadro's number and (dn / dc) is the refractive index increment of the system. The refractive index is n=1.500 for TCB at 145°C and λ=665 nm. When analyzing polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn / dc=0.1048 ml / mg and A2=0.0015, and when analyzing ethylene-butene copolymer, dn / dc=0.1048 * (1-0.00126 *w2) ml / mg and A2 = 0.0015, where w2 is the weight percent of butene comonomer.

[0059] A high-temperature Agilent (or Viscotek Corporation) viscometer, with four capillaries arranged in a Wheatstone bridge configuration and equipped with two pressure transducers, is used to determine specific viscosities. One transducer measures the total pressure drop across the detector, and the other transducer, located between the two sides of the bridge, measures the differential pressure. The specific viscosity η of a solution passing through the viscometer is S is calculated from these outputs. The intrinsic viscosity [η] at each point in the chromatogram is calculated using the formula [η] = η S The viscosity MW at each point is calculated using the following formula: / c, where c is the concentration, determined from the broadband channel output of the IR5. JPEG2025526711000018.jpg14170 where α ps is 0.67 and K ps is 0.000175.

[0060] Branching index (g' vis ) is calculated using the output of the GPC-IR5-LS-VIS method as follows: avg is calculated using the following formula: JPEG2025526711000019.jpg1431The summation in the equation is over the chromatographic slices, i, within the integration range.

[0061] The branching index g' vis is defined as follows: JPEG2025526711000020.jpg1322In formula, M Vis the viscosity average molecular weight based on molecular weight determined by LS analysis, and K and α above are those of reference linear polymers, which for purposes of this disclosure and claims thereto are: α=0.705 and K=0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers; α=0.695 and K=0.000579 for linear ethylene polymers; α=0.705 and K=0.0002288 for linear propylene polymers; and α=0.695 and K=0.000181 for linear butene polymers. Concentrations are in g / cm 3 The w2b value is calculated as above, the molecular weight is calculated in g / mol, and the intrinsic viscosity (K in the Mark-Houwink equation) is calculated in dL / g unless otherwise specified.

[0062] In one or more specific embodiments, the ethylene-propylene random copolymers (RCPs) produced by the present disclosure may have: a) the ethylene content, based on the total weight of the copolymer, can be 0.1 to 10 wt %, for example, 0.2 to 10 wt %, 0.5 to 10 wt %, 1 to 10 wt %, 2 to 10 wt %, or 3 to 8 wt %; b) the Mw determined by GPC-4D may be from about 5,000 to about 1,000,000 g / mol (e.g., from about 25,000 to about 750,000 g / mol, for example, from about 50,000 to about 500,000 g / mol, for example, from about 80,000 to about 300,000 g / mol, for example, from about 100,000 to about 250,000 g / mol, or from 5,000 to 500,000 g / mol, or from 5,000 to 350,000 g / mol, or from 10,000 to 250,000 g / mol); c) the molecular weight distribution, MWD, (Mw / Mn), as determined by GPC-4D, is greater than about 2, and can be from about 2 to about 30, such as from about 3 to about 20, for example, from about 4 to about 10; d) the melt flow rate (MFR) measured by ASTM D1238 (230°C, 2.16 kg) can be from about 0.1 dg / min to about 1,000 dg / min, from about 1 dg / min to about 100 dg / min, from about 20 dg / min to about 70 dg / min, or from about 5 to about 10 dg / min; and e) The Tm determined by differential scanning calorimetry DSC-2 described below is greater than about 80°C, for example, about 120°C to about 165°C, for example, about 140°C to about 160°C, for example, about 145°C to about 155°C.

[0063] In one or more specific embodiments, the ethylene-propylene elastomers and rubbers (EP) produced by the present disclosure may have: a) an ethylene content of 0.1 to 50 wt%, for example 1 to 35 wt%, 2 to 20 wt%, 3 to 10 wt%, 10 to 40 wt%, 10 to 25 wt%, 15 to 35 wt%, or 20 to 40 wt%, based on the total weight of the copolymer; b) the Mw as determined by GPC-4D may be from about 5,000 to about 1,000,000 g / mol (e.g., from about 25,000 to about 750,000 g / mol, e.g., from about 50,000 to about 500,000 g / mol, e.g., from about 80,000 to about 300,000 g / mol, or from 5,000 to 500,000 g / mol, or from 5,000 to 350,000 g / mol, or from 10,000 to 250,000 g / mol); c) the molecular weight distribution, MWD, (Mw / Mn), as determined by GPC-4D, is greater than about 2, and can be from about 2 to about 30, such as from about 3 to about 20, for example, from about 4 to about 10; d) The melt flow rate (MFR) determined by ASTM D1238 (230°C, 2.16 kg) can be from about 0.1 dg / min to about 1,000 dg / min, from about 1 dg / min to about 100 dg / min, from 20 dg / min to 70 dg / min, or from about 5 to about 10 dg / min.

