Metallocene catalysts, catalyst systems and methods of using the same

Abstract

This paper discloses catalyst compounds (I) or (II) represented by formula (I) or formula (II). M is a Group 4 metal. R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Each is independently hydrogen, or a C1-C50 substituted or unsubstituted hydrocarbon group, a haloalkyl group, a silyl divalent carbon group, an aryloxy group, a methoxy group, or R. 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 , and R 7 and R 8 One or more X groups form a cyclic saturated or unsaturated ring. Each X is independently a halogen or a C1-C50 substituted or unsubstituted hydrocarbon group, hydride, amino group, alkoxy group, sulfide group, phosphate group, halogen group, or a combination thereof, or two X groups are linked together to form a metallic ring, or two X groups are linked together to form a chelated ligand, diene ligand, or alkylidene group. A method for producing polyolefin polymers using a catalyst compound in a catalyst system is also disclosed.

Description

[0001] This application is a divisional application of patent application No. 201780073369.7, filed on September 6, 2017, entitled "Metallocene catalyst, catalyst system and method of using the same".

[0002] Cross-reference to related applications

[0003] This application claims the benefit of application No. 62 / 404,506, filed on October 5, 2016, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0004] The present invention discloses novel catalyst compounds containing H-Si bridges, catalyst systems containing such catalyst compounds, and their uses. Background Technology

[0005] Polyolefins are widely used commercially due to their strong physical properties. For example, various types of polyethylene, including high-density, low-density, and linear low-density polyethylene, are among the most commercially useful. Polyolefins are typically prepared using catalysts that polymerize olefin monomers.

[0006] Low-density polyethylene (LDPE) is typically prepared under high pressure using free radical initiators or in a gas-phase process using Ziegler-Natta or vanadium catalysts. The density of LPE is typically about 0.916 g / cm³. 3 Typical low-density polyethylene produced using free radical initiators is industrially known as "LDPE". LDPE is also called "branched" or "uniformly branched" polyethylene because of the relatively large number of long branches extending from the main polymer backbone. Polyethylene with similar density but without branching is called "linear low-density polyethylene" ("LLDPE"), and is typically prepared using conventional Ziegler-Natta catalysts or metallocene catalysts. "Linear" refers to polyethylene having very few (if any) long branches, typically referred to as 0.97 g / L or higher. Vis value, for example, 0.98 or higher. Higher density polyethylene is high-density polyethylene (“HDPE”), for example, with a density greater than 0.940 g / cm³. 3 Polyethylene, typically prepared using Ziegler-Natta or chromium catalysts, is a high-density polyethylene (“VLDPE”). VLDPE can be produced by many different methods, yielding products with densities typically ranging from 0.890 to 0.915 g / cm³. 3 Polyethylene of high density.

[0007] Copolymers of polyolefins such as polyethylene have comonomers, such as hexene, incorporated into the polyethylene backbone. These copolymers offer different physical properties compared to polyethylene alone and are typically produced in low-pressure reactors using methods such as solution, slurry, or gas-phase polymerization. Polymerization can be carried out in the presence of catalyst systems such as Ziegler-Natta catalysts, chromium-based catalysts, or metallocene catalysts. The comonomer content of the polyolefin (e.g., wt% of comonomers incorporated into the polyolefin backbone) affects the properties of the polyolefin (and the composition of the copolymer) and depends on the characteristics of the polymerization catalyst. As used herein, “low comonomer content” is defined as a polyolefin having less than about 8 wt% comonomers based on the total weight of the polyolefin. High molecular weight fractions produced by a second catalyst compound can have high comonomer content. As used herein, “high comonomer content” is defined as a polyolefin having more than about 8 wt% comonomers based on the total weight of the polyolefin.

[0008] Copolymer compositions, such as resins, have a compositional distribution, which represents the distribution of comonomers that form short branches along the copolymer backbone. A composition is said to have a "broad" compositional distribution when the amount of short branches between copolymer molecules varies. A compositional distribution is called "narrow" when the amount of comonomers per 1000 carbons is similar in copolymer molecules of different chain lengths.

[0009] Similar to comonomer content, compositional distribution affects the properties of copolymer compositions, such as stiffness, toughness, environmental stress cracking resistance, and heat sealability. The compositional distribution of polyolefin compositions can be easily measured using methods such as temperature elution fractionation (TREF) or crystallization fractionation (CRYSTAF).

[0010] Similarly, as with the comonomer content, the compositional distribution of a copolymer composition depends on the characteristics of the catalyst used to form the polyolefin in the composition. Ziegler-Natta catalysts and chromium-based catalysts produce compositions with a broad compositional distribution (BCD), while metallocene catalysts typically produce compositions with a narrow compositional distribution (NCD).

[0011] Furthermore, high molecular weight polyolefins (such as polyethylene) generally possess desirable mechanical properties compared to their lower molecular weight counterparts. However, high molecular weight polyolefins can be difficult to process and expensive to produce. Polyolefin compositions with a bimodal molecular weight distribution are ideal because they combine the advantageous mechanical properties of the high molecular weight (“HMW”) fraction with the improved processability of the low molecular weight (“LMW”) fraction. As used herein, “high molecular weight” is defined as a number-average molecular weight (Mn) value of 100,000 or higher. “Low molecular weight” is defined as an Mn value of less than 100,000.

[0012] For example, a useful bimodal polyolefin composition comprises a first polyolefin with a low molecular weight and low comonomer content, and a second polyolefin with a high molecular weight and high comonomer content. Components with this broad orthogonal compositional distribution (BOCD), where the comonomers are primarily incorporated into the high molecular weight chain, can provide improved physical properties such as toughness and resistance to environmental stress cracking (ESCR).

[0013] Several methods exist for preparing polyolefins with bimodal or broad molecular weight distributions, such as melt blending, reactors arranged in series or parallel, or single reactors with bimetallic catalysts. However, these methods, such as melt blending, suffer from drawbacks due to the need for complete homogenization of the polyolefin composition and high costs.

[0014] There is a need in the art for linear polyolefin copolymers with high comonomer content and high molecular weight. There is also a need for BOCD polyolefin copolymer compositions with increased density split and high comonomer content. Summary of the Invention

[0015] In at least one embodiment, the catalyst compound is represented by formula (I) or formula (II):

[0016] (I) (II)

[0017] M is a Group 4 metal.

[0018] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Each is independently hydrogen, or a C1-C50 substituted or unsubstituted hydrocarbon group, a haloalkyl group, a silyl divalent carbon group, an alkoxy group, a silyl alkoxy group, or R. 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 , and R 7 and R 8 One or more connections in the ring form a cyclic saturated or unsaturated ring.

[0019] Each X is independently a halogen or a C1-C50 substituted or unsubstituted hydrocarbon group, hydride, amino, alkoxy, sulfide, phosphate, halogen or combination thereof, or two X are linked together to form a metal ring, or two X are linked together to form a chelate ligand, diene ligand or alkylidene group.

[0020] In another embodiment, a method for preparing a polyolefin composition includes contacting one or more olefins with a catalyst system comprising: (a) a catalyst compound represented by formula (I) or (II); and (b) a bridged or unbridged metallocene catalyst compound other than the catalyst compound represented by formula (I) or (II).

[0021] In particular, this application relates to the following aspects:

[0022] Item 1. Catalyst compounds represented by formula (I) or formula (II):

[0023] (I) (II)

[0024] M is a Group 4 metal.

[0025] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Each is independently hydrogen, or a C1-C50 substituted or unsubstituted hydrocarbon group, haloalkyl group, silyl divalent carbon group, alkoxy group, silyloxy group, or R. 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 , and R 7 and R 8 One or more connections in the ring form a cyclic saturated or unsaturated ring.

[0026] Each X is independently a halogen or a C1-C50 substituted or unsubstituted hydrocarbon group, hydrogen group, amino group, alkoxy group, sulfide group, phosphate group, halogen group or combination thereof, or two X groups are linked together to form a metal ring, or two X groups are linked together to form a chelate ligand, diene ligand or alkylidene group.

[0027] Item 2. The catalyst compound of Item 1, wherein R 9It is a C1-C20 substituted or unsubstituted hydrocarbon group.

[0028] Item 3. The catalyst compound of Item 2, wherein R 9 It is an unsubstituted phenyl or straight-chain or branched C1-C5 alkyl group.

[0029] Item 4. Catalyst compound of Item 1, wherein each X is independently a halide or a C1-C10 substituted or unsubstituted hydrocarbon group.

[0030] Item 5. The catalyst compound of Item 1, wherein R 6 Or R 7 and R 2 Or R 3 Each of them is a C1-C20 substituted or unsubstituted hydrocarbon group.

[0031] Item 6. The catalyst compound of Item 5, wherein R 6 Or R 7 and R 2 Or R 3 Each of them is a straight-chain or branched C3-C10 unsubstituted hydrocarbon group.

[0032] Item 7. Catalyst compound of Item 1, wherein M is Ti, Hf or Zr.

[0033] Item 8. Catalyst compound of Item 7, where M is Hf.

[0034] Item 9. The catalyst compound of Item 6, wherein the catalyst compound represented by formula (I) or formula (II) includes one or more of the following:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] Item 10. A catalyst system comprising:

[0043] (a) the catalyst compound of any one of items 1-9; and

[0044] (b) Bridged or unbridged metallocene catalyst compounds other than those in (a).

