Methods of making diphenylsilane bridged c1 symmetric catalysts and polymers made therefrom

Abstract

Diaryl silane bridged metallocene catalysts, methods of making the same, and propylene polymers (copolymers) made therefrom. The obtained silane-bridged metallocene catalyst has very high activity in the polymerization of olefins, especially ethylene and propylene. The diarylsilane bridged metallocene may be synthesized by substituting a dichlorocyclopentadienyl fragment with lithium indenyl. Direct lithiation / substitution with an aryl or alkyl lithium reagent provides a dilithiated ligand that undergoes metallization with a Group IV metal precursor.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 370,829, filed on August 9, 2022, the disclosure of which is incorporated herein by reference. Background of the Invention Field of the Invention

[0004] Embodiments of the present invention generally relate to asymmetric metallocene catalyst compounds. More specifically, embodiments of the present invention relate to asymmetric, bridged metallocenes having substituted indacenyl ligands and propylene polymers prepared therefrom.

[0005] Related technical description

[0006] Traditional bridged metallocene synthesis relies on replacing the leaving group X with an introduced lithium salt of indene, indacene or cyclopentadiene. In recent years, silane-bridged metallocenes have been found to be highly efficient in producing propylene polymers with desirable physical and mechanical properties.

[0007] Diphenylsilane-bridged metallocenes have been particularly studied. However, due to the difficulties associated with their preparation, they remain a rather elusive synthetic target. The challenge of installing a diphenylsilane bridge is related to the increased proton acidity of the key CpHSi(Ph)2X (X=Cl, OTf) intermediate, where the addition of a second nucleophile (e.g., indenyllithium or fluorenyllithium) produces a mixture of products. The addition of a second nucleophile also favors deprotonation of Cp rather than the intended nucleophilic substitution of the Si-X group. This deprotonation significantly complicates the synthesis and requires many lengthy purification steps.

[0008] Related references include: CN101235106B, which details the synthesis of 1-indenyl analogs of diphenylsilane; US 9,790,240 B2, which describes mixed C2-symmetric systems of diphenylsilane derivatives; Izmer, V. et al. (2001), "ansa-Metallocenes with a Ph2Si Bridge: Molecular Structures of HfCl2[Ph2Si(η 5 -C5H4)]and HfCl2[Ph2Si(C 13 H9)(η 5-C5H4)]2," J. Chem. Soc., Dalton Trans., pp. 1131-1136; WO2001 / 005870A1 and WO2002 / 002575A1 describe C2-symmetrical complexes with arylsilane bridges; Heuer, B. et al. (2005), "Alternating Ethene / Propene Copolymers by C1-SymmetricMetallocene / MAO Catalysts," Macromolecules, v. 38 (8), pp. 3054-3059; EP 0754698A2; EP 1046642A2, which describes Cp-fluorenyl analogs with a diphenylsilane bridge; US2019 / 0161559A1 and WO2018 / 151904A1 describe bis-Cp analogs with a diphenylsilane bridge, US2020 / 043758, WO2014 / 099303, US 9,266,910B2; and KR 2020003044.

[0009] There remains a need for new and more reliable methods for synthesizing diphenylsilane-bridged metallocenes for use in preparing propylene polymers. SUMMARY OF THE INVENTION

[0011] Provided herein are diarylsilane-bridged metallocene catalysts, methods for their preparation, and propylene polymers (copolymers) prepared therefrom. The resulting silane-bridged metallocene catalysts are very active in the polymerization of olefins, particularly ethylene and surprisingly propylene. In at least one embodiment, a catalyst system comprising a metallocene compound described in formula (I) is provided:

[0012]

[0013] wherein M is a Group 4 metal; each of X1 and X2 is a monovalent anionic ligand, or X1 and X2 are joined to form a metallocycle ring; R 1 is hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

[0014] J 1 and J 2 are independently hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl. Optional J 1 and J 2 Can join to form four, five or six membered rings.

[0015] Each R 2 -R 6 Can be hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

[0016] Each R 7 -R 16 Can be hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, unsubstituted C4-C 62Aryl, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl; optionally, R 11 and R 12 Can be joined to form a silafluorene moiety.

[0017] Each R 17 , R 18 , R 19 , and R 20 may independently be hydrogen, halogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

[0018] BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to understand the above-recorded features of the present invention in detail, a more specific description of the present invention briefly summarized above can be carried out by reference to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings only illustrate typical embodiments of the present invention and are therefore not to be considered as limiting its scope, as the present invention may admit of other equally effective embodiments.

[0020] Figure 1 The dilithium salt prepared in a single step ("one-pot") according to one or more embodiments described herein is shown.1 H NMR spectrum.

[0021] Figure 2 The catalyst I2 prepared in the experimental section below is shown 1 H NMR spectrum.

[0022] Detailed Description

[0023] According to one or more embodiments provided herein, diarylsilane-bridged metallocenes can be synthesized by replacing the dichlorocyclopentadienyl fragment with an indenyl lithium. In the next step, direct lithiation / substitution with an aryl or alkyl lithium reagent provides a dilithiated ligand that undergoes metallation with a Group IV metal precursor.

[0024] It has been surprisingly and unexpectedly discovered that significant diversification of the silane groups of ansa-type metallocenes can be achieved. It has also been surprisingly and unexpectedly discovered that diphenylsilane-bridged metallocenes can be synthesized using fewer steps than conventional syntheses. Even more surprisingly and unexpectedly, homopolypropylene and ethylene-propylene copolymers can be prepared from silane-bridged metallocenes having improved molecular weight capabilities while maintaining excellent catalyst activity and polymer melting point temperatures.

[0025] The general synthetic method provided herein avoids and eliminates the electronic effects of the prior art that promote deprotonation rather than nucleophilic substitution. The general synthetic method described herein also allows for the significant diversification of arylsilane derivatives, particularly diarylsilane derivatives. The general synthesis of the catalyst can also be applied to mixed asymmetric diaryl or monoaryl derivatives. The resulting silane-bridged metallocene catalyst has very high activity in the polymerization of olefins, particularly ethylene and surprisingly propylene.