[0064] In one or more specific embodiments, the propylene homopolymer (hPP) produced by the present disclosure may have: a) the Mw determined by GPC-4D may be from about 5,000 to about 1,000,000 g / mol (e.g., from about 25,000 to about 750,000 g / mol, for example, from about 50,000 to about 500,000 g / mol, for example, from about 80,000 to about 300,000 g / mol, for example, from about 80,000 to about 200,000 g / mol, or from 5,000 to 500,000 g / mol, or from 5,000 to 350,000 g / mol, or from 10,000 to 250,000 g / mol); b) the molecular weight distribution, MWD, (Mw / Mn), as determined by GPC-4D, is greater than about 2, and can be from about 2 to about 30, such as from about 3 to about 20, for example, from about 4 to about 10; c) g' measured by GPC-4D vis is greater than about 0.6, such as from about 0.7 to about 1, such as from 0.8 to 0.95, such as from about 0.7 to about 0.90; d) a melt flow rate (MFR) determined by ASTM D1238 (230°C, 2.16 kg) can be from about 0.1 dg / min to about 3,000 dg / min, from about 1 dg / min to about 100 dg / min, from about 10 dg / min to about 100 dg / min, or from about 5 to about 10 dg / min; e) The melting point (Tm) determined by differential scanning calorimetry (DSC-2) described below is greater than about 120°C, and can be, for example, from about 130°C to about 165°C, for example, from about 140°C to about 160°C, or from about 145°C to about 155°C. [Example]

[0065] The above discussion can be further illustrated by reference to the following non-limiting examples. Three silane-bridged metallocene structures (I1, I2, and I3) were prepared and used to produce propylene homopolymers and ethylene-propylene copolymers. Two comparative metallocene catalysts (C1 and C2) were also prepared and tested. The structures of these five catalysts are shown below.

[0066] The structures of the comparative metallocene catalysts (C1 and C2) are shown below.

[0067] JPEG2025526711000021.jpg81170

[0068] The structures of the silane-bridged metallocene structures (I1, I2, and I3) of the present disclosure are shown below.

[0069] Catalysts C1, C2, and I1 were prepared from silafluorenyl dichloride using the following traditional route. JPEG2025526711000022.jpg50170

[0070] Catalysts I2 and I3 were prepared using the following modified one-pot technique. JPEG2025526711000023.jpg131170

[0071] Figure 1 shows a representative spectrum of the in-situ substitution-lithiation to prepare catalyst I2. Figure 2 shows the spectrum of isolated catalyst I2, confirming the very high purity of I2. The above spectra demonstrate the very high purity of the isolated material.

[0072] Catalysts C1 and C2 were prepared according to previously reported procedures, e.g., those described in US Pat. No. 9,266,910 and WO 2021 / 034459 A1.

[0073] Catalyst I1 was prepared according to Scheme 1 below. JPEG2025526711000024.jpg77170

[0074] Preparation of 9-chloro-9-(2,3,4,5-tetramethylcyclopentadienyl)-silafluorene: To a pre-cooled, stirred solution of dichlorosilafluorene (0.505 g, 2.01 mmol) in diethyl ether (40 mL) was added sodium tetramethylcyclopentadienide (0.290 g, 2.01 mmol, 1 equiv.). The reaction was stirred at room temperature for 1.5 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane and filtered through Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as an off-white solid (0.489 g, 72% yield). 1 H NMR(C6D6):δ7.46-7.39(m, 4H), 7.12(td, 2H, J=7.6, 1.4Hz), 7.01(td, 2H, J=7.4, 1.0Hz), 3.64-3.27(br s, 1H), 1.87(s, 6H), 1.54(s, 6H)

[0075] Preparation of 4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)silafluorene: To a stirred solution of 9-chloro-9-(2,3,4,5-tetramethylcyclopentadienyl)-silafluorene (0.140 g, 0.416 mmol) in tetrahydrofuran (10 mL) was added a solution of lithium 4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacenide (0.128 g, 0.416 mmol, 1 equiv.) in tetrahydrofuran (5 mL). The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered through Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then concentrated under high vacuum. The resulting residue was stirred in hexane (5 mL) and filtered through Celite. The hexane extract was concentrated under a stream of nitrogen and then under high vacuum to give the product as an off-white foam (0.237 g, 94% yield). 1H NMR(C6D6):δ7.78(s, 1H), 7.52-7.37(m, 7H), 7.26(d, 1H, J=7.1Hz), 7.15-7.09(m, 1H), 7.01(td, 1H, J=7.3, 1.0Hz), 6.95(td, 1H, J=7.3, 1.0Hz), 6.49(dd, 1H, J=7.0, 1.2Hz), 6.38(s, 1H), 4.23(s, 1H), 4.00(s, 1H), 3.12-2.82(m, 4H), 2.37(s, 3H), 2.05-1.88(m, 2H), 1.86(s, 3H), 1.50(s, 3H), 1.43(s, 3H), 1.37(s, 3H), 1.30(s, 9H)