[0045] Item 11. The catalyst system of Item 10, wherein the metallocene catalyst compound of (b) is composed of the formula: Cp A Cp B M X n The unbridged metallocene catalyst compound is represented, where each Cp A and Cp B Independently selected from cyclopentadienyl ligands and isovalent ligands of the cyclopentadienyl group, Cp A and Cp B One or two of them may contain heteroatoms, and Cp A and Cp B One or two of them can be replaced by one or more R" groups, where M Selected from Groups 3-12 atoms and lanthanides, where X It is an anionic group, where n is 0 or an integer from 1 to 4, and R" is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, arylthio, aryl, substituted aryl, heteroaryl, arylalkyl, arylalkylene, alkylaryl, alkylarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, group containing heteroatoms, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boron, phosphin, phosphine, amino, amine, ether and thioether.

[0046] Item 12. The catalyst system of Item 11, wherein each Cp A and Cp B It is independently selected from cyclopentadienyl, indene, fluorenyl, benzo[a]indene, fluorenyl, octahydrofluorenyl, phenanthreneyl, 3,4-benzo[a]fluorenyl, 9-phenylfluorenyl, 7-H-dibenzo[a]fluorenyl and their hydrogenated forms.

[0047] Item 13. The catalyst system of Item 10, wherein the metallocene catalyst compound is composed of the formula: Cp A (A)Cp B M X n The represented bridged metallocene catalyst compound, wherein each Cp A and Cp B Independently selected from cyclopentadienyl ligands and isovalent ligands of the cyclopentadienyl group, Cp A and Cp BOne or two of them may contain heteroatoms, and Cp A and Cp B One or two of them can be replaced by one or more R" groups, where M Selected from Groups 3-12 atoms and lanthanides, where X It is an anionic group, where n is an integer from 0 to 4, and (A) is a bridging group containing at least one element from group 13, 14, 15 or 16.

[0048] Item 14. The catalyst system of Item 13, wherein (A) is selected from P(=S)R P(=Se)R P(=O)R R 2C, R 2Si, R 2Ge, R 2CCR 2. R 2CCR 2CR 2. R 2CCR 2CR 2CR 2. R C=CR R C=CR CR 2. R 2CCR =CR CR 2. R C=CR CR =CR R C=CR CR 2CR 2. R 2CSiR 2. R 2SiSiR 2. R 2SiOSiR 2. R 2CSiR 2CR 2. R 2SiCR 2SiR 2. R C=CR SiR 2、R 2CGeR 2、R 2GeGeR 2、R 2CGeR 2CR 2、R 2GeCR 2GeR 2、R 2SiGeR 2、R C=CR GeR 2、R B、R 2C-BR 、R 2C-BR -CR 2、R 2C-O-CR 2、R 2CR 2C-O-CR 2CR 2、R 2C-O-CR 2CR 2、R 2C-O-CR =CR 、R 2C-S-CR 2、R 2CR 2C-S-CR 2CR 2、R 2C-S-CR 2CR 2、R 2C-S-CR =CR 、R 2C-Se-CR 2、R 2CR 2C-Se-CR 2CR 2、R 2C-Se-CR 2CR 2、R 2C-Se-CR =CR 、R 2C-N=CR R 2C-NR -CR 2. R 2C-NR -CR 2CR 2. R 2C-NR -CR =CR R 2CR 2C-NR -CR 2CR 2. R 2C-P=CR R 2C-PR -CR 2. O, S, Se, Te, NR PR AsR SbR OO, SS, R N-NR R P-PR OS, O-NR O-PR S-NR S-PR and R N-PR , where R It is hydrogen or contains C1-C. 20 The alkyl group, substituted alkyl group, haloalkyl group, substituted haloalkyl group, silyl divalent carbon group or germanyl divalent carbon group or two or more adjacent R groups. They can be linked to form substituted or unsubstituted, saturated, partially unsaturated, or aromatic, cyclic or polycyclic rings.

[0049] Item 15. The catalyst system of Item 14, where (A) is R 2SiSiR 2 or R 2SiOSiR 2.

[0050] Item 16. A catalyst system of any one of items 10-12, wherein the metallocene catalyst of (b) comprises one or more of the following:

[0051]

[0052] Item 17. A catalyst system of Item 10 or any one of Items 13-16, wherein the metallocene catalyst of (b) comprises one or more of the following:

[0053]

[0054] Item 18. The catalyst system of any one of items 10-17 further includes an activator and a support material.

[0055] Item 19. Catalyst system, comprising:

[0056] Catalyst compound of any one of items 1 to 9;

[0057] Activator; and

[0058] Carrier material.

[0059] Item 20. A catalyst system of any one of items 18-19, wherein the activator comprises one or more of the following substances:

[0060] N,N-Dimethylphenylamine tetra(perfluorophenyl)borate,

[0061] N,N-Dimethylphenylamine tetra(perfluoronaphthyl)borate

[0062] N,N-Dimethylphenylamine tetra(perfluorobiphenyl)borate

[0063] N,N-Dimethylphenylamine tetra(3,5-bis(trifluoromethyl)phenyl)borate,

[0064] Triphenylcarbomontetra(perfluoronaphthyl)borate

[0065] Triphenylcarbium tetra(perfluorobiphenyl) borate,

[0066] Triphenylcarbium tetra(3,5-bis(trifluoromethyl)phenyl)borate,

[0067] Triphenylcarbium tetra(perfluorophenyl)borate,

[0068] Trimethylammonium tetra(perfluoronaphthyl)borate

[0069] Triethylammonium tetra(perfluoronaphthyl)borate

[0070] Tripropylammonium tetra(perfluoronaphthyl)borate

[0071] Tris(n-butyl)ammonium tetra(perfluoronaphthyl)borate,

[0072] Tris(tert-butyl)ammonium tetra(perfluoronaphthyl)borate,

[0073] N,N - diethylanilinium tetrakis(perfluoronaphthyl)borate,

[0074] N,N - dimethyl-(2,4,6 - trimethylanilinium)tetrakis(perfluoronaphthyl)borate, and

[0075] tetrakis(perfluoronaphthyl)boric onium.

[0076] Item 21. The catalyst system according to any one of Items 18 - 19, wherein the activator comprises an alkylaluminoxane.

[0077] Item 22. The catalyst system according to any one of Items 18 - 21, wherein the support material is selected from Al2O3, ZrO2, SiO2 or SiO2 / Al2O2.

[0078] Item 23. The catalyst system according to Item 22, wherein the support material is fluorinated.

[0079] Item 24. A method for polymerizing an olefin to produce at least one polyolefin composition, the method comprising: contacting at least one olefin with the catalyst system according to any one of Items 10 - 23; and obtaining a polyolefin.

[0080] Item 25. The method according to Item 24, wherein:

[0081] R 6 or R 7 at least one of which is a C1 - C20 substituted or unsubstituted hydrocarbon group, and

[0082] R 2 or R 3 at least one of which is a C1 - C20 substituted or unsubstituted hydrocarbon group.

[0083] Item 26. The method according to Item 25, wherein:

[0084] R 6 or R 7 at least one of which is a straight - chain or branched C3 - C10 unsubstituted hydrocarbon group, and

[0085] R 2 or R 3 at least one of which is a straight - chain or branched C3 - C10 unsubstituted hydrocarbon group.

[0086] Item 27. The method according to any one of Items 24 - 26, wherein the polyolefin composition is a multimodal polyolefin composition comprising a high - molecular - weight fraction, the high - molecular - weight fraction containing greater than about 10 wt% hexene, and the high - molecular - weight fraction is prepared from a catalyst compound represented by formula (I) or formula (II).

[0087] The method of Item 28.27, wherein the high molecular weight fraction contains about 15 wt% or more of hexene.

[0088] Item 29. The method of any one of items 24-28, where each Cp A and Cp B It is indene and is derived from equation (III) )express:

[0089] (III )

[0090] M is a Group 4 metal.

[0091] Each X is independently a halide or a C1-C50 substituted or unsubstituted hydrocarbon group, hydride group, amino group, alkoxy group, sulfide group, phosphate group, halide group, diene, amine, phosphine, ether, or combination thereof, or two X groups linked together to form a metal ring, or two X groups linked together to form a chelate ligand, diene ligand, or alkylidene group, and

[0092] R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 and R 23 Each can be independently a hydrogen group, a hydrocarbon group, a substituted hydrocarbon group, or a heteroatom group.

[0093] Item 30. The method of any one of items 24-29, further comprising an alkylaluminoxane present in a molar ratio of aluminum to a Group 4 metal of the catalyst compound of 100:1 or higher.

[0094] Item 31. The method according to any one of items 24-30, wherein the catalyst system further comprises an activator represented by the following formula:

[0095] (Z) d + (A d- )

[0096] Where Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + It is Brønsted acid; A d- It is a noncoordinate anion with charge d-; d is an integer from 1 to 3.

[0097] Item 32. The method of any one of items 24-31, wherein the catalyst system further comprises an activator represented by the following formula:

[0098] (Z) d + (A d- )

[0099] Where A d- It is a noncoordinate anion with charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the following formula: (Ar3C + ), where Ar is an aryl group or surrounded by heteroatoms, C1-C 40 Hydrocarbon group or substituted C1-C 40 Aromatic groups substituted with hydrocarbon groups.