[0026] The general preparation of silyl-bridged metallocenes requires four steps, as illustrated below:

[0027]

[0028] The reactivity of diphenylsilane analogs was previously known to favor deprotonation over substitution, as shown below:

[0029]

[0030] It has now been surprisingly and unexpectedly discovered that diphenylsilane bridged metallocenes can be synthesized in only 3 steps. To this end, the dichlorocyclopentadienyl fragment is first substituted with indenyl lithium. Next, direct lithiation / substitution using an aryl or alkyl lithium reagent provides a dilithiated ligand, which is transmetallated with at least one Group (IV) metal salt to provide a metallocene precursor containing a diaryl bridge, as shown below:

[0031]

[0032] Such new metallocene compounds and new synthesis techniques, as well as the polymers produced therefrom, will now be described in more detail below. Each of the appended claims defines a separate invention, which for infringement purposes is recognized as including equivalents to the various elements or limitations expressly described in the claims. Depending on the context, all references to the "invention" below may in some cases refer only to certain specific embodiments. In other cases, it will be recognized that references to the "invention" will refer to the subject matter recited in one or more, but not necessarily all, of the claims. Each of the inventions will now be described in more detail below, including specific embodiments, versions or examples, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person of ordinary skill in the art to make and use the invention when combining the information in this disclosure with publicly available information and techniques.

[0033] The diphenylsilane-bridged metallocenes provided herein may be supported or unsupported, and may be represented by formula (I):

[0034]

[0035] in:

[0036] M is a Group 4 metal.

[0037] Each of X1 and X2 may be a monovalent anionic ligand, or X1 and X2 may be joined to form a metallocycle ring.

[0038] R 1 It can be hydrogen, unsubstituted or unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

[0039] Each J 1 and J 2Can be hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl. Optional J 1 and J 2 Can join to form four, five or six membered rings.

[0040] Each R 2 -R 6 Can be hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

[0041] Each R 7 -R 16 Can be hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl. Optionally, R 11 and R 12 Can be joined.

[0042] Each R 17 , R 18 , R 19 , and R 20 may independently be hydrogen, halogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

[0043] For the purposes of nomenclature, the following coding scheme is used for indenyl. It should be noted that indenyl can be considered a cyclopentadienyl fused to a benzene ring. Draw the structure below and name it after the anion.

[0044]

[0045] Also for simplicity, the ring structure below is a substituted indenyl, wherein the substitutions at positions 5 and 6 form the ring structure. With respect to specific compound nomenclature, 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., as described below. Each structure is drawn and named with the anion.

[0046] Non-limiting examples of indacenyl and cyclopenta[b]naphthyl groups include:

[0047]

[0048]

[0049] The synthetic routes provided herein allow for a significant diversity of C1 symmetric catalysts by means of bridge modification. For example, using the synthetic routes provided herein, it is now possible to obtain complexes such as the following.

[0050]

[0051]

[0052]

[0053] Activator

[0054] The bridged metallocene compound can be activated to carry out polymerization catalysis in any manner sufficient to allow coordination polymerization or cationic polymerization. Coordination polymerization can be achieved when one ligand can be captured, and the other will either allow the insertion of unsaturated monomers, or will similarly be captured to be replaced with a ligand (labile ligand) that allows the insertion of unsaturated monomers, for example, an alkyl, silyl or hydride. Conventional activators for coordination polymerization techniques are suitable, for example, Lewis acids such as aluminoxane compounds, and ionized anion precursor compounds that capture one (ligand) so that the bridged metallocene metal center is ionized as a cation and provide a balanced non-coordinating anion.

[0055] For example, a suitable activator may include a cationic component. In any embodiment, the cationic component may have the formula [R 1 R 2 R 3 AH] + , where A is nitrogen, R 1 and R 2 Together is -(CH2) a - group, wherein a is 3, 4, 5, or 6 and together with the nitrogen atom forms a four-, five-, six- or seven-membered non-aromatic ring to which optionally one or more aromatic or heteroaromatic rings may be fused via adjacent ring carbon atoms, and R 3 is C1, C2, C3, C4 or C5 alkyl, or N-methylpyrrolidinium or N-methylpiperidinium. Alternatively, in any embodiment, the cationic component may have the formula [R n AH4_ n ] +, wherein 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.

[0056] Suitable activators may also be or comprise an anionic component, [Y]. The anionic component may be a non-coordinating anion (NCA) having the formula [B(R 4 )4] - , where R 4 is an aryl group or a substituted aryl group, one or more of which are the same or different and are selected from alkyl, aryl, halogen atoms, halogenated aryl, and halogenated alkylaryl groups. The substituents may be perhalogenated aryl groups, or perfluorinated aryl groups, including perfluorophenyl, perfluoronaphthyl and perfluorobiphenyl.

[0057] Suitable activators may also be or include + (Ad - ) is a non-coordinating anion (NCA) represented by , wherein Z is (LH) or a reducible Lewis acid, L is a Lewis base; H is hydrogen; (LH)+ is a Bronsted acid; Ad- is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.

[0058] Suitable activators may also be or contain a non-coordinating anion (NCA) represented by the formula (Z)d+(Ad-), wherein Ad- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula (Ar3C+), wherein Ar is an aromatic group or a heteroatom, C1-C 40 Hydrocarbon, or substituted C1-C 40 Hydrocarbyl-substituted aryl.

[0059] The ratio of activator(s) to catalyst metal centers may be at least 1:100, or at least 1:250, or at least 1:1500.

[0060] The cationic and anionic components of the catalyst system disclosed herein together form an activator compound. In any embodiment, the activator can be N,N-dimethylanilinium-tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium-tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium-tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonium-tetrakis(perfluorophenyl)borate, triphenylcarbonium-tetrakis(perfluoronaphthyl)borate, triphenylcarbonium-tetrakis(perfluorobiphenyl)borate, or triphenylcarbonium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0061] Detailed descriptions of suitable catalyst systems are also found in International Publication Nos. WO2021 / 162748; WO2013 / 134038; WO2000 / 024793, each of which is incorporated herein by reference.

[0062] Carrier

[0063] The silane-bridged metallocene can be supported or unsupported. When it is 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.

[0064] polymerization

[0065] Any conventional solution, slurry, or gas phase polymerization method can be used to prepare ethylene copolymers using the diphenylsilane bridged metallocene catalyst provided herein. Preferably, a solution or gas phase method is used. For preparing propylene homopolymers or ethylene-propylene random copolymers using the diphenylsilane bridged metallocene catalyst provided herein, any conventional solution or slurry or gas phase polymerization method can be used. Preferably, a solution or slurry method is used.

[0066] Solution polymerization is a bulk polymerization process, which refers to a polymerization process in which the monomers and / or comonomers being polymerized are used as solvents or diluents, using little or no inert solvent as a liquid or diluent. A small portion of the inert solvent may be used as a carrier for the catalyst and scavenger.