[0076] Preparation of lithium(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenidyl)(2,3,4,5-tetramethylcyclopentadienidyl)silafluorene: To a precooled, stirred solution of 4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)-silafluorene (0.237 g, 0.393 mmol) in diethyl ether (10 mL) was added n-butyllithium (0.33 mL, 2.74 M in hexanes, 0.90 mmol, 2.3 equiv.). The reaction was stirred at room temperature for 2 hours. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in hexane (2 mL). The resulting suspension was filtered through a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as an orange solid (0.125 g, 45% yield), which contained diethyl ether (0.82 equiv.). 1H NMR (400 MHz, C4H8O):δ7.99(d, 2H, J=7.0Hz), 7.79(d, 2H, J=7.7Hz), 7.46(d, 2H, J=8.4Hz), 7.34(d, 2H, J=8.4Hz), 7.23(td, 2H, J=7.5, 1.4Hz), 7.16(s, 1H), 7.11(td, 2H, J=7.2, 1.1Hz), 5.90(s, 1H), 2.76(t, 2H, J=7.0Hz), 2.70(t, 2H, J=7.0Hz), 2.20(s, 3H), 1.92(s, 6H), 1.85(s, 6H), 1.84-1.77(m, 2H), 1.35(s, 9H)

[0077] Preparation of silafluorenyl(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst I1): To a stirred suspension of zirconium chloride (0.048 g, 0.206 mmol, 1.15 equiv.) in diethyl ether (5 mL) was added a suspension of lithium(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenidyl)(2,3,4,5-tetramethylcyclopentadienidyl)silafluorene (0.125 g, 0.179 mmol, containing 0.82 equiv. of diethyl ether) in diethyl ether (10 mL). The reaction was stirred at room temperature for 6 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered through Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes, then concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange-yellow solid (0.102 g, 74% yield). 1H NMR (400 MHz, CD2Cl2):δ8.73(d, 1H, J=8.0Hz), 8.45(dd, 1H, J=7.5, 0.9 Hz), 8.11(ddd, 2H, J=9.4, 7.8, 1.2Hz), 7.94(s, 1H), 7.69-7.57(m, 3H), 7.56-7.43(m, 5H), 6.84(s, 1H), 2.97(t, 4H, J=7.2 Hz), 2.47(s, 3H), 2.32(s, 3H), 2.23(s, 3H), 2.07-1.97(m, 5H), 1.95(s, 3H), 1.38(s, 9H)

[0078] Catalyst I2 (R=Ph) was prepared according to Scheme 1 below. JPEG2025526711000025.jpg87170

[0079] Solid Me4CpLi (2.02 g, 15.8 mmol) was slowly added to a pre-cooled (-30 °C) solution of PhSiCl3 (3.35 g, 15.8 mmol) in THF. The reaction mixture was allowed to warm to room temperature and stirred overnight. After 18 h, the solvent was removed in vacuo, and the residue was extracted with pentane (2 × 20 mL) and filtered through Celite. Removal of the solvent afforded the final product, which appeared to be of good purity (93% yield). 1 H NMR (C6D6) spectrum: δ 7.47 (m, 2H), 7.02 (m, 1H), 6.97 (m, 2H), 3.21 (bs, 1H), 1.92 (bs, 6H), 1.47 (bs, 1H)

[0080] Preparation of 4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]-chloro-phenyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane: In a 20 mL vial, solid lithium 4-(4-tert-butyl-phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indecenyl (0.781 g, 2.5 mmol) was dissolved in 2 mL of THF and 5 mL of diethyl ether. After cooling, this solution was slowly transferred (via pipette) to a pre-cooled (-30 °C) solution of dichloro-phenyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (1.5 g, 5.1 mmol) in diethyl ether. Upon complete addition, the reaction mixture was pale yellow and slightly cloudy. After 1 h, the solvent was removed in vacuo, and the residue was extracted with pentane and concentrated in vacuo. The yellow pentane solution was placed in a freezer. After 18 hours, yellow crystals precipitated, the solution was decanted, the crystals were washed with 10 mL of pentane and dried under vacuum to give the spectrally pure product in 49% yield. 1 H NMR (C6D6):δ7.74(s, 1H), 7.48(s, 2H), 7.41(s, 4H), 7.08(s, 1H), 7.00(s, 2H), 6.77(s, 1H), 3.99(s, 1H), 3.81(s, 1H), 2.87(d, 4H), 2.16(s, 3H), 1.99(s, 3H), 1.86(m, 2H), 1.72(s, 3H), 1.55(s, 3H), 1.44(s, 3H), 1.30(s, 9H)