[0100] Item 33. The method of any one of items 24 to 32, wherein the method is carried out at a temperature of about 0°C to about 300°C, a pressure of about 0.35 MPa to about 10 MPa, and for a time of up to about 300 minutes.

[0101] Item 34. The method of any one of items 24-33, wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

[0102] Item 35. The method of any one of items 24-34 further includes introducing a first catalyst compound represented by formula (I) or formula (II) as a slurry into the reactor. Attached Figure Description

[0103] Figure 1 This is the TREF diagram of the polyethylene copolymer prepared by supported catalyst 1.

[0104] Figure 2 This is a 4D GPC diagram of the polyethylene copolymer prepared by supported catalyst 1. Invention Details

[0105] For the purposes of this specification, the periodic table group numbering scheme is used as described in Chemical & Engineering News 27 (1985), 63(5), page 5. Therefore, “Group 4 metal” refers to an element in Group 4 of the periodic table, such as Hf, Ti, or Zr.

[0106] "Catalyst productivity" is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing W g of catalyst (cat) over a time period of T hours, and can be expressed as: P / (T W) and gPgcat -1 hr -1Units are used to express the conversion rate. Conversion rate is the amount of monomer converted into the polymer product and is expressed as mol% and is calculated based on the polymer yield (by weight) and the amount of monomer added to the reactor. Catalyst activity is a measure of the magnitude of catalyst activity and is reported as the mass of product polymer (P) produced per mass of loaded catalyst (cat) (gP / g loaded cat). In at least one embodiment, the catalyst activity is at least 800 g polymer / g loaded catalyst / hour, for example about 1,000 g or more polymer / g loaded catalyst / hour, for example about 2,000 g or more polymer / g loaded catalyst / hour, for example about 3,000 g or more polymer / g loaded catalyst / hour, for example about 4,000 g or more polymer / g loaded catalyst / hour, for example about 5,000 g or more polymer / g loaded catalyst / hour.

[0107] "Alkene," or "olefin," is a straight-chain, branched, or cyclic compound having at least one double bond between carbon and hydrogen. For the purposes of this specification, ethylene should be considered... -Olefins. When a polymer or copolymer is referred to as containing olefins, the olefins present in such polymer or copolymer are polymeric forms of olefins. For example, when a copolymer is said to have an ethylene content of 35 wt% to 55 wt%, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and that said derived units are present in 35 wt% to 55 wt% based on the weight of the copolymer. A “polymer” has two or more identical or different monomer units. A “homopolymer” is a polymer having identical monomer units. A “copolymer” is a polymer having two or more monomer units that are different from each other. A “terpolymer” is a polymer having three monomer units that are different from each other. The term “different” used to indicate monomer units means that the monomer units differ from each other by at least one atom or are different isomers. Thus, as used herein, the definition of “copolymer” includes terpolymers, etc. Oligomers are generally polymers with low molecular weights, such as Mn less than 25,000 g / mol or less than 2,500 g / mol, or a small number of monomer units, such as 75 monomer units or less or 50 monomer units or less. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene-derived units, "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene-derived units, and so on.

[0108] "Catalyst system" is a combination of at least one catalyst compound represented by formula (I) and / or formula (II) with a second system component such as a second catalyst compound and / or an activator. The catalyst system may have at least one activator, at least one support material, and / or at least one co-activator. When a catalyst system is described as containing components in a neutral, stable form, those skilled in the art will fully understand that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. For the purposes of this specification, "catalyst system" includes both neutral and ionic forms of the catalyst system components.

[0109] As used herein, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, wt% is the weight percentage, and mol% is the molar percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol. Molecular weight distribution (“MWD”) equals the expression M... w / M n Expression M w / M n It is the weight-average molecular weight (M w ) and number-average molecular weight (M n The ratio of ).

[0110] The distribution and timing of molecular weight (Mw, Mn, Mw / Mn, etc.), comonomer content (C2, C3, C6, etc.), and long-chain branching (g) were determined by high-temperature gel permeation chromatography (Polymer Char GPC-IR) using an infrared detector (IR5, 18-angle light scattering detector) equipped with a multi-channel bandpass filter and a viscometer. Using three Agilent PLEASE 10 lenses. A mMixed-B LS column was used to provide polymer separation. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) with 300 ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was passed through a 0.1... The sample was filtered through a Teflon filter and degassed using an online degasser before entering the GPC instrument. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 200 mL / min. L. The entire system, including the transfer line, column, and detector, is contained in an oven at 145°C. Weigh the given amount of polymer sample and seal it in a standard vial, then add 80... L-flow marker (heptane). After loading the vial into the autosampler, the polymer is automatically dissolved in the instrument, followed by the addition of 8 mL of TCB solvent. The polymer is dissolved at 160°C, with continuous shaking for approximately 1 hour for most PE samples or 2 hours for PP samples. The TCB density used for concentration calculation is 1.463 g / mL at room temperature and 1.284 g / mL at 145°C. Sample solution concentrations range from 0.2 to 2.0 mg / mL, with lower concentrations used for higher molecular weight samples.

[0111] Concentration at each point in the chromatogram ( c The IR5 broadband signal strength subtracted from the baseline ( I ), calculate using the following equation:

[0112] c= I

[0113] in It is a mass constant determined using PE or PP standards. The mass recovery rate is calculated from the ratio of the integral area of ​​the concentration chromatography to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection loop volume.

[0114] The conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with column calibration, which is performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M. The MW for each elution volume is calculated using the following equation.

[0115]

[0116] Variables with the subscript "PS" represent polystyrene, while variables without a subscript represent the test sample. In this method, as well as ,and a and K It was calculated based on a series of empirical formulas published in the literature (T. Sun, P. Brant, R.R. Chance, and W.W. Graessley, Macromolecules, Vol. 34, No. 19, pp. 6812-6820, (2001)). Specifically, a / K =PE is 0.695 / 0.000579 and =PP is 0.705 / 0.0002288.

[0117] The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to the CH2 and CH3 channels to a series of PE and PP homopolymer / polymer standards, whose nominal values ​​are predetermined by NMR or FTIR, such as the EMCC commercial grade for LLDPE.

[0118] 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 a Zimm model for static light scattering (MB Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971).

[0119]

[0120] here, R( ) is at the scattering angle The excess Rayleigh scattering intensity is measured at point , c is the polymer concentration determined from IR5 analysis, and A2 is the second virial coefficient. P( K is the form factor of a monodisperse random coil. o These are the optical constants of the system:

[0121]

[0122] Where N A Here, Avogadro's number and (dn / dc) represent the refractive index increment of the system. At 145℃ and The refractive index of TCB at 665nm, n=1.500.

[0123] A high-temperature Agilent (or Viscotek Corporation) viscometer features four capillaries arranged in a Wheatstone bridge configuration, each with two pressure sensors, used to determine specific viscosity. One sensor measures the total pressure drop across the detector, while the other measures the pressure difference between the two sides of the bridge. The specific viscosity of the solution flowing through the viscometer is then determined. s Calculated from their outputs. The intrinsic viscosity at each point in the chromatogram [ Calculated by the following formula:

[0124] [ ]= s / c

[0125] Where c is the concentration, determined by the IR5 broadband channel output. The viscosity MW at each point is calculated by the following formula:

[0126] .

[0127] In the disclosure of this application, a catalyst may be described as a catalyst precursor, a precatalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is an electrically neutral ligand that donates one or more pairs of electrons to a metal ion.

[0128] For the purposes of this specification, in relation to catalyst compounds, the term "substituted" means that a hydrogen group has been replaced by a hydrocarbon group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (MeCp) is a Cp group substituted with a methyl group, and ethanol is an ethyl group substituted with an -OH group.

[0129] For the purposes of this specification, "alkoxy" includes those in which the alkyl group is a C1-C10 hydrocarbon group. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group can be saturated or unsaturated. In at least one embodiment, the alkyl group may contain at least one aromatic group. The terms "alkoxy" or "alkoxy group" preferably refer to an alkyl ether or aryl ether group, wherein the term alkyl is a C1-C10 alkyl group. Examples of suitable alkyl ether groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, etc.

[0130] This specification discloses transition metal complexes. The term complex is used to describe molecules in which an auxiliary ligand is coordinated to a central transition metal atom. The ligand is stably bonded to the transition metal to maintain its influence during the use of catalysts such as in polymerization. The ligand can coordinate to the transition metal via covalent bonds and / or electron-donating coordination or intermediate bonds. Transition metal complexes are typically activated to exert their polymerization function using activators, which are thought to generate cations by removing anionic groups (commonly referred to as leaving groups) from the transition metal.

[0131] In this invention, the following abbreviations may be used: dme is 1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylaluminoxane, sMAO is supported methylaluminoxane, p-Me is p-methyl, Bn is benzyl (i.e., CH2Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (and 23°C, unless otherwise stated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

[0132] Throughout this specification, the terms "hydrocarbon residue," "hydrocarbon group," "alkyl residue," and "alkyl" are used interchangeably. Similarly, the terms "group," "residue," and "substituent" are used interchangeably. For the purposes of this specification, "hydrocarbon residue" is defined as a C1-C100 group, which may be straight-chain, branched, or cyclic, and when cyclic, is aromatic or non-aromatic. Examples of such groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., including their substituted analogs. A substituted hydrocarbon group is a group in which at least one hydrogen atom of the hydrocarbon group has been replaced by at least one non-hydrogen group, such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group such as N. 2, O Se Te P 2, As 2, Sb 2, S B 2, Si 3, Ge 3, Sn 3, Pb 3, or at least one heteroatom is inserted into the hydrocarbon ring.