[0067] The term "solution polymerization" refers to a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent, monomer(s), or a blend thereof. Solution polymerization is typically homogeneous, which refers to a polymerization process in which the polymer product is dissolved in the polymerization medium. Such a system is preferably not turbid, as described in Oliveira, J. et al. (2000), Ind. Eng. Chem. Res., v. 29, p. 4627. A homogeneous polymerization process is typically one in which at least 90% by weight of the product is dissolved in the reaction medium.

[0068] The term "slurry polymerization" means a polymerization process wherein a supported catalyst is employed and monomer is polymerized on the supported catalyst particles and at least 95 weight percent of the polymer product derived from the supported catalyst is in the form of pellets as solid particles (not dissolved in the diluent).

[0069] If the polymerization is carried out as a slurry (suspension) or solution polymerization, an inert solvent or diluent may be used. Suitable diluents / solvents include non-coordinating inert liquids. Examples include straight chain 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 those commercially available (ISOPAR TM ); perhalogenated hydrocarbons, such as perfluorinated C 4-10 Alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, 1,3,5-trimethylbenzene and xylene. Suitable diluents / solvents also include liquid olefins that can act as monomers or comonomers, including 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 solvents, 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. In a further embodiment, the diluent / solvent is not an aromatic compound, preferably the aromatic compound is present in the diluent / solvent in less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0% by weight, based on the weight of the diluent / solvent. Mineral spirits or hydrogenated diesel fractions can also be used as solvents. Toluene can also be used. The polymerization is preferably carried out in liquid monomer(s). If an inert solvent is used, the monomer(s) are usually metered in gaseous or liquid form.

[0070] Comonomer

[0071] The at least one other comonomer may include any one or more of C4-C 20 Olefins. C4-C 20 The comonomers may be linear, branched or cyclic. Suitable C4-C 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 concentration in reactor C2 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 %. Reactors C4-C 20 The comonomer concentration may range from 0.1-50 wt %; 1 to 35 wt %, 2-20 wt %, or 3-10 wt %.

[0072] Specific examples of comonomers 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, preferably 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 their corresponding homologues and derivatives, and preferably norbornene, norbornadiene, and dicyclopentadiene.

[0073] In a preferred embodiment, one or more dienes (diene comonomers) are added to the polymerization process. The diene may be present in the polymer at up to 10 wt %, preferably 0.00001 to 8.0 wt %, preferably 0.002 to 8.0 wt %, more preferably 0.003 to 8.0 wt %, based on the gross weight of the composition. In some embodiments, 500 ppm or less of the diene is added to the polymerization, preferably 400 ppm or less, preferably 300 ppm or less. In other embodiments, at least 50 ppm of the diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.

[0074] Suitable diene comonomers include any hydrocarbon structure, preferably C4-C 30, having at least two unsaturated bonds, wherein at least one of the unsaturated bonds is easily inserted into the polymer chain during chain growth. It is further preferred that the diene comonomer is selected from α, ω-diene monomers (i.e., divinyl monomers). More preferably, the diene comonomer is a linear di-vinyl monomer, most preferably those containing 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, eicosadiene, hexicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, and 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 polybutadiene (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 rings containing the diene with or without substituents at various ring positions.

[0075] polymer

[0076] In some embodiments, the polymer produced by the diphenylsilane-bridged metallocene provided herein can be a homopolymer of propylene or a copolymer of propylene having about 0.1 wt % to about 50 wt % (e.g., about 1 wt % to 20 wt %) of C2 or C4-C6 oligomers based on the total amount of the polymer. 20 One or more of the olefin comonomers, based on the total amount of the propylene copolymer, for example, about 0.5 wt % to about 18 wt %, for example, about 1 wt % to about 15 wt %, for example, about 3 wt % to about 10 wt %) of C2 or C4-C 20 One or more olefin comonomers (e.g. ethylene or C4-C 12 α-olefins, such as ethylene, butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene, or C4-C 14 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, 1,13-tetradecadiene).

[0077] The propylene homopolymer or propylene copolymer produced herein may have a certain level of isotacticity and may be isotactic or highly isotactic. As used herein, "isotactic" is defined as the isotacticity described in US2008 / 0045638, paragraph

[0613] et seq. 13 C NMR analysis, having at least 10% isotactic pentads. As used herein, "highly isotactic" is defined as 13 C NMR analysis, having at least 60% isotactic pentads. In at least one embodiment, propylene homopolymers having at least about 85% isotacticity, such as at least about 90% isotacticity, can be produced herein. In other embodiments, the propylene polymer produced can be atactic. Atactic polypropylene is defined as polypropylene having at least about 85% isotacticity, such as at least about 90% isotacticity. 13 C NMR analysis showed less than 10% isotactic or syndiotactic pentads.

[0078] Unless otherwise indicated, the molecular weight distribution and moments (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content and branching index (g') were determined by using an infrared detector IR5 based on a multi-channel bandpass filter, with an infrared detector assembly IR5 having a coverage area of ​​about 2700 cm -1 To about 3000cm -1The band area (representing saturated CH stretching vibration)), 18-angle light scattering detector and viscometer high temperature gel permeation chromatography (Polymer CharGPC-IR) were measured. Three Agilent PLgel 10-μm mixed-B LS columns were used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) containing ~300ppm antioxidant BHT was used as the mobile phase, with a nominal flow rate of ~1.0mL / min and a nominal injection volume of ~200μL. The entire system including the transfer line, column and detector can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard bottle to which ~10μL of flow marker (heptane) is added. After the bottle is loaded into the autosampler, the oligomer or polymer can be automatically dissolved in the instrument with ~8mL of added TCB solvent at ~160°C through continuous shaking. The sample solution concentration can be from 0.2 to 2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration c at each point in the chromatogram can be calculated by subtracting the IR5 broadband signal from the baseline, / , using the equation: c = αI, where α is a mass constant determined using a polyethylene or polypropylene standard. Mass recovery can be calculated by the ratio of the integrated area of ​​the concentration chromatogram within the elution volume and the injected mass (which is equal to the predetermined concentration multiplied by the injection loop volume). Conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with a column calibration (which is performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole). The MW at each elution volume is calculated using the following equation:

[0079]