[0081] Preparation of dilithium-diphenyl(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane: To a precooled, stirred solution of chloro(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)phenylsilane (0.661 g, 1.17 mmol) in tetrahydrofuran (approximately 40 mL) was added phenyllithium (1.7 mL of a 2.1 M solution in dibutyl ether). The reaction immediately turned clear orange and was stirred at room temperature for 1 hour. After 1 hour, the solvent was removed in vacuo to give an orange solid. The solid was washed with 2×10 mL of hexane and dried under vacuum to give a yellow solid. 1 The H NMR spectrum showed a clean product with some residual THF and dibutyl ether in essentially quantitative yield. This material was used directly in the next step without further purification. 1 H NMR (THF-d8) δ 7.88(s, 4H), 7.54(s, 2H), 7.41(s, 2H), 7.16(s, 6H), 6.74(s, 1H), 6.01(s, 1H), 2.83(s, 2H), 2.64(s, 2H), 2.00(s, 6H), 1.93(s, 3H), 1.62(s, 6H), 1.40(s, 9H). The last set of protons in the indacene backbone was masked by residual dibutyl ether signals in the aliphatic region.

[0082] Preparation of diphenylsilyl-(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst I2): To a stirred suspension of dilithium-diphenyl(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (1.05 g, 1.31 mmol, containing 1.2 equivalents of BuO and 0.6 equivalents of THF) in diethyl ether (approximately 30 mL) at −30° C., ZrCl(OEt) (0.5 g, 1.31 mmol) was added slowly. The reaction mixture was allowed to warm to room temperature and stirred overnight. After 18 h, the solvent was removed in vacuo to give a bright yellow residue. The residue was extracted with dichloromethane (2×25 mL), filtered over Celite, and concentrated to give a yellow solid. The solid was triturated with pentane (20 mL) by brief stirring and filtered through a glass frit. The solid was dried under vacuum to give the final product in 66% yield. 1 H NMR(CD2Cl2) δ8.07(s, 4H), 7.51(s, 10H), 7.00(s, 1H), 6.91(s, 1H), 2.95(s, 2H), 2.74(s, 1H), 2.61(s, 1H), 2.12(s, 3H), 2.03(s, 3H), 1.97(m, 5H), 1.89(s, 3H), 1.74(s, 3H), 1.42(s, 9H)

[0083] Catalyst I3 (R=Me) was prepared according to Scheme 3 below. JPEG2025526711000026.jpg94167

[0084] Preparation of dilithium-(1-((4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(methyl)(phenyl)silyl)-2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl): To a precooled, stirred solution of chloro(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)phenylsilane (0.156 g, 0.277 mmol) in tetrahydrofuran (approximately 8 mL) was added methyllithium (0.537 mL of a 1.6 M solution, 3.1 equivalents). The reaction immediately turned clear orange and was stirred at room temperature for 20 minutes. After 20 minutes, the solvent was removed in vacuo to give an orange solid. The solid was washed with 2×10 mL of hexane and dried under vacuum to give a yellow solid. 1 H NMR showed essentially quantitative yield and high purity product with approximately 2 equivalents of residual THF. This material was used directly in the next step. 1 H NMR(THF-d8) δ7.65(s, 2H), 7.53(s, 2H), 7.41(s, 2H), 7.16(s, 4H), 5.95(s, 1H), 2.81(m, 4H), 2.11(s, 3H), 1.98(s, 6H), 1.85(m, 8H), 1.40(s, 9H), 0.88(s, 3H)