[0133] The term "alkenyl" refers to a straight-chain, branched, or cyclic hydrocarbon group having one or more carbon-carbon double bonds. These alkenyl groups can be substituted. Examples of suitable alkenyl groups include, but are not limited to, vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and their substituted analogues.

[0134] The term “aryl” or “aryl group” refers to a carbon-containing aromatic ring and its substituted variants, including but not limited to phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, a heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been substituted by a heteroatom, preferably N, O, or S. As used herein, the term “aromatic” also refers to pseudoaromatic heterocycles. These are heterocyclic substituents that have properties and structures (almost planar) similar to aromatic heterocyclic ligands, but are not aromatic by definition; again, the term aromatic also refers to substituted aromatics.

[0135] When a specified alkyl, alkenyl, alkoxy, or aryl isomer is present (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), reference to one member of that group (e.g., n-butyl) should explicitly disclose the remaining isomers in that group (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, reference to an alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0136] The term "ring atom" refers to an atom that is part of a cyclic ring structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms. A heterocycle is a ring structure containing heteroatoms, as opposed to a heteroatom-substituted ring, in which hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring.

[0137] As used herein, "complex" also generally refers to catalyst precursors, precatalysts, catalysts, catalyst compounds, transition metal compounds, or transition metal complexes. These terms are used interchangeably. Activators and co-catalysts are also used interchangeably.

[0138] Scavengers are compounds that can be added to a catalyst system to promote polymerization by removing impurities. Some scavengers can also act as activators and can be called co-activators. Co-activators that are not scavengers can also be used in combination with activators to form an active catalyst system. In at least one embodiment, the co-activator can be premixed with a transition metal compound to form an alkylated transition metal compound.

[0139] In this description, catalysts may be described as catalyst precursors, precatalyst compounds, catalyst compounds, or transition metal compounds, and these terms are used interchangeably. Polymerization catalyst systems are catalyst systems that can polymerize monomers into polymers.

[0140] The term "continuous" refers to a system that operates without interruption or cessation over a period of time. For example, a continuous method for producing polymers involves continuously introducing reactants into one or more reactors and continuously removing the polymer product.

[0141] "Solution polymerization" refers to a polymerization method in which polymerization takes place in a liquid polymerization medium, such as an inert solvent or monomers or blends thereof. Solution polymerization is typically homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in a polymerization medium. Such a system is preferably not turbid, as disclosed in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng. Chem. Res. (2000), 29, 4627.

[0142] Bulk polymerization refers to a polymerization method in which the monomers and / or comonomers being polymerized are used as solvents or diluents, with little or no inert solvents or diluents used. A small portion of the inert solvent may be used as a carrier for catalysts and scavengers. Bulk polymerization systems contain less than about 25 wt%, for example less than about 10 wt%, for example less than about 1 wt%, for example 0 wt% of inert solvents or diluents.

[0143] Catalyst compounds

[0144] This specification provides novel catalyst compounds containing H-Si bridges and catalyst systems containing such catalyst compounds, as well as their applications.

[0145] In at least one embodiment, this specification discloses catalyst compounds represented by formula (I) or formula (II), and catalyst systems comprising such compounds:

[0146] (I) (II)

[0147] M is a Group 4 metal.

[0148] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 , and R 9 Each of these groups is independently hydrogen, or a C1-C50 substituted or unsubstituted hydrocarbon group, a haloalkyl group, a silyl divalent carbon group, an aryloxy group, an alkoxy group, a silyl alkoxy group, or an R group. 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 , and R 7 and R 8 One or more links in the group form a saturated or unsaturated ring. Each X is independently a halogen or a C1-C50 substituted or unsubstituted hydrocarbon group, hydride, amino, alkoxy, sulfide, phosphate, halogen or combination thereof, or two Xs are linked together to form a metal ring, or two Xs are linked together to form a chelate ligand, diene ligand or alkylidene group.

[0149] In at least one implementation, R 9 It is a C1-C20 substituted or unsubstituted hydrocarbon group. R9 It can be an unsubstituted phenyl or a straight-chain or branched C1-C5 alkyl group.

[0150] R 6 Or R 7 and R 2 Or R 3 Each of these can be a C1-C20 substituted or unsubstituted hydrocarbon group. R 6 Or R 7 and R 2 Or R 3 Each of them can be a straight-chain or branched C3-C10 unsubstituted hydrocarbon group.

[0151] Each X can be independently a halogen or a C1-C10 substituted or unsubstituted hydrocarbon group.

[0152] In at least one embodiment, M is Ti, Hf, or Zr.

[0153] The catalyst compound represented by formula (I) or formula (II) can be:

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] In at least one embodiment, the catalyst system includes a catalyst compound represented by formula (I) or formula (II) and a second catalyst compound, wherein the second catalyst compound is a bridged or unbridged metallocene catalyst compound that is different from the catalyst compound represented by formula (I) or formula (II).

[0162] The second catalyst compound can be an unbridged metallocene catalyst compound represented by the following formula: Cp A Cp B M X n M Selected from atoms in groups 3 to 12 and lanthanides. X It is an anion leaving group, where n is 0 or an integer from 1 to 4. Each Cp A and CpB Independently selected from cyclopentadienyl ligands and ligands isovalent to the cyclopentadienyl group. Cp A and Cp B One or two of them may contain heteroatoms. Cp A and Cp B One or both of them may be substituted by one or more R" groups. Each R" is independently selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, aryl, substituted aryl, heteroaryl, aralkyl, arylene alkyl, alkylaryl, alkylene aryl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, groups containing heteroatoms, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boronyl, phosphinyl, phosphine, amino, amine, ether, and thioether.

[0163] Cp A and Cp B One or both of them may be selected from cyclopentadienyl, indene, fluorenyl, benzoindene, fluorenyl, octahydrofluorenyl, phenanthreneyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 7-H-dibenzofluorenyl and their hydrogenated forms.

[0164] In at least one embodiment, the second catalyst compound is a bridged metallocene catalyst compound represented by the following formula: Cp A (A)Cp B M X n Cp A Cp B M X And n as described above. Cp A and Cp B One or both of them may be replaced by one or more R" groups. Each R" is as described above. (A) is a bridging group containing at least one element from group 13, 14, 15 or 16. (A) may be selected from P(=S)R , P(=Se)R , P(=O)R R 2C, R 2Si,R 2Ge,R 2CCR 2, R 2CCR 2CR 2, R 2CCR 2CR 2CR 2,R C=CR ,R C=CR CR 2,R 2CCR =CR CR 2,R C=CR CR =CR ,R C=CR CR 2CR 2,R 2CSiR 2,R 2SiSiR 2,R 2SiOSiR 2,R 2CSiR 2CR 2,R 2SiCR 2SiR 2,R C=CR SiR 2,R 2CGeR 2,R 2GeGeR 2,R 2CGeR 2CR 2,R 2GeCR 2GeR 2,R 2SiGeR 2,R C=CR GeR 2,R B,R 2C-BR ,R 2C-BR -CR 2,R 2C-O-CR 2,R 2CR 2C-O-CR 2CR 2,R 2C-O-CR 2CR 2,R 2C-O-CR =CR ,R 2C-S-CR 2,R 2CR 2C-S-CR 2CR 2,R 2C-S-CR 2CR 2,R 2C-S-CR =CR ,R 2C-Se-CR 2,R 2CR 2C-Se-CR 2CR 2,R 2C-Se-CR 2CR 2,R 2C-Se-CR =CR ,R 2C-N=CR ,R 2C-NR -CR 2,R 2C-NR -CR 2CR 2,R 2C-NR -CR =CR ,R 2CR 2C-NR -CR 2CR 2,R 2C-P=CR ,R 2C-PR -CR 2,O,S,Se,Te,NR ,PR ,AsR ,SbR ,OO,SS,R N-NR R P-PR OS, O-NR O-PR S-NR S-PR and R N-PR R It is hydrogen or contains C1-C. 20 The alkyl group, substituted alkyl group, haloalkyl group, substituted haloalkyl group, silyl divalent carbon group or germanyl divalent carbon group or two or more adjacent R groups. They can be linked to form substituted or unsubstituted, saturated, partially unsaturated, or aromatic, cyclic or polycyclic rings. In at least one embodiment, (A) is R. 2SiSiR 2 or R 2SiOSiR 2.

[0165] The second catalyst compound can be one or more of the following:

[0166]

[0167] The second catalyst compound can be one or more of the following:

[0168]

[0169] This specification also discloses catalyst systems comprising activators and support materials. This specification also discloses methods for polymerizing olefins to prepare polyolefin compositions (e.g., resins) by contacting olefins with a catalyst system comprising formula (I) or formula (II).

[0170] The polyolefin composition may be a multimodal polyolefin composition comprising a high molecular weight fraction, which is more than about 10 wt% of a comonomer, such as hexene. The high molecular weight fraction is generated by a catalyst compound represented by formula (I) or formula (II). In at least one embodiment, the high molecular weight fraction comprises about 15 wt% or more of a comonomer.