[0080] The variables with the subscript "PS" represent polystyrene and those without the subscript represent the test sample. PS =0.67 and K PS = 0.000175, α and K for other materials are calculated as described in the literature (e.g., Sun, T. et al. (2001), Macromolecules, v.34, p. 6812), except that for the purposes of the present disclosure and claims thereto, 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 3Unless otherwise indicated, molecular weight is expressed in g / mole and intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0081] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels calibrated using a series of PE and PP homopolymer / copolymer standards (whose nominal values ​​are predetermined by NMR or FTIR). In particular, this provides the methyl groups per 1000 total carbons (CH3 / 1000TC) as a function of molecular weight. The amount of short chain branching (SCB) per 1000TC as a function of molecular weight (SCB / 1000TC) is then calculated by applying a chain end correction to the CH3 / 1000TC function, assuming that each chain is linear and terminated by a methyl group at each end. The weight % comonomer is then obtained by the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc., respectively, for comonomers such as C3, C4, C6, C8:

[0082] w2=f*SCB / / 1000TC

[0083] The bulk composition of the polymer analyzed by GPC-IR and GPC.4D is obtained by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

[0084]

[0085] The same correction of the ratio of CH3 and CH2 signals as previously mentioned in obtaining CH3 / 1000TC as a function of molecular weight is then applied to obtain bulk CH3 / 1000TC. The bulk methyl chain ends per 1000TC (bulk CH3 ends / 1000TC) are obtained by weight average and chain end correction over the molecular weight range. Then

[0086] w2b=f*body CH3 / 1000TC

[0087] Main body SCB / 1000TC = main body CH3 / 1000TC - main body CH3 end / 1000TC

[0088] And the body SCB / 1000TC is converted to body w2 in the same manner as described above.

[0089] The LS detector was an 18-angle Wyatt Technology high temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972.):

[0090]

[0091] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K o is the optical constant of the system:

[0092]

[0093] Where N A is the Avogadro constant, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ=665nm is n=1.500. For the analysis of polyethylene homopolymers, ethylene-hexene copolymers and ethylene-octene copolymers, dn / dc=0.1048 ml / mg and A2=0.0015; for the analysis of ethylene-butene copolymers, dn / dc=0.1048*(1-0.00126*w2) ml / mg and A2=0.0015, where w2 is the weight percent butene comonomer.

[0094] The specific viscosity is determined using a high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure sensors. One sensor measures the total pressure drop across the detector, and the other, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is calculated from their outputs S The intrinsic viscosity [η] at each point in the chromatogram is calculated by the equation [η] = ηs / c, where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is calculated as To calculate, where α ps is 0.67 and K ps It is 0.000175.

[0095] Branching coefficient (g' vis ) is calculated as follows using the output of GPC-IR5-LS-VIS. The average intrinsic viscosity [η] of the sample avgCalculated by the following formula:

[0096]

[0097] where the sum is taken over all chromatographic slices i between the integration limits.

[0098] Branching coefficient g' vis Defined as:

[0099]

[0100] Among them, M v is the viscosity average molecular weight based on the molecular weight determined by LS analysis, and K and α are for 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 Unless otherwise indicated, molecular weight is expressed in g / mole and intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g. The calculation of w2b values ​​is as discussed above.

[0101] In one or more specific embodiments, the ethylene-propylene random copolymers (RCP) produced herein may have:

[0102] a) an ethylene content of 0.1 to 10 wt %, based on the total weight of the copolymer, e.g., 0.2-10 wt %; 0.5-10 wt %; 1-10 wt %; 2-10 wt %; or 3-8 wt %;

[0103] b) an Mw of about 5,000 to about 1,000,000 g / mol (e.g., about 25,000 to about 750,000 g / mol, e.g., about 50,000 to about 500,000 g / mol, e.g., about 80,000 to about 300,000 g / mol, e.g., about 100,000 to about 250,000 g / mol, or 5,000 to 500,000 g / mol, or 5,000 to 350,000 or 10,000 to 250,000) as determined by GPC-4D;

[0104] c) a molecular weight distribution, MWD, (Mw / Mn), as determined by GPC-4D, of greater than about 2, e.g., from about 2 to about 30, e.g., from about 3 to about 20, e.g., from about 4 to about 10;

[0105] d) a melt flow rate (MFR) of about 0.1 dg / min to about 1000 dg / min, about 1 dg / min to about 100 dg / min, about 20 dg / min to about 70 dg / min, or about 5 dg / min to about 10 dg / min as measured by ASTM D1238 (230° C., 2.16 kg); and

[0106] e) a Tm greater than about 80°C, such as from about 120°C to about 165°C, such as from about 140°C to about 160°C, such as from about 145°C to about 155°C, as determined by Differential Scanning Calorimetry Procedure DSC-2 described below.

[0107] In one or more specific embodiments, the ethylene-propylene elastomers and rubbers (EP) produced herein may have:

[0108] a) an ethylene content of 0.1 to 50 wt %, based on the total weight of the copolymer, such as 1-35 wt %, 2-20 wt %, 3-10 wt %, 10-40 wt %; 10-25 wt %; 15-35 wt %, or 20-40 wt %;

[0109] b) an Mw of about 5,000 to about 1,000,000 g / mol (e.g., about 25,000 to about 750,000 g / mol, e.g., about 50,000 to about 500,000 g / mol, e.g., about 80,000 to about 300,000 g / mol, or 5,000 to 500,000 g / mol, or 5,000 to 350,000 or 10,000 to 250,000) as determined by GPC-4D;

[0110] c) a molecular weight distribution, MWD, (Mw / Mn), as determined by GPC-4D, of greater than about 2, such as from about 2 to about 30, such as from about 3 to about 20, such as from about 4 to about 10; and

[0111] d) a melt flow rate (MFR) of about 0.1 dg / min to about 1000 dg / min, about 1 dg / min to about 100 dg / min, 20 dg / min to 70 dg / min, or about 5 to about 10 dg / min as measured by ASTM D1238 (230° C., 2.16 kg).