[0085] Preparation of (1-((4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(methyl)(phenyl)silyl)-2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)zirconium dichloride) (Catalyst I3) ZrCl4(OEt2)2 (0.11 g, 0.288 mmol) was added slowly to a stirred suspension (ca. 30 mL) of dilithium-(1-((4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(methyl)(phenyl)silyl)-2,3,4,5-tetramethylcyclopenta-2,4-dienyl) (0.20 g, 0.286 mmol) in diethyl ether at −30 °C. The reaction mixture was allowed to warm to room temperature and stirred overnight. After 18 h, the solvent was removed in vacuo to give a bright yellow residue. The residue was extracted with dichloromethane (2 × 5 mL), filtered over Celite, and concentrated to give a yellow solid. The solid was briefly triturated with hexane (10 mL) and filtered over a glass frit. 1 The H NMR spectrum showed the expected product in 45% yield. The two isomers observed can be attributed to the syn / anti relationship of the asymmetric silane to the indacenyl ligand. 1 H NMR (CD2Cl2) δ 8.04 (s, 4H), 7.63-7.48 (overlapping m, 13H, both isomers), 6.89 (s, 1H, isomer 1), 6.84 (s, 1H, isomer 1), 6.83 (s, 1H, isomer 2), 3.12-2.50 (m, 8H, both isomers), 2.35 (s, 3H, isomer 1), 2.17 (s, 3H, isomer 2), 2.05-2.03 (two s, 6H, both isomers), 2.01-2.00 (two s, 6H, both isomers), 1.97 (s, 3H), 1.89 (s, 3H), 1.77 (s, 3H), 1.61(s, 3H), 1.42(s, 9H, isomer 1), 1.41(s, 9H, isomer 2), 1.28(s, 3H, isomer 1), 1.14(s, 3H, isomer 2)

[0086] (Procedure for solution polymerization reaction) Propylene polymerization in solution was carried out using high-throughput conditions. A pre-weighed glass vial insert and a disposable stirring paddle were attached to each reactor vessel in a reactor containing 48 individual reactors. The reactor was then closed, and propylene (typically 1–4 mL) was introduced. A solvent (typically isohexane) was then added to bring the total reaction volume, including subsequent additions, to 5 mL, and the reactors were heated to their set temperatures (usually about 50°C to about 110°C). The contents of the vessels were stirred at 800 rpm. An activator solution (typically 1.1–1000 molar equivalents of methylalumoxane (MAO) in toluene) was then injected into the reactor along with 500 μL of toluene. The catalyst (typically 0.50 mM in toluene, e.g., 20–40 nmol of catalyst) and a separate aliquot of toluene (500 μL) were then added to initiate the reaction. The equivalent weight is determined based on the molar equivalents relative to the number of moles of transition metal in the catalyst complex. The reaction was then allowed to proceed until a predetermined pressure was absorbed by the reaction. At this point, the reaction was stopped by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and inert atmosphere glove box, and volatile components were removed at elevated temperature and reduced pressure using a Genevac HT-12 centrifuge and a Genevac VC3000D vacuum evaporator. The vial was then weighed to determine the yield of the polymer product. The resulting polymer was analyzed by Rapid GPC (see below) to determine molecular weight and by DSC (see below) to determine melting point.

[0087] Table 1 shows the catalytic activity and polymerization results for homopolypropylene (hPP), which was polymerized using the control catalysts C1 and C2 and the catalysts I1 to I3 of the present disclosure. Table 2 shows the polymerization results for EP copolymers, which were polymerized using the same catalysts as above. Table 1: hPP solution polymerization using unsupported catalysts (70°C, MAO activator) Table 2: Solution polymerization of ethylene-propylene copolymer using unsupported catalyst (70°C, MAO activator) JPEG2025526711000028.jpg124154

[0088] The results in Tables 1 and 2 show that catalysts I1-I3 are highly active in propylene polymerization, producing polymer properties comparable to those of comparative / control catalysts C1 and C2 and equal or better polymer crystallinity. For EP copolymers, catalysts I1 and I3 showed improved ethylene response, particularly higher uptake at equivalent ethylene partial pressures, compared to the control catalysts C1 and C2.

[0089] Example 2: Supported Catalyst Catalysts C1-C2 and I1-I3 were supported on conventional silica supports and used for the polymerization of propylene under industrially relevant slurry and bulk slurry conditions.

[0090] (Preparation of Silica-Supported MAO (SMAO)) In a Celstir, 10.0 g of DM-L403 silica (AGC, dehydrated at 200°C) was suspended in approximately 100 mL of dry toluene and cooled to -30°C. While stirring, 15.8 g of a cooled solution of 30% MAO was slowly added (over 10 minutes) to the stirred silica mixture. The reaction was stirred for 1.5 hours. After 1.5 hours, the temperature was increased to 100°C, and the reaction was stirred for an additional 2.5 hours. Upon cooling, the resulting slurry was filtered, and the solids were washed with toluene (2 x 50 mL), pentane (2 x 50 mL), and dried under vacuum for at least 2 hours to yield SMAO as a white, free-flowing powder.