[0171] The catalyst systems and methods described in this specification may include a second catalyst compound, which is an unbridged metallocene catalyst compound represented by the following formula: Cp A Cp B MX n , where each Cp A and Cp B It is indene and is obtained through formula (III) )express:

[0172] (III )

[0173] M is a Group 4 metal. Each X is independently a halide or a C1-C50 substituted or unsubstituted hydrocarbon group, hydride, amino, alkoxy, sulfide, phosphate, halide, diene, amine, phosphine, ether, or a combination thereof, or two Xs linked together to form a metal ring or two Xs linked together to form a chelate ligand, diene ligand, or alkylidene group. R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 , and R 23 Each of these can be independently hydrogen, a hydrocarbon group, a substituted hydrocarbon group, or a heteroatom group.

[0174] In at least one embodiment, in any of the methods described herein, a catalyst compound is used, for example, the catalyst compound is not different. For the purposes of this application, a catalyst compound is considered different from another catalyst compound if they differ by at least one atom. For example, "bisindenylzirconium chloride" is different from "(indenyl)(2-methylindenyl)zirconium chloride," which is different from "(indenyl)(2-methylindenyl)hafnium chloride." For the purposes of this specification, catalyst compounds that differ only in their isomers, such as racemic-dimethylsilylbis(2-methyl-4-phenyl)dimethylhafnium and meso-dimethylsilylbis(2-methyl-4-phenyl)dimethylhafnium, are considered the same.

[0175] In at least one embodiment, two or more different catalyst compounds are present in the catalyst system used herein. In at least one embodiment, two or more different catalyst compounds are present in the reaction zone, wherein the method described herein is implemented. When two transition metal catalysts are used as a mixed catalyst system in a reactor, it is preferable to select two transition metal compounds that are compatible with each other. Any suitable screening method can be used, for example by... 1 H or 13C NMR is used to determine which transition metal compounds are compatible. For transition metal compounds, it is preferred to use the same activator; however, two different activators can be used in combination, such as a noncoordinate anion activator and an aluminoxane. If one or more transition metal compounds contain an X1 or X2 ligand that is not a hydrogen group, a hydrocarbon group, or a substituted hydrocarbon group, the aluminoxane should be contacted with the transition metal compound before adding the noncoordinate anion activator.

[0176] The catalyst compound represented by formula (I) or formula (II) and the second catalyst compound can be used in any ratio (A:B). If the second catalyst compound is (B), then the catalyst compound represented by formula (I) or formula (II) can be (A). Alternatively, if the second catalyst compound is (A), then the catalyst compound represented by formula (I) or formula (II) can be (B). The preferred molar ratio (A:B) of the transition metal compound (A):B is in the range of about 1:1000 to about 1000:1, for example, about 1:100 to about 500:1, for example, between about 1:10 and about 200:1, for example, between about 1:1 and about 100:1, or between 1:1 and 75:1, or between 5:1 and 50:1. The specific ratio chosen depends on the exact precatalyst selected, the activation method, and the desired final product. In one specific embodiment, when two catalyst compounds are used, both catalyst compounds are activated with the same activator, and the useful molar percentage based on the molecular weight of the catalyst compounds is about 10 to about 99.9% (A) relative to about 0.1 to about 90% (B), for example about 25% to about 99% (A) relative to about 0.5% to about 50% (B), for example about 50% to about 99% (A) relative to about 1% to about 25% (B), for example about 75% to about 99% (A) relative to about 1% to about 10% (B).

[0177] Methods for preparing catalyst compounds

[0178] Synthesis of Si(H)-bridged cyclopentadienyl ligands and their metal complexes: Type R (H)Si(R"CpH)2(where R) =Me, Ph; R"=n-propyl, Me3SiCH2-) silyl (hydride) bridged cyclopentadienyl ligand in tetrahydrofuran solvent at ambient temperature via R Quantitative synthesis was achieved via a direct salt metathesis reaction of (H)SiCl2 with two equivalents of lithium-R"-cyclopentadiene (Scheme 1). The structures of all four compounds were confirmed by 1H NMR spectroscopy. Due to the asymmetric chemical state at Si(H) disrupting the symmetry of the compounds, the NMR spectra showed signals with an increased number of appropriate proton integrals or unresolved multiplets. The Si-H resonance of these compounds changed from δ=3.68ppm to 4.56ppm, indicating that the Si(H) hydrides are sensitive to electronic and steric environments. Cyclopentadienyl Si(H) ligands can be synthesized via a one-step or two-step synthetic scheme (Scheme 1). Electron-rich, sterically hindered cyclopentadienyl (Me4C) ligands were synthesized. p) Bonding to the Si(H) center under milder reaction conditions prevents Si-Cl reduction. Therefore, Me(H)Si(Me4CpH)(Me3SiCH2CpH) (Scheme 1) was obtained in a moderate (56.8%) yield by treating Me(H)SiCl2 with Li(Me4Cp) in tetrahydrofuran solvent, followed by reaction with Me3SiCH2Cp-Li, while bonding the electron-rich and sterically hindered tetramethylcyclopentadienyl group to the Si(H) center under milder conditions. The Si(H) protons appear as multiplets (δ = 4.67–4.72 ppm) in the 1H NMR spectrum. All other peak assignments and integral values ​​further support the structural interpretation of the ligand.

[0179]

[0180] Scheme 1. General synthetic route for Si(H)-bridged cyclopentadienyl ligands (where R =Me, Ph and R"=Pr,-CH2SiMe3).

[0181] The synthesized ligands were conveniently deprotonated at -25°C with appropriate or two equivalents of n-butyllithium, and all the corresponding lithium salts were obtained by... 1 A comprehensive characterization was performed using 1H NMR spectroscopy (Scheme 2).

[0182]

[0183] Scheme 2. General synthetic route for Si(H)-bridged metallocenes (where M = Hf, Zr; R) =Me, Ph; R"=n-Pr, -CH2SiMe3; R1=R3=R4=Me, H; R2=Me, n-Pr, -CH2SiMe3).

[0184] At 3.2–3.6 ppm, no two cyclopentadiene matrices further support the formation of the compounds. The synthesized bridged cyclopentadiene ligand lithium salts are excellent precursors for metallocene synthesis. All disclosed hafnium- and zirconium-based dichloride derivatives have been synthesized by salt elimination reactions under milder conditions by treating equimolar ratios of ligand precursors or lithium salts of bridged cyclopentadiene ligands with MCl4 (M = Hf or Zr). The corresponding dimethyl metallocenes (1–6) (Scheme 2) were synthesized at -25 °C using stoichiometric or 2-equivalent MeMgBr solutions. The catalyst compounds of structures 1–6 were obtained by... 1 H NMR spectroscopy identification.

[0185] Activator

[0186] The catalyst system described in this specification may have one or more activators. The terms "co-catalyst" and "activator" are used interchangeably herein and are defined as any compound that can activate any of the aforementioned catalyst compounds by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

[0187] Supported catalyst systems can be formed by combining two or more of the aforementioned metal catalyst components with an activator in any manner known in the literature, including by loading them for slurry or gas-phase polymerization. An activator is defined as any compound that can activate any of the aforementioned catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators include, for example, aluminoxanes, alkylaluminums, ionized activators which can be neutral or ionic, and conventional co-catalysts. Preferred activators typically include aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that extract reactive... - Bonded metal ligands enable metal compounds to become cations and provide uncoordinated or weakly coordinated anions for charge balance.

[0188] Aluminoxane activator

[0189] Supported catalyst systems can be formed by combining the above-described catalysts with activators in any manner known in the literature, including their use in slurry or gas-phase polymerization. An activator is defined as any compound that can activate any of the above-described catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators, for example, include aluminoxanes, alkylaluminums, ionized activators which can be neutral or ionic, and conventional co-catalysts. Preferred activators typically include aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that extract reactive... - Bonded metal ligands enable metal compounds to become cations and provide uncoordinated or weakly coordinated anions for charge balance.

[0190] Aluminoxane activator

[0191] Aluminoxane activators are used as activators in the catalyst system described herein. Aluminoxanes typically contain -Al(R...) 1 Oligomeric compounds of the )-O- subunit, wherein R 1 It is an alkyl group. Examples of aluminum oxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the extractable ligand is alkyl, halide, alkoxy, or amino. Mixtures of different aluminum oxanes and modified aluminum oxanes can also be used. Visually transparent methylaluminoxanes are preferred. Turbid or gelled aluminum oxanes can be filtered to produce a clear solution, or clear aluminum oxanes can be decanted from a turbid solution. A useful aluminum oxane is type 3A modified methylaluminoxane (MMAO) cocatalyst (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered by U.S. Patent No. US5,041,584).

[0192] When the activator is an aluminoxane (modified or unmodified), some embodiments typically select the maximum amount of activator on the catalyst compound (per metal catalytic site), where the Al / M ratio is up to 5000 times the molar excess Al / M. The minimum molar ratio of activator to catalyst compound is 1:1. Preferred alternative ranges include 1:1 to 500:1, or 1:1 to 200:1, or 1:1 to 100:1, or 1:1 to 50:1.

[0193] In an alternative embodiment, aluminoxanes are used sparingly or not at all in the polymerization method described herein. Preferably, the aluminoxanes are present in zero molar percentage, or in a molar ratio of aluminum to the transition metal of the catalyst compound of less than 500:1, preferably less than 300:1, more preferably less than 100:1, and more preferably less than 1:1.