[0112] In one or more specific embodiments, the propylene homopolymer (hPP) produced herein may have:

[0113] a) an Mw of about 5,000 to about 1,000,000 g / mol (e.g., about 25,000 to about 750,000 g / mol, e.g., about 50,000 to about 500,000 g / mol, e.g., about 80,000 to about 300,000 g / mol, e.g., about 80,000 to about 200,000 g / mol, or 5,000 to 500,000 g / mol, or 5,000 to 350,000, or 10,000 to 250,000) as determined by GPC-4D;

[0114] b) a molecular weight distribution, MWD, (Mw / Mn), as determined by GPC-4D, of greater than about 2, e.g., from about 2 to about 30, e.g., from about 3 to about 20, e.g., from about 4 to about 10;

[0115] c) a g' as determined by GPC-4D of 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 vis ;

[0116] d) a melt flow rate (MFR) of about 0.1 dg / min to about 3000 dg / min, about 1 dg / min to about 100 dg / min, about 10 dg / min to about 100 dg / min, or about 5 to about 10 dg / min as determined by ASTM D1238 (230° C., 2.16 kg); and

[0117] e) a melting point (Tm) of greater than about 120°C, such as from about 130°C to about 165°C, such as from about 140°C to about 160°C, such as from about 145°C to about 155°C, as determined by Differential Scanning Calorimetry Procedure DSC-2 described below. Example

[0118] The foregoing discussion may be further described with reference to the following non-limiting examples. Three silane-bridged metallocene structures (I1, I2 and I3) were prepared and used to prepare propylene homopolymers and ethylene-propylene copolymers. Two comparative metallocene catalysts (C1 and C2) were also prepared and tested. Five (5) catalyst structures are shown below.

[0119] Comparison of metallocene catalysts (C1 and C2):

[0120] Silane-bridged metallocene structures of the present invention

[0121]

[0122] s(I1, I2 and I3):

[0123] Catalysts C1, C2 and I1 were prepared from silafluorenyldichloride using the following conventional route:

[0124]

[0125] Catalysts I2 and I3 were prepared using the following modified one-pot technique:

[0126]

[0127]

[0128] Figure 1 Representative spectra showing the in situ substitution-lithiation of catalyst I2. Figure 2 The spectrum of the isolated catalyst 12 is shown, which demonstrates excellent purity. The spectrum illustrates that the purity of the isolated material is excellent.

[0129] Catalysts C1 and C2 were prepared according to previously reported procedures, for example as described in US 9,266,910 and in WO 2021 / 034459 A1.

[0130] Catalyst I1 was prepared according to Scheme 1 below:

[0131]

[0132] Preparation of 9-chloro-9-(2,3,4,5-tetramethylcyclopentadienyl)-silafluorene:

[0133] To pre-cooled, stirring dichlorosilane (0.505g, 2.01mmol) in ether (40mL) solution, add tetramethylcyclopentadiene sodium (0.290g, 2.01mmol, 1 equivalent). The reaction was stirred at room temperature for 1.5 hours. The reaction was concentrated under nitrogen flow and then under high vacuum. Pentane was used to extract the residue and filter the residue on Celite. The filtrate was concentrated under nitrogen flow and then under high vacuum to provide the product, which was an off-white solid (0.489g, 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).

[0134] Preparation of 4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl) (2,3,4,5-tetramethylcyclopentadienyl) silafluorene:

[0135] To a stirred tetrahydrofuran (10 mL) solution of 9-chloro-9-(2,3,4,5-tetramethylcyclopentadienyl)-silanol (0.140 g, 0.416 mmol) was added a tetrahydrofuran (5 mL) solution of 4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene lithium (0.128 g, 0.416 mmol, 1 equivalent). The reaction was stirred overnight at room temperature. The reaction was concentrated under a nitrogen stream and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and the residue was filtered on cinnabar. The combined dichloromethane extracts were concentrated under a nitrogen stream and then under high vacuum. The resulting residue was stirred in hexane (5 mL) and filtered on cinnabar. The hexane extract was concentrated under a nitrogen stream and then under high vacuum to provide a product, which was an off-white foam (0.237 g, 94% yield). 1 H 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).

[0136] Preparation of (4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene) (2,3,4,5-tetramethylcyclopentadienyl) silafluorene lithium:

[0137] To a pre-cooled, stirred solution of (4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene) (2,3,4,5-tetramethylcyclopentadienyl) silafluorene (0.237 g, 0.393 mmol) in diethyl ether (10 mL) was added n-butyl lithium (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 under high vacuum. The residue was stirred in hexanes (2 mL). The resulting suspension was filtered on a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to provide the product as an orange solid (0.125 g, 45% yield) containing diethyl ether (0.82 equiv). 1 H NMR (400MHz, C4H8O): δ7.99 (d, 2H, J = 7.0Hz), 7.79 (d, 2H, J = 7.7Hz), 7.46 (d, 2 H,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).

[0138] Preparation of silafluorenyl (4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride (catalyst I1):

[0139] To a suspension of zirconium chloride (0.048 g, 0.206 mmol, 1.15 equivalents) in diethyl ether (5 mL) in stirring was added 4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene) (2,3,4,5-tetramethylcyclopentadienyl) lithium silafluorene (0.125 g, 0.179 mmol, containing 0.82 equivalents of diethyl ether) in diethyl ether (10 mL). The reaction was stirred at room temperature for 6 hours. The reaction was concentrated under a nitrogen stream and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and the residue was filtered over celite. The combined dichloromethane extracts were concentrated under a nitrogen stream and then under high vacuum. The residue was stirred in hexane and then concentrated under a nitrogen stream and then under high vacuum to provide the product as an orange-yellow solid (0.102 g, 74% yield). 1H NMR (400MHz, CD2Cl2): δ8.73(d, 1 H,J=8.0Hz),8.45(dd,1H,J=7.5,0.9Hz),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,5 H), 6.84 (s, 1H), 2.97 (t, 4H, J = 7.2Hz), 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).

[0140] Catalyst I2 (R = Ph) was prepared according to Scheme 1 below:

[0141]

[0142] Me4CpLi solid (2.02 g, 15.8 mmol) was slowly added to a pre-cooled (-30 ° C) THF solution of PhSiCl3 (3.35 g, 15.8 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight. After 18 hours, the solvent was removed in vacuo and the residue was extracted with pentane (2×20 mL) and filtered on celite. The solvent was removed to provide the final product, which was shown to have good purity (93% yield). 1 H NMR(C6D6)δ7.47(m,2H)7.02(m,1H)6.97(m,2H),3.21(bs,1H)1.92(bs,6H)1.47(bs,1H).