[0091] (Supported catalysts C1, C2, I1, I 2、 and general preparation of I3) In a 25 mL scintillation vial, 0.6 g of previously prepared SMAO was suspended in 10 mL of anhydrous toluene and placed on a shaker. Next, 0.310 mL of triisobutylaluminum solution (1 M in hexane) was added, and the resulting mixture was vigorously stirred at room temperature for 15 minutes. After 15 minutes, the metallocene catalyst (based on a 12 μmol / g loading) was slowly added to the silica mixture as a toluene solution (approximately 2 mL). The resulting slurry was vigorously stirred for 3 hours. After 3 hours, the slurry was filtered over a glass frit, and the solid was washed with toluene (2 × 5 mL) and pentane (2 × 5 mL) and dried under vacuum to yield the supported catalyst as an orange / red, free-flowing solid. Optionally, the resulting solid was suspended in mineral oil to make a 5 wt. % slurry, which was used for polymerization in a laboratory reactor.

[0092] (Bulk Polymerization Procedure) A 1 L autoclave reactor equipped with a mechanical stirrer was used for polymer preparation. Prior to start-up, the reactor was maintained at 90°C under a nitrogen purge for 30 minutes. After cooling to ambient temperature, propylene (500 mL), scavenger (1 M TIBAL, 0.2 mL triisobutylaluminum), and optional hydrogen (charged from a 50 mL bomb at the desired pressure) were introduced into the reactor and mixed for 5 minutes. Next, the desired amount of supported catalyst (typically 12.5-25.0 mg) was introduced into the reactor by flushing a predetermined amount of catalyst slurry (5 wt. % in mineral oil) from the catalyst tube with 100 mL of liquid propylene. The reactor was held at room temperature for 5 minutes (prepolymerization stage), and then the temperature was increased to 70°C. The reaction was allowed to proceed at that temperature for the desired time (typically 30 minutes). After the prescribed time, the temperature was reduced to 25°C, the excess propylene was vented, and the polymer granules were collected and dried under vacuum at 60°C overnight.

[0093] (Slurry Polymerization Procedure) Slurry propylene polymerization was carried out under high-throughput conditions according to the following general procedure. A pre-weighed glass vial insert and a disposable stirring paddle were attached to each reactor vessel in a reactor containing 48 individual reactors. The reactors were then closed, and propylene (typically 1–4 mL) was introduced. Triisobutylaluminum (TIBAL) was then introduced as a scavenger (typically 2.5–10 μmol) and added as a solution in toluene or isohexane. Solvent (typically isohexane) was then added to bring the total reaction volume, including the latter addition, to 5 mL, and the reactor was heated to the set temperature (usually about 50°C to about 110°C). At this stage, ethylene (typically 70–140 psi) was added to the reactor. The contents of the vessel were stirred at 800 rpm. A supported catalyst (typically 0.75 mg) was introduced as a toluene slurry (typically at a concentration of 3.0 mg / mL) to initiate the reaction. The equivalent weight is determined based on the molar equivalent relative to the number of moles of transition metal in the catalyst complex. The reaction was then allowed to proceed until a predetermined pressure was absorbed by the reaction, or 30 minutes for homopolymer polymerization. At this point, the reaction was stopped by pressurizing the vessel with compressed air or carbon dioxide. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and inert atmosphere glove box and volatile components were removed at elevated temperature and reduced pressure using a Genevac HT-12 centrifuge and a Genevac VC3000D vacuum evaporator. The vial was then weighed to determine the yield of the polymer product. The resulting polymer was analyzed by Rapid GPC (see below) to determine molecular weight and DSC (see below) to determine melting point. [Table 3] Results of slurry polymer polymerization using supported catalysts Table 4. Bulk slurry polymerization results of propylene using supported catalysts (70°C, 2 mmol H2) JPEG2025526711000030.jpg53169

[0094] The data in Table 3 confirm the excellent activity and operability of the disclosed arylsilane-substituted catalysts I1-I3. Significant improvements in EP rubber molecular weight properties were also demonstrated, particularly for catalysts I2 and I3. For homopolypropylene polymerizations using catalyst I2, a significant improvement in activity (approximately 18,000 g / g) was observed under bulk slurry conditions compared to the control catalyst C1 (13,200 g / g) (Table 4). Polymers produced with the silafluorenyl crosslinking system I1 showed a slight improvement in melting point (Tm = 159°C) compared to the control C1.

[0095] It was surprising and unexpected that the silane-bridged metallocenes I1, I2, and I3 exhibited excellent activity in producing hPP and EP copolymers. It was also surprising and unexpected that the silane-bridged metallocenes I1, I2, and I3 could produce hPP with higher melting points (≧153° C.) and higher molecular weight (Mw) ethylene-propylene copolymers, which may result in improved impact properties.