[0194] Ionized / noncoordinated anion activators

[0195] The term "noncoordinate anion" (NCA) refers to an anion that does not coordinate with a cation or only weakly coordinates with a cation, thus remaining sufficiently unstable to be replaced by a neutral Lewis base. A "compatible" noncoordinate anion is one that does not degrade to a neutral anion upon decomposition of the initially formed complex. Furthermore, the anion does not transfer anionic substituents or fragments to the cation, thereby preventing the formation of neutral transition metal compounds and neutral byproducts from the anion. The useful noncoordinate anions described in this invention are compatible, stabilize transition metal cations in the sense of balancing their ionic charge +1, and remain sufficiently unstable to allow for substitution during polymerization. Ionizing activators used herein typically contain NCAs, particularly compatible NCAs.

[0196] The use of neutral or ionic activators, such as tris(n-butyl)ammonium tetra(pentafluorophenyl)borate, trifluorophenylboron quasi-metallic precursors or trifluoronaphthylboron nonmetallic precursors, polyhalogenated heteroborane anions (WO 98 / 43983), boric acid (US 5,942,459), or combinations thereof, is also within the scope of this invention. The use of neutral or ionic activators alone or in combination with aluminoxane or modified aluminoxane activators is also within the scope of this invention. For a description of useful activators, see US 8,658,556 and US 6,211,105.

[0197] Preferred activators include N,N-dimethylphenylamine tetra(perfluoronaphthyl)borate, N,N-dimethylphenylamine tetra(perfluorobiphenyl)borate, N,N-dimethylphenylamine tetra(perfluorophenyl)borate, N,N-dimethylphenylamine tetra(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbazide tetra(perfluoronaphthyl)borate, triphenylcarbazide tetra(perfluorobiphenyl)borate, triphenylcarbazide tetra(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbazide tetra(perfluorophenyl)borate, [Me3NH + ][B(C6F5)4 - ]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidine; and tetra(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0198] In a preferred embodiment, the activator includes triarylcarbamates (e.g., triphenylcarbamate, triphenylcarbamate tetra(pentafluorophenyl)borate, triphenylcarbamate tetra(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbamate tetra(perfluoronaphthyl)borate, triphenylcarbamate tetra(perfluorobiphenyl)borate, triphenylcarbamate tetra(3,5-bis(trifluoromethyl)phenyl)borate).

[0199] In another embodiment, the activator comprises one or more of tetraalkylammonium tetra(pentafluorophenyl)borate, N,N-dialkylphenylammonium tetra(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylphenylammonium)tetra(pentafluorophenyl)borate, tetraalkylammonium-(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylphenylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetra(perfluoronaphthyl)borate, and N,N-dialkylphenylammonium tetra(perfluoronaphthyl)borate. Tetraalkylammonium tetra(perfluorobiphenyl)borate, N,N-dialkylphenylammonium tetra(perfluorobiphenyl)borate, trialkylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylphenylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylphenylammonium)tetra(3,5-bis(trifluoromethyl)phenyl)borate, di-(isopropyl)ammonium tetra(pentafluorophenyl)borate (wherein the alkyl group is methyl, ethyl, propyl, n-butyl, sec-butyl or tert-butyl).

[0200] A typical activator-to-catalyst ratio, for example, is about 1:1 molar ratio for all NCA activators and catalysts. Preferred alternative ranges include 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1, and alternatively 1:1 to 1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 5:1.

[0201] Optional cleaning agents or activators

[0202] In addition to these activator compounds, the catalyst system described herein may include scavengers or co-activators. Scavengers or co-activators include alkyl aluminum or organoaluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc.

[0203] Optional carrier material

[0204] In at least one embodiment, the catalyst system comprises an inert support material. The support material may be a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clay, organoclay, or any other organic or inorganic support material, or mixtures thereof.

[0205] In at least one embodiment, the support material is a finely chopped inorganic oxide. Inorganic oxide materials suitable for the catalyst system of the present invention include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina are magnesium oxide, titanium dioxide, zirconium oxide, etc. However, other suitable support materials can be used, such as finely chopped functionalized polyolefins, such as finely chopped polyethylene. Particularly useful supports include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, succinate, zeolite, talc, clay, etc. Moreover, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. In at least one embodiment, the support material is selected from Al₂O₃, ZrO₂, SiO₂, SiO₂ / Al₂O₂, or mixtures thereof. The support material may be fluorinated.

[0206] As used herein, the phrases “fluorinated support” and “fluorinated support composition” refer to a support that has been treated with at least one inorganic fluorinated compound, ideally particulate and porous. For example, a fluorinated support composition may be a silica support in which some of the silica hydroxyl groups have been replaced by fluorine or a fluorinated compound. Suitable fluorinated compounds include, but are not limited to, inorganic and / or organic fluorinated compounds.

[0207] The fluorine compound suitable for providing fluorine to the support can be an organic or inorganic fluorine compound, and ideally an inorganic fluorine-containing compound. This inorganic fluorine-containing compound can be any compound containing fluorine atoms, as long as it does not contain carbon atoms. Particularly desirable compounds are those selected from NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2, NH4HF2, and combinations thereof. In at least one embodiment, ammonium hexafluorosilicate and ammonium tetrafluoroborate are used.

[0208] The preferred material is the carrier material, and the most preferred material is an inorganic oxide, having a thickness of about 10 to about 700 μm. 2 / g surface area, about 0.1 to about 4.0 cc / g pore volume and about 5 to about 500 The average particle size is m. In at least one embodiment, the surface area of ​​the carrier material is about 50 to about 500 m². 2 / g, pore volume from about 0.5 to about 3.5 cc / g, average particle size from about 10 to about 200 The surface area of ​​the carrier material can be from approximately 100 to approximately 400 m². 2 / g, pore volume from about 0.8 to about 3.0 cc / g, average particle size from about 5 to about 100 The average pore size of the support material can be from about 10 to about 1000 Å, for example from about 50 to about 500 Å, for example from about 75 to about 350 Å. In at least one embodiment, the support material is amorphous silica with a high surface area (surface area = 300 m²). 2 / gm; pore volume 1.65 cm³ 3 / gm). Non-limiting exemplary silica is sold by Davison Chemical Division of WRGrace and Company under the trade names DAVISON 952 or DAVISON 955. In other embodiments, DAVISON 948 is used.

[0209] The support material should be dry, i.e., free of absorbed water. Drying of the support material can be achieved by heating or calcining between about 100°C and about 1000°C, for example, at least about 600°C. When the support material is silica, it is heated to at least 200°C, for example, from about 200°C to about 850°C, for example, about 600°C; and sustained for about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material should have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present invention. The calcined support material is then contacted with at least one polymerization catalyst system comprising, for example, at least one catalyst compound and an activator.

[0210] A support material having reactive surface groups (typically hydroxyl groups) is slurried in a nonpolar solvent, and the resulting slurry is contacted with a solution of at least one catalyst compound (e.g., one or two catalyst compounds) and an activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Then, the solution of the catalyst compound is contacted with the separated support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In at least one embodiment, the slurry of the support material is first contacted with the catalyst compound for about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Then, the slurry of the supported catalyst compound is contacted with the activator solution.

[0211] The mixture of catalyst, activator and support can be heated to about 0°C to about 70°C, for example about 23°C to about 60°C, for example, room temperature. The contact time can be about 0.5 hours to about 24 hours, for example about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0212] Suitable nonpolar solvents are materials in which all reactants used herein, such as activators and catalyst compounds, are at least partially soluble and are liquids at the reaction temperature. Non-limiting examples of nonpolar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane; cycloalkanes, such as cyclohexane; and aromatic compounds, such as benzene, toluene, and ethylbenzene.

[0213] Aggregation methods

[0214] The embodiments described in this specification include polymerization methods in which monomers (e.g., ethylene or propylene) and optional comonomers are contacted with a catalyst system comprising at least one catalyst compound and an activator, as described above. The at least one catalyst compound and activator can be combined in any order and are typically combined prior to contact with the monomers.

[0215] Monomers that can be used in this invention include substituted or unsubstituted C2-C40. -Olefins, preferably C2-C20 -Olefins, preferably C2-C12 -Olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and their isomers. In a preferred embodiment, the olefin comprises a monomer, which is propylene, and one or more optional comonomers, said comonomers comprising one or more ethylene or C4-C40 olefins, preferably C4-C20 olefins, or preferably C6-C12 olefins. The C4-C40 olefin monomers may be linear, branched, or cyclic. The C4-C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may include one or more heteroatoms and / or one or more functional groups. In another preferred embodiment, the olefin comprises an ethylene monomer and optional comonomers, said comonomers comprising one or more C3 to C40 olefins, preferably C4 to C20 olefins, or preferably C6 to C12 olefins. The C3 to C40 olefin monomers may be linear, branched, or cyclic. C3 to C40 cyclic alkenes can be strained or unstrained, monocyclic or polycyclic, and can include heteroatoms and / or one or more functional groups.

[0216] Exemplary C2 to C40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxaindolediene, their substituted derivatives and isomers, 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 substituted derivatives, preferably norbornene, norbornadiene and dicyclopentadiene.