[0143] 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:

[0144] 4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene lithium (0.781 g, 2.5 mmol) was dissolved in 2 mL THF and 5 mL ether in a 20 mL bottle. Once cooled, the solution was slowly transferred (via a pipette) to a pre-cooled (-30 ° C) ether solution of dichloro-phenyl-(2,3,4,5-tetramethylcyclopenta-2,4-diene-1-yl)silane (1.5 g, 5.1 mmol). The reaction mixture was light yellow and slightly turbid when the addition was complete. After 1 hour, the solvent was removed in vacuo and the residue was extracted with pentane and the residue was concentrated in vacuo. The yellow pentane solution was placed in a refrigerator. After 18 hours, yellow crystals were deposited - the solution was poured out and the crystals were washed with 10 mL pentane and dried in vacuo to provide a spectrally pure product in a yield of 49%. 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).

[0145] Preparation of dilithium-diphenyl-(4-(4-tert-butylphenyl)2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane:

[0146] To a pre-cooled, stirred solution of chloro(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene)(2,3,4,5-tetramethylcyclopentadienyl)phenylsilane (0.661 g, 1.17 mmol) in tetrahydrofuran (~40 mL) was added phenyllithium (1.7 mL of a 2.1 M solution in butyl ether). The reaction immediately turned light orange and stirred at room temperature for 1 hour. After 1 hour, the solvent was removed in vacuo to provide an orange solid. The solid was washed with 2×10 mL of hexanes and dried in vacuo to provide a yellow solid. 1 H NMR showed pure product in essentially quantitative yield with some residual THF and butyl ether. The material was used directly in the next step without further purification. 1H NMR (THF-d8) δ7.88 (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 group of protons in the indacene skeleton is masked by the residual butyl ether signal in the aliphatic region.

[0147] Preparation of diphenylsilyl-(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride (catalyst I2):

[0148] ZrCl4(OEt2)2 (0.5 g, 1.31 mmol) was slowly added to a stirred suspension of dilithium-diphenyl(4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene)(2,3,4,5-tetramethylcyclopentadienyl)silane (1.05 g, 1.31 mmol, containing 1.2 eq. Bu2O and 0.6 eq. THF) in diethyl ether (~30 mL) at -30°C. The reaction mixture was allowed to warm to room temperature and stirred overnight. After 18 hours, the solvent was removed in vacuo to provide a bright yellow residue. The residue was extracted with dichloromethane (2×25 mL), filtered over celite and concentrated to provide a yellow solid. The solid was triturated with pentane (20 mL), stirred briefly and filtered on a glass frit. The solid was dried in vacuo to provide 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).

[0149] Catalyst I3 (R = Me) was prepared according to Scheme 3 below:

[0150]

[0151] Preparation of dilithium-(1-((4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene-1-yl)(methyl)(phenyl)silyl)-2,3,4,5-tetramethylcyclopenta-2,4-diene-1-yl):

[0152] To a pre-cooled, 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 (~8 mL) was added methyllithium (0.537 mL of a 1.6 M solution, 3.1 equiv). The reaction immediately turned light orange and stirred at room temperature for 20 minutes. After 20 minutes, the solvent was removed in vacuo to provide an orange solid. The solid was washed with 2×10 mL of hexanes and dried in vacuo to provide a yellow solid. 1 H NMR showed high purity product in essentially quantitative yield with approximately 2 equivalents of residual THF. The 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).

[0153] Preparation of (1-((4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene-1-yl)(methyl)(phenyl)silyl)-2,3,4,5-tetramethylcyclopenta-2,4-diene-1-yl)zirconium dichloride (catalyst I3):

[0154] ZrCl4(OEt2)2 (0.11 g, 0.288 mmol) was slowly added to a stirred suspension of dilithium-(1-((4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene-1-yl)(methyl)(phenyl)silyl)-2,3,4,5-tetramethylcyclopenta-2,4-diene-1-yl) (0.20 g, 0.286 mmol) in diethyl ether (~30 mL) at -30 °C. The reaction mixture was allowed to warm to room temperature and stirred overnight. After 18 hours, the solvent was removed in vacuo to provide a bright yellow residue. The residue was extracted with dichloromethane (2×5 mL), filtered over celite and concentrated to provide a yellow solid. The solid was triturated with hexane (10 mL), stirred briefly and filtered on a glass filter. 1 H NMR showed 45% yield of the desired product. Two isomers were observed, which may be due to the cis / trans relationship of the asymmetric silane with respect to the indacene ligand. 1H NMR (CD2Cl2) δ8.04 (s, 4H), 7.63-7.48 (overlapping m, 13H, two 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, two isomers), 2.35 (s, 3H, isomer 1), 2.17 (s, 3H, isomer 2), 2. 05-2.03 (two s, 6H, two isomers of s), 2.01-2.00 (two s, 6H, two isomers of s), 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).

[0155] Solution polymerization procedure

[0156] Use high throughput conditions to carry out solution propylene polymerization. Pre-weighed glass insert bottles and disposable stirring paddles are installed in each reaction vessel of the reactor containing 48 separate reaction vessels. Then close the reactor and introduce propylene (usually 1-4mL). Then add solvent (usually isohexane) to make the total reaction volume including subsequent addition reach 5mL and the reactor vessel is heated to their setting temperature (usually about 50 ℃ to about 110 ℃). Stir the contents of the container at 800rpm. A toluene solution of the activator (typically 1.1-1000 molar equivalents of methylaluminoxane (MAO) along with 500 microliters of toluene) is then injected into the reaction vessel. The catalyst (typically 0.50 mM in toluene, e.g., 20-40 nmol of catalyst) and another aliquot of toluene (500 microliters) are then added to initiate the reaction. The equivalents are determined based on molar equivalents relative to the moles of transition metal in the catalyst complex. The reaction is then allowed to continue until the reaction has consumed a predetermined amount of pressure. At this point, the reaction is quenched by pressurizing the vessel with compressed air. Following the polymerization reaction, the glass insert bottle containing the polymer product and solvent is removed from the pressure chamber and inert atmosphere glove box, and the volatile components are removed using a Genevac HT-12 centrifuge and a Genevac VC3000D vacuum evaporator operated at elevated temperature and reduced pressure. The bottle is then weighed to determine the yield of the polymer product. The resulting polymer is analyzed by fast GPC (see below) to determine the molecular weight and by DSC (see below) to determine the melting point.

[0157] Table 1 shows the catalyst activity and polymerization results of homopolypropylene (hPP) polymerized using comparative catalysts C1, C2 and inventive catalysts I1 to I3. Table 2 shows the results of EP copolymers polymerized using the same catalysts.