[0096] (Test procedure used) Rapid GPC Procedure: To determine various molecular weight-related values by GPC, high-temperature size 5 exclusion chromatography was performed using an automated "Rapid GPC" system, which is generally described in U.S. Patent Nos. 6,491,816, 6,491,823, 6,475,391, 6,461,515, 6,436,292, 6,406,632, 6,175,409, 6,454,947, 6,260,407, and 6,294,388, each of which is incorporated herein by reference in its entirety for U.S. purposes. The apparatus consisted of three 30 cm x 7.5 mm linear columns, each containing PLgel 10 μm, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580 to 3,390,000 g / mol. The system was operated at an elution flow rate of 2.0 mL / min and an oven temperature of 165°C. 1,2,4-Trichlorobenzene was used as the eluent. The polymer samples were dissolved in 1,2,4-trichlorobenzene at concentrations of 0.1 to 0.9 mg / mL. 250 μL of the polymer solution was injected into the system. The polymer concentration in the eluent was monitored using an evaporative light scattering detector (shown in the example in Table 3) or a Polymer Char IR4 detector. The reported molecular weights are relative to linear polystyrene standards and are uncorrected.

[0097] DSC Procedure, DSC-1: The melting points (Tm) of samples polymerized under the high-throughput conditions described above were measured using differential scanning calorimetry (DSC) using commercially available equipment such as a TA Instruments TA-Q200 DSC. Typically, 5-10 mg of molded or plasticized polymer was sealed in an aluminum pan and loaded into the instrument at room temperature. The sample was pre-annealed at about 220°C for about 15 minutes and then cooled to room temperature overnight. The sample was then heated to about 220°C at a heating rate of about 100°C / min, held at this temperature for at least about 5 minutes, and then cooled at a rate of about 50°C / min, typically to a temperature at least about 50°C below the crystallization temperature. Melting points were recorded during the heating period.

[0098] DSC Procedure, DSC-2: The peak melting point, Tm, (also referred to as melting point) and peak crystallization temperature, Tc, (also referred to as crystallization temperature) described for the reactor batches were determined using the following DSC procedure in accordance with ASTM D3418-03. Differential scanning calorimetry (DSC-2) data may be obtained using a TA Instruments model DSC2500 instrument. Samples weighing approximately 5-10 mg were sealed in aluminum hermetic sample pans and loaded into the instrument at approximately room temperature. DSC data are recorded by first gradually heating the sample to approximately 200°C at a rate of approximately 10°C / min. The sample was held at about 200°C for 5 minutes, then cooled to about -50°C at a rate of about 10°C / min, followed by an isothermal hold for about 5 minutes, then heated to about 200°C at a rate of about 10°C / min, held at about 200°C for about 5 minutes, and then cooled to about 25°C at a rate of about 10°C / min. Both the first and second cycle thermal events were recorded. The melting points and crystallization temperatures reported in this disclosure were obtained during the second heating / cooling cycle unless otherwise noted. In the event of a discrepancy between DSC Procedure-1 and DSC Procedure-2, DSC Procedure-2 is used.

[0099] Certain embodiments and features have been described using a set of upper and lower numerical limits. It is understood that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits, and ranges appear in one or more of the claims below. All numerical values are intended to be "about" or "approximately" values, taking into account experimental error and variations that one of ordinary skill in the art would expect.

[0100] Various terms have been defined above. If a term used in the claims is not defined above, that term should be given the broadest definition that one of ordinary skill in the art would give that term, as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this disclosure are incorporated by reference in their entirety to the extent they are not inconsistent with this disclosure and in all jurisdictions where such incorporation is permitted.

[0101] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof, the scope of which is determined by the following claims.