[0217] In at least one embodiment, one or more dienes are present in the polymer prepared herein at a maximum of about 10 wt%, for example, about 0.00001 to about 1.0 wt%, for example, about 0.002 to about 0.5 wt%, for example, about 0.003 to about 0.2 wt%, based on the total weight of the resin. In at least one embodiment, about 500 ppm or less of dienes are added to the polymer, for example, about 400 ppm or less, for example, about 300 ppm or less. In at least one embodiment, at least about 50 ppm of dienes, or about 100 ppm or more, or 150 ppm or more, are added to the polymer.

[0218] Diene monomers include any hydrocarbon structure having at least two unsaturated bonds, preferably C4 to C30, wherein the at least two unsaturated bonds are readily incorporated into the polymer by stereoregular or non-stereoregular catalysts. More preferably, the diene monomer is selected from... , - Diene monomer (i.e., divinyl monomer). In at least one embodiment, the diene monomer is a linear divinyl monomer, such as those containing 4 to 30 carbon atoms. Non-limiting examples of dienes include butadiene, pentadiene, hexadiene, heptadecadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, heptadecanadiene, octadecadiene, nonadecadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, heptadecadiene, heptadecadiene, icosadecanadiene, triadecadiene, and triadecadiene. 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). Non-limiting examples of cyclic dienes include cyclopentadiene, ethimide norbornene, norbornene, norbornene, divinylbenzene, dicyclopentadiene, or dienes containing higher rings with or without substituents at each ring position.

[0219] In at least one embodiment, when butene is a comonomer, the butene source can be a mixed butene stream comprising various butene isomers. 1-Butene monomer is expected to be preferentially consumed by the polymerization process compared to other butene monomers. Using such a mixed butene stream would offer economic benefits because these mixed streams are typically waste streams from refining processes, such as C4 raffinate streams, and are therefore much cheaper than pure 1-butene.

[0220] The polymerization methods described herein can be carried out in any suitable manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization method known in the art can be used. These processes can be operated in batch, semi-batch, or continuous modes. Homogeneous polymerization methods and slurry methods are preferred. (The homogeneous polymerization method is preferably one in which at least about 90 wt% of the product is soluble in the reaction medium). Bulk homogeneous methods are particularly preferred. (The bulk method is preferably a method in which the monomer concentration in all feeds to the reactor is 70 vol% or more). Alternatively, no solvent or diluent is present or added to the reaction medium (except for small amounts used as a carrier for the catalyst system or other additives, or amounts typically found in the monomer; e.g., propane in propylene). In another embodiment, the method is a slurry process. As used herein, the term "slurry polymerization method" refers to a polymerization method in which a supported catalyst is used and the monomer is polymerized on supported catalyst particles. At least 95 wt% of the polymer product derived from the supported catalyst is in the form of solid particles (insoluble in diluent). The method described herein may include introducing a first catalyst compound represented by formula (I) or formula (II) as a slurry into the reactor.

[0221] Suitable diluents / solvents for polymerization include noncoordinate inert liquids. Non-limiting 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, for example, those commercially available (Isopar). TM The solvent includes: fully halogenated hydrocarbons, such as perfluorinated C4 to C10 alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that can be used as monomers or comonomers, including but not limited to 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, an aliphatic hydrocarbon solvent is used as the solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, or mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, or mixtures thereof. In another embodiment, the solvent is not aromatic, and the amount of the aromatic compound in the solvent is less than about 1 wt%, for example less than about 0.5 wt%, for example about 0 wt% based on the weight of the solvent.

[0222] In at least one embodiment, based on the total volume of the feed stream, the feed concentration of the monomers and comonomers used for polymerization is about 60 vol% solvent or less, preferably about 40 vol% or less, or about 20 vol% or less. Preferably, the polymerization is carried out by a bulk method.

[0223] The polymerization reaction can preferably be carried out at any temperature and / or pressure suitable for obtaining the desired polyolefin. Typical temperatures and / or pressures include temperatures between about 0°C and about 300°C, for example between about 20°C and about 200°C, for example between about 35°C and about 150°C, 40°C and about 120°C, for example between about 45°C and about 80°C; and pressures between about 0.35 MPa and about 10 MPa, for example between about 0.45 MPa and about 6 MPa, or preferably between about 0.5 MPa and about 4 MPa.

[0224] In a typical polymerization reaction, the reaction run time is at most about 300 minutes, for example about 5 to about 250 minutes, for example about 10 to about 120 minutes.

[0225] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure between about 0.001 and 50 psig (0.007 to 345 kPa), for example between about 0.01 and about 25 psig (0.07 to 172 kPa), for example between about 0.1 and 10 psig (0.7 to 70 kPa).

[0226] In at least one embodiment, the polymer is prepared using little or no aluminoxane in the method. Preferably, the aluminoxane is present in zero molar percentage. Alternatively, the aluminoxane is present in a molar ratio of aluminum to the transition metal of the catalyst represented by formula (I) or (II) of less than about 500:1, for example less than about 300:1, for example less than about 100:1, for example less than about 1:1.

[0227] In a preferred embodiment, the polyolefin composition is prepared using little or no scavenger in the method. Preferably, the scavenger (e.g., trialkylaluminum) is present at 0 mol%. Alternatively, the scavenger is present in a molar ratio of the scavenger metal to the transition metal of the catalyst represented by formula (I) or (II) of less than about 100:1, for example less than about 50:1, for example less than about 15:1, for example less than about 10:1.

[0228] In a preferred embodiment, the polymerization is carried out at a temperature of 0 to 300°C (preferably 25 to 150°C, more preferably 40 to 120°C, more preferably 45 to 80°C); 2) at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, more preferably 0.45 to 6 MPa, more preferably 0.5 to 4 MPa); 3) in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof); cyclic or alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, or mixtures thereof; preferably wherein the aromatic compound is present in the solvent in an amount of less than 1 wt%, preferably less than 0.5 wt%, more preferably 0 wt%, based on the weight of the solvent); 4) wherein the catalyst system used in the polymerization contains less than 0.5 mol% of aluminum oxane, preferably 0 mol% of aluminum oxane. Alternatively, the aluminum oxane catalyst represented by formula (I) or formula (II) has a molar ratio of aluminum to transition metal of less than 500:1, preferably less than 300:1, more preferably less than 100:1, and more preferably less than 1:1; 5) polymerization is preferably carried out in one reaction zone; 6) the productivity of the catalyst compound is at least 80,000 g / mmol / hr (preferably at least 150,000 g / mmol / hr, more preferably at least 200,000 g / mmol / hr, more preferably at least 250,000 g / mmol / hr, and more preferably at least 300,000 g / mmol / hr); 7) optional scavengers (e.g., trialkylaluminum compounds) are absent (e.g., present at zero mol%). Alternatively, the scavenger is present in a scavenger metal to transition metal molar ratio of less than 100:1, preferably less than 50:1, more preferably less than 15:1, and more preferably less than 10:1; 8) optional hydrogen is present in a polymerization reactor at a molecular pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)). In a preferred embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A “reaction zone,” also called a “polymerization zone,” is the vessel in which polymerization occurs, such as a batch reactor. When multiple reactors are used in series or parallel configurations, each reactor is considered a separate polymerization zone. For multi-stage polymerization in batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, polymerization is carried out in one reaction zone.

[0229] Other additives may also be used in the polymerization as needed, such as one or more scavengers, accelerators, modifiers, chain transfer agents (such as diethylzinc), reducing agents, oxidizing agents, hydrogen, alkylaluminum or silanes.

[0230] The chain transfer agent can be an alkylaluminoxane, a compound represented by the formula AlR3, ZnR2 (where each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or isomers thereof) or a combination thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or a combination thereof.

[0231] Gas-phase polymerization: Typically, in fluidized bed processes for producing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed under reaction conditions in the presence of a catalyst. The gas stream is removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product is removed from the reactor, and new monomers are added to replace the monomers used in polymerization. (See, for example, U.S. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are incorporated herein by reference in their entirety.)

[0232] Slurry-phase polymerization: Slurry polymerization methods are typically operated at pressures ranging from 1 to approximately 50 atmospheres (15 psi to 735 psi, 103 kPa to 5068 kPa) or even higher, and at temperatures ranging from 0°C to approximately 120°C. In slurry polymerization, a suspension of solid granular polymer is formed in a liquid polymerization dilution medium to which monomers and comonomers, along with a catalyst, are added. The suspension, including the diluent, is removed intermittently or continuously from the reactor, where volatile components are separated from the polymer and optionally recycled back to the reactor after distillation. The liquid diluent used in the polymerization medium is typically an alkane having 3-7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under polymerization conditions. When propane is used as the medium, the method should be operated above the critical temperature and pressure of the reaction diluent. Hexane or isobutane media are preferred.

[0233] Polyolefin products

[0234] This specification also relates to catalyst compounds represented by formula (I) or formula (II) and polyolefin compositions, such as resins, prepared by the methods described herein.

[0235] In at least one embodiment, the method includes preparing a propylene homopolymer or propylene copolymer, such as propylene-ethylene and / or propylene- -Olefin (preferably C3-C20) copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers) with Mw / Mn greater than about 1, for example greater than about 2, for example greater than about 3, for example greater than about 4.