[0158] Table 1: Solution polymerization, non-supported catalyst for hPP (70°C, MAO activation)

[0159]

[0160]

[0161] Table 2: Ethylene-propylene copolymerization, solution polymerization, unsupported catalyst (70°C, MAO activation)

[0162]

[0163] The results in Tables 1 and 2 demonstrate that catalysts I1-I3 are highly active in propylene polymerization, providing comparable polymer properties and equal or better polymer crystallinity relative to comparative / control catalysts C1 and C2. With respect to EP copolymers, catalysts I1 and I3 show improvements in ethylene response relative to control catalysts C1, C2, particularly higher incorporation at the same ethylene partial pressure.

[0164] Example 2: Supported Catalyst

[0165] Catalysts C1-C2 and I1-I3 are supported on conventional silica supports and are used to polymerize propylene under industrially relevant slurry and bulk slurry conditions.

[0166] Preparation of silica supported MAO (SMAO)

[0167] In a celstir, 10.0 g of DM-L403 silica (AGC, dehydrated at 200° C.) was suspended in about 100 mL of dry toluene and cooled to -30° C. While stirring, 15.8 g of a 30% MAO cold solution was slowly added to the stirred silica mixture (within 10 minutes). The reaction was stirred for 1.5 hours. After 1.5 hours, the temperature was raised 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 (2×50 mL), pentane (2×50 mL) and dried in a vacuum for at least 2 hours to provide the resulting SMAO, which was a white free-flowing powder.

[0168] General preparation of supported catalysts C1, C2, I1, I2 and I3

[0169] In a 25mL scintillation bottle, 0.6g of the previously prepared SMAO was suspended in 10mL of anhydrous toluene and placed on a shaking table. Then 0.310mL of triisobutylaluminum solution (1M in hexane) was added and the resulting mixture was stirred at room temperature for 15 minutes. After 15 minutes, the metallocene catalyst based on 12μmol / g loading was slowly added as a toluene solution (about 2mL) to the silica mixture. The resulting slurry was stirred for 3 hours. After 3 hours, the slurry was filtered on a glass filter, the solid was washed with toluene (2×5mL) and pentane (2×5mL) and the solid was dried in a vacuum to provide a supported catalyst, which was an orange / red free-flowing powder. Optionally, the resulting solid was suspended in mineral oil to prepare a 5% by weight slurry, which was used for laboratory reactor polymerization.

[0170] Ontological polymerization procedure

[0171] Use 1L autoclave reactor equipped with mechanical stirrer to prepare polymer.Before operation, reactor is placed under nitrogen purge while maintaining 90 ℃ temperature for 30 minutes.Once cooled back to ambient temperature, propylene feed (500mL), scavenger (0.2mL 1M TIBAL, triisobutylaluminum) and optional hydrogen (filled from 50mL high pressure container (bomb) with required pressure) are introduced to reactor and mixed for 5 minutes.Then by using 100mL liquid propylene to flush a predetermined amount of catalyst slurry (5 wt % in mineral oil) from catalyst tube, the required amount of loaded catalyst (usually 12.5-25.0mg) is introduced into reactor.The reactor is kept at room temperature for 5 minutes (prepolymerization stage), and then the temperature is raised to 70 ℃ before.The reaction is continued at this temperature for the required time period (usually 30 minutes).After the given time, the temperature is reduced to 25 ℃, excess propylene is discharged and polymer pellets are collected, and the polymer pellets are dried overnight at 60 ℃ under vacuum.

[0172] Slurry Polymerization Procedure

[0173] Slurry propylene polymerization is carried out under high throughput conditions according to the following general procedure. Pre-weighed glass insert bottles and disposable stirring paddles are installed in each reaction vessel of a reactor containing 48 separate reaction vessels. Then the reactor is closed and propylene (usually 1-4mL) is introduced. Then triisobutylaluminum (TIBAL) is introduced as a scavenger (usually 2.5-10 μmol), either as a toluene solution or as an isohexane solution. Then solvent (usually isohexane) is added to make the total reaction volume including subsequent additions reach 5mL and the reactor vessel is heated to their set temperature (usually about 50°C to about 110°C). Ethylene (usually 70-140psi) is added to the reactor at this stage. The contents of the container are stirred at 800rpm. The catalyst (usually 0.75mg) of the load is introduced as a toluene slurry (usually 3.0mg / mL concentration) to initiate the reaction. Equivalents are determined based on the molar equivalent relative to the mole of transition metal in the catalyst complex. Then the reaction is continued until the reaction has consumed a predetermined amount of pressure or in the case of homopolymerization, it is continued for 30 minutes. At this point, the reaction is quenched by using either compressed air or carbon dioxide to pressurize the container. After the polyreaction, remove the glass insert bottle containing the polymer product and solvent from the pressure chamber and the inert atmosphere glove box, and use the Genevac HT-12 centrifuge and the Genevac VC3000D vacuum evaporator operated under the temperature and pressure of reduction to remove volatile components. The bottle is then weighed to determine the yield of the polymer product. Analyze the resulting polymer by fast GPC (see below) to determine the molecular weight and analyze the resulting polymer by DSC (see below) to determine the fusing point.

[0174] Table 3: Results of slurry polymerization using supported catalysts

[0175]

[0176]

[0177]

[0178] Table 4: Results of bulk-slurry polymerization of propylene using supported catalysts (70°C, using 2 mmol H2)

[0179]

[0180] The data in Table 3 demonstrate the excellent activity and operability of the arylsilane substituted catalysts I1-I3 of the present invention. Significant improvements in EP rubber molecular weight capabilities are also demonstrated, particularly with catalysts I2 and I3. For homopolypropylene polymerizations using catalyst I2, a significant improvement in activity (about 18,000 g / g) was observed over control catalyst C1 (13,200 g / g) under bulk slurry conditions (Table 4). The polymer produced using silafluorenyl bridged system I1 shows a slight improvement in melting point (Tm = 159°C relative to control C1).

[0181] It is completely surprising and unexpected that the silane-bridged metallocenes I1, I2 and I3 show excellent activity for preparing hPP and EP copolymers. It is also completely surprising and unexpected that the silane-bridged metallocenes I1, I2 and I3 are able to produce higher melting point hPP (≥153°C) and ethylene-propylene copolymers with higher molecular weight (Mw), which allows for improved impact properties.