Claims

1. A catalyst system comprising a metallocene compound described by formula (I): During the ceremony, M is a Group 4 metal; X is each a monovalent anionic ligand, or two Xs are bonded to form a metallocyclic ring; R 1 is hydrogen, unsubstituted C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, unsubstituted C6-C 62 aryl, substituted C6-C 62 aryl, unsubstituted C 4 -C 62 heteroaryl, substituted C 4 -C 62 heteroaryl, -NR'2, -SR ’ , -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C 1 -C 10 alkylene, and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl; J 1 and J 2 However, independently, hydrogen, unsubstituted C 1 -C 40 Hydrocarbil, C 1 -C 40 Substituted hydrocarbyl, unsubstituted C6-C 62 Aryl substitution C6-C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 The heteroaryl compounds are -NR'2, -SR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C 1 -C 10 It is an alkylene, where each R' is hydrogen, halogen, or C. 1 -C 10 Alkyl, or C 6 -C 10 It is an alphabet, and optionally, J 1 and J 2 They may combine to form a 4, 5, or 6-membered ring; Each R 2 -R 6 However, hydrogen, unsubstituted C 1 -C 40 Hydrocarbil, C 1 -C 40 Substituted hydrocarbyl, unsubstituted C6-C 62 Aryl substitution C6-C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C 1 -C 10 It is an alkylene, where each R' is hydrogen, halogen, or C. 1 -C 10 Alkyl, or C 6 -C 10 It is an allele; Each R 7 -R 16 However, hydrogen, unsubstituted C 1 -C 40 Hydrocarbil, C 1 -C 40 Substituted hydrocarbyl, unsubstituted C6-C 62 Aryl substitution C6-C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C 1 -C 10 It is an alkylene, where each R' is hydrogen, halogen, or C. 1 -C 10 Alkyl, or C 6 -C 10 It is aryl; optionally, R 11 and R 12 They can combine to form a silafluorene moiety; and, Each R 17 , R 18 R 19 and R 20 is independently hydrogen, halogen, unsubstituted C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, unsubstituted C6-C 62 aryl, substituted C6-C 62 aryl, unsubstituted C 4 -C 62 heteroaryl, substituted C 4 -C 62 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C 1 -C 10 alkylene, and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, a catalyst system.

2. further comprising an activator and an optional support material, wherein the activator is an aluminoxane or an NCA represented by the formula: (Z)d + (Ad - ) and is: In the formula, Z is (L-H) or a reducible Lewis acid. L is a Lewis base, H is hydrogen, (L-H) + It is a Brønsted acid, Ad - is charge d - It is a non-coordinating anion having, and d is an integer from 1 to 3, and The above support material is Al 2 O 3 , ZrO 2 SiO 2 SiO 2 / Al 2 O 3 SiO 2 / TiO 2 The catalyst system according to claim 1, selected from silica clay, silicon oxide / clay, and mixtures thereof.

3. The aforementioned activator is of formula (Z)d + (Ad - This is an NCA represented as: Ad - is charge d - It is a non-coordinating anion having, d is an integer from 1 to 3, and Z is the expression: (Ar 3 C + A reducing Lewis acid represented by ), wherein Ar is an aryl or heteroatom substituted with C 1 ~C 40 Hydrocarbyl or substituted C 1 ~C 40 The catalyst system according to claim 2, wherein the catalyst is hydrocarbyl.

4. A method for producing propylene homopolymer or propylene copolymer, Propylene, and one or more C species of any choice. 2 or C 4 ~C 40 A step of introducing an olefin comonomer, the catalyst system according to claim 1, and optionally hydrogen into a reactor with a reactor pressure of 0.7 bar to 70 bar (70,000 to 7,000,000 Pa) and a reactor temperature of 20°C to 150°C, and A method for producing a propylene homopolymer or propylene copolymer, comprising the step of obtaining a propylene homopolymer or a propylene copolymer.

5. Said C 4 -C 40 The manufacturing method according to claim 4, wherein the olefin comonomer is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclobutane, 1-heptene, 1-octene, 1-decene, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadien.

6. The manufacturing method according to claim 4, wherein the Mw value of the propylene homopolymer or propylene copolymer, as measured by gel permeation chromatography, is 5,000 to 500,000 g / mol, or 5,000 to 350,000 g / mol, or 10,000 to 250,000 g / mol.

7. The manufacturing method according to claim 4, wherein the Mw value of the propylene homopolymer or propylene copolymer, as measured by gel permeation chromatography, is 10,000 to 250,000 g / mol.

8. The manufacturing method according to claim 4, wherein the melt flow rate (MFR) of the propylene homopolymer or propylene copolymer according to ASTM D1238 (230°C, 2.16 kg) is 0.1 dg / min to 3000 dg / min, or 1 dg / min to 1000 dg / min, or 10 dg / min to 100 dg / min, or 20 dg / min to 70 dg / min.

9. The manufacturing method according to claim 6, wherein the molecular weight distribution (Mw / Mn) of the propylene homopolymer or propylene copolymer is 2 to 30, or 3 to 20, or 4 to 10, and the propylene homopolymer or copolymer has a melting point (Tm) exceeding 80°C, or exceeding 130°C, or exceeding 150°C.

10. The production method according to claim 6, wherein the propylene copolymer contains 0.1 to 50% by mass, 1 to 35% by mass, 2 to 20% by mass, or 3 to 10% by mass of the comonomer.

11. The catalyst system according to claim 1, wherein R11 and R12 combine to form a silafluorene moiety.

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