[0182] Test procedures used:

[0183] Fast GPC Procedure: To determine various molecular weight related values ​​by GPC, an automated "Fast GPC" system was used to perform high temperature size 5 exclusion chromatography, as generally described in U.S. Pat. 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 fully incorporated herein by reference for U.S. purposes. The equipment was a series 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 580-3390000 g / mol. The system was operated at an eluent 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 sample was dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1-0.9 mg / mL. 250 μL of the polymer solution was injected into the system. An evaporative light scattering detector (as shown in the examples in Table 3) or a Polymer Char IR4 detector was used to monitor the concentration of the polymer in the eluent. The molecular weights shown are relative to linear polystyrene standards and are uncorrected.

[0184] DSC Procedure, DSC-1: For high throughput samples, differential scanning calorimetry (DSC) is used to measure melting points (Tm) using commercially available equipment such as TA Instruments TA-Q200 DSC. Typically, 5 to 10 mg of molded polymer or plasticized polymer is sealed in an aluminum pan at about room temperature and loaded into the equipment. The sample is pre-annealed at about 220°C for about 15 minutes and then allowed to cool to about room temperature overnight. The sample is then heated to about 220°C at a heating rate of about 100°C / minute, maintained at this temperature for at least about 5 minutes, and then cooled to a temperature below the crystallization temperature, typically at least about 50°C, at a rate of about 50°C / minute. Melting points are collected during heating.

[0185] DSC Procedure, DSC-2: The peak melting point Tm (also referred to as the melting point) and the peak crystallization temperature Tc (also referred to as the crystallization temperature) described for the reactor batch are determined using the following DSC procedure according to ASTM D3418-03. Differential Scanning Calorimetry (DSC-2) data can be obtained using a TA Instruments model DSC2500 machine. A sample weighing about 5 to 10 mg is sealed in an aluminum sealed sample pan at about room temperature and loaded into the instrument. DSC data are recorded as follows: the sample is first gradually heated to about 200°C at a rate of about 10°C / minute. The sample is maintained at about 200°C for 5 minutes, then cooled to about -50°C at a rate of about 10°C / minute, followed by isothermal heating for about 5 minutes and heating to about 200°C at about 10°C / minute, maintained at about 200°C for about 5 minutes and then cooled to about 25°C at a rate of about 10°C / minute. Both the first and second cycle thermal events are recorded. Unless otherwise indicated, melting and crystallization temperatures reported herein are obtained during the second heating / cooling cycle. In case of a conflict between DSC Procedure-1 and DSC Procedure-2, DSC Procedure-2 was used.

[0186] Certain embodiments and features are described using numerical upper limits and numerical lower limits. Ranges from any lower limit to any upper limit are understood to be encompassed unless otherwise indicated. Certain lower limits, upper limits, and ranges appear in one or more claims below. All numerical values ​​are "about" or "approximately" the indicated value, and take into account experimental errors and deviations that would be expected by a person of ordinary skill in the art.

[0187] Various terms have been defined above. When a term used in a claim is not defined above, it should be given the broadest definition given to that term by persons skilled in the art as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0188] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope of the invention is determined by the following claims.

Claims

1. A catalyst system comprising a metallocene compound described in formula (I): in: M is a Group 4 metal; Each of X1 and X2 is a monovalent anionic ligand, or X1 and X2 are joined to form a metallocycle ring; R 1 is hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl; J 1 and J 2 are independently hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl, optional J 1 and J 2 Can join to form four-, five-, or six-membered rings; Each R 2 -R 6 is hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl; Each R 7 -R 16 is hydrogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl; optionally, R 11 and R 12 can be joined to form a silafluorene moiety; and Each R 17 , R 18 , R 19 , and R 20 are independently hydrogen, halogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, 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 , where R' is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl.

2. The catalyst system according to claim 1, further comprising an activator.

3. The catalyst system of claim 2, wherein the activator is either an aluminoxane or a salt of a non-coordinating (NCA) anion.

4. The catalyst system according to claim 3, wherein the activator is a + (Ad - ) represents NCA, Wherein Z is (LH) or a reducible Lewis acid, L is a Lewis base; H is hydrogen; (LH)+ is a Brønsted acid; Ad- is a non-coordinating anion having a charge d-; and d is an integer of 1-3.

5. The catalyst system of claim 3, wherein the activator is an NCA represented by the formula (Z)d+(Ad-), wherein Ad- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula (Ar3C+), wherein Ar is an aromatic group or a heteroatom, C1-C 40 Hydrocarbon, or substituted C1-C 40 Hydrocarbyl-substituted aryl.

6. The catalyst system of claim 2, wherein the activator is an alumoxane and the ratio of alumoxane to metal is at least 1:100, or at least 1:250, or at least 1:

500.

7. The catalyst system according to any one of claims 1 to 6, further comprising a support material.

8. The catalyst system according to claim 7, wherein the support material is selected from the group consisting of Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon oxide / clay and mixtures thereof.

9. A method for preparing a propylene homopolymer or copolymer, comprising: Propylene, one or more C2 or C4-C 40 an olefin comonomer, and a catalyst system according to any one of claims 1 to 8, and optionally hydrogen is introduced into a reactor at a reactor pressure of 0.7 bar to 70 bar and a reactor temperature of 20° C. to 150° C.; and Propylene homopolymers or copolymers are obtained.

10. The method according to claim 9, wherein C4-C 40 The olefin comonomer is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 2-methyl-1-pentene, vinylcyclobutane, 1-heptene, 1-octene, 1-decene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene.

11. The process according to any one of claims 9-10, wherein the propylene homopolymer or copolymer has a Mw value of 5000 to 500000 g / mol, or 5000 to 350000 or 10000 to 250000 as measured by gel permeation chromatography.

12. The process according to any one of claims 9-10, wherein the propylene homopolymer or copolymer has a Mw value of 10000 to 250000 as measured by gel permeation chromatography.

13. The method of any one of claims 9-10, wherein the propylene homopolymer or copolymer has a melt flow rate (MFR) according to ASTM D1238 (230°C, 2.16 kg) of 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 about 70 dg / min.

14. The process of any one of claims 11-13, wherein the propylene homopolymer or copolymer has a molecular weight distribution (Mw / Mn) of about 2 to about 30, or about 3 to about 20, or about 4 to about 10.

15. The process according to any one of claims 9 to 12, wherein the propylene homopolymer or copolymer has a melting point (Tm) greater than 80°C, or greater than 130°C, or greater than 150°C.

16. The process according to any one of claims 11-12, wherein the propylene copolymer has a comonomer content of 0.1 to 50 wt.-%.

17. The process of any one of claims 11-12, wherein the propylene copolymer has a comonomer content of 1 to 35 wt%, or 2 to 20 wt%, or 3 to 10 wt%.

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