[0236] In at least one embodiment, the method includes preparing an olefin polymer, preferably a polyethylene and polypropylene homopolymer and copolymer, using a catalyst compound represented by formula (I) or formula (II). In at least one embodiment, the polymer prepared herein is a homopolymer or copolymer of ethylene, preferably having one or more C3 to C20 olefin comonomers (e.g., between about 0.5 and 20 mol%, for example between about 1 and about 15 mol%, for example between about 3 and about 10 mol%). The olefin comonomers may be C3 to C12. - An olefin monomer, such as one or more of propylene, butene, hexene, octene, decene, or dodecene, preferably propylene, butene, hexene, or octene. The olefin monomer can be ethylene or C4 to C12. - One or more of the following olefins, preferably ethylene, butene, hexene, octene, decene or dodecene, preferably ethylene, butene, hexene or octene.

[0237] In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably at least about 10 mol% hexene (comonomer content), for example at least about 15 mol% hexene.

[0238] The polymers produced herein may have a 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), and / or a Mw / Mn ratio between about 1 and about 40 (e.g., between about 1.2 and about 20, e.g., between about 1.3 and about 10, e.g., between about 1.4 and about 5, e.g., between about 1.5 and about 4, e.g., between about 1.5 and about 3).

[0239] In a preferred embodiment, the polymer prepared herein exhibits a single-peak or multi-peak molecular weight distribution, as determined by gel permeation chromatography (GPC). "Single-peak" means that the GPC trajectory has a single peak or inflection point. "Multi-peak" means that the GPC trajectory has at least two peaks or inflection points. An inflection point is the point where the sign of the second derivative of the curve changes (e.g., from negative to positive, or vice versa).

[0240] In a preferred embodiment, the compositional distribution width index (CDBI) of the polymer prepared herein is 50% or higher, preferably 60% or higher, and most preferably 70% or higher. CDBI is a measure of the monomer compositional distribution within the polymer chain and is measured by the method described in PCT Publication WO 93 / 03093, published February 18, 1993, particularly in columns 7 and 8, and in Wild et al., J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Patent 5,008,204, including ignoring fractions with a weight-average molecular weight (Mw) below 15,000 when determining the CDBI.

[0241] In another embodiment, the polymer prepared herein exhibits two peaks in a TREF measurement. Two peaks in a TREF measurement, as used in this specification and the appended claims, mean the presence of two distinct normalized ELS (evaporated mass light scattering) response peaks in a graph of the normalized ELS response (vertical or y-axis) versus elution temperature (horizontal or x-axis). Using the TREF method described below, the x-axis is heated from left to right. In this context, "peak" means the general slope of the graph changes from positive to negative as temperature increases. Between the two peaks is a local minimum, where the general slope of the graph changes from negative to positive as temperature increases. The "general trend" of the graph is intended to exclude multiple local minima and maxima that may occur at intervals of 2°C or less. Preferably, the two distinct peaks are separated by at least 3°C, more preferably by at least 4°C, and even more preferably by at least 5°C. Additionally, the two distinct peaks appear on the graph at temperatures above 20°C and below 120°C, where the elution temperature is 0°C or lower. This limitation avoids confusion with apparent peaks on low-temperature plots, which are caused by materials that remain soluble at the lowest elution temperature. Two peaks on such a plot indicate a bimodal compositional distribution (CD). TREF analysis was performed using a CRYSTAF-TREF 200+ instrument obtained from Polymer Char, SA, Valencia, Spain. A general description of the principles of TREF analysis and the specific equipment used is in Monrabal, B.; del Hierro, P. Anal. Bioanal. Chem. (2011) Vol. 399, p. 1557. If the above method does not show two peaks, an alternative TREF measurement method can be used, i.e., see B. Monrabal, “Crystallization Analysis Fractionation: A New Technique for the Analysis of Branching Distribution in Polyolefins,” Journal of Applied Polymer Science, Vol. 52, pp. 491–499 (1994).

[0242] blends

[0243] In at least one embodiment, the polymer (such as polyethylene or polypropylene) prepared in this application is mixed with one or more additional polymers before forming the film, molded part, or other article. Other useful polymers include polyethylene, isotactic polypropylene, high isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene, and / or butene, and / or hexene, polybutene, random copolymers of ethylene-vinyl acetate, LDPE, LLDPE, HDPE, ethylene-vinyl acetate, ethylene methyl acrylate, acrylic copolymers, polymethyl methacrylate or any other polymer that can be polymerized by high pressure free radicals, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene block copolymers, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0244] In at least one embodiment, a polymer (e.g., polyethylene or polypropylene) is present in the above blend in an amount between about 10 and about 99 wt%, based on the weight of the total polymer in the blend, for example, about 20-95 wt%, for example, about 30-90 wt%, for example, about 40-90 wt%, for example, about 50-90 wt%, for example, about 60-90 wt%, for example, about 70-90 wt%.

[0245] The blends described herein can be produced by mixing the polymers of this specification with one or more polymers (as described above), by connecting reactors in series to prepare reactor blends, or by using more than one catalyst in the same reactor to produce multiple polymers. The polymers can be mixed together before being fed into an extruder, or they can be mixed in the extruder.

[0246] The blends of the present invention can be formed using conventional equipment and methods, such as by dry mixing the individual components, such as polymers, followed by melt mixing in a mixer, or by directly mixing the components in a mixer, for example, for use in a mixture. Examples include Banbury mixers, Haake mixers, Brabender internal mixers, or single-screw or twin-screw extruders, which may include feed extruders and side-arm extruders used directly downstream of the polymerization process, and may include mixed powders or resin pellets in the hopper of a film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and / or, as needed, in the product formed from the blend, such as a film. These additives are well known in the art and may include, for example: fillers; antioxidants (e.g., hindered phenols such as IRGANOX available from Ciba-Geigy). TM 1010 or IRGANOXTM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy) TM 168); anti-blocking additives; tackifiers, such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearates, and hydrogenated rosin; UV stabilizers; heat stabilizers; antiblocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc; mixtures thereof, etc.

[0247] In at least one embodiment, the polyolefin composition, such as a resin, as a multimodal polyolefin composition, comprises low molecular weight fractions and / or high molecular weight fractions. The low molecular weight fraction may be a high-density fraction. The high molecular weight fraction may be a low-density fraction. In at least one embodiment, the high molecular weight fraction is generated by a catalyst compound represented by formula (I) or formula (II). As described above, the low molecular weight fraction can be generated by a second catalyst compound, which is a bridged or unbridged metallocene catalyst compound different from the catalyst compound represented by formula (I) or formula (II). The high molecular weight fraction may be polypropylene or polyethylene, such as linear low-density polyethylene, or copolymers thereof. The low molecular weight fraction may be polypropylene or polyethylene, or copolymers thereof.

[0248] In at least one embodiment, the high molecular weight fraction generated by the catalyst compound represented by formula (I) or formula (II) has a high comonomer content of about 10 wt% to about 20 wt%, for example about 11 wt% to about 20 wt%, for example about 12 wt% to about 18 wt%, for example about 13 wt% to about 16 wt%, for example about 14 wt% to about 16 wt%, for example about 15 wt%.

[0249] membrane

[0250] Any of the aforementioned polymers, such as the aforementioned polyethylene or blends thereof, can be used for a variety of end applications. These applications include, for example, single-layer or multi-layer blow molding, extrusion, and / or shrink films. These films can be formed using any suitable extrusion or co-extrusion technology, such as bubble film processing technology, in which the composition can be extruded in a molten state through an annular die before cooling to form a tubular blown film (which it may), then expanded to form a uniaxially or biaxially oriented melt, which can then be axially cut and unfolded to form a flat film. The film can subsequently be unoriented, uniaxially oriented, or biaxially oriented, with the degree of orientation being the same or different. One or more layers of the film can be oriented to the same or different degrees in the transverse and / or longitudinal directions. Uniaxial orientation can be accomplished using typical cold stretching or hot stretching methods. Biaxial orientation can be accomplished using tenter frame equipment or a twin-bubble process and can be performed before or after the individual layers are laminated together. For example, a polyethylene layer can be extruded, coated, or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be co-extruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated onto oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and optionally, the combination can be further oriented. Typically, the film is oriented in the machine direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the transverse direction (TD) at a ratio of up to 15, preferably between 7 and 9. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions.

[0251] The depth of the film can vary depending on the intended application; however, depths ranging from 1 to 50 μm are common. A film of 10 to 50 μm might be suitable. Films used for packaging are typically 10 to 50 μm in size. The depth of the sealing layer is typically 0.2 to 50 m. m. A sealing layer may be present on both the inner and outer surfaces of the membrane, or the sealing layer may exist only on the inner or outer surface.

[0252] In another implementation, corona treatment or electron beam radiation can be used. Radiation, flame treatment, or microwaves can be used to modify one or more layers. In a preferred embodiment, one or two surface layers are modified by corona treatment.

[0253] test

[0254] The following abbreviations can be used as follows: eq. refers to equivalent.

[0255] Melt index (MI), also known as I2, is reported in dg / min and is determined according to ASTM D1238, 190°C, 2.16 kg load.

[0256] High load melt index (HLMI), also known as I 21Reported in dg / min, measured according to ASTM D1238, 190°C, 21.6 kg load.

[0257] Melt index ratio (MIR) is MI divided by HLMI, determined by ASTM D1238.

[0258] Unless otherwise specified, all reagents were purchased from Sigma Aldrich (St. Louis, MO) and used as obtained. All solvents were anhydrous. Unless otherwise specified, all reactions were carried out under an inert nitrogen atmosphere. All deuterated solvents were obtained from Cambridge Isotopes (Cambridge, MA) and dried with 3 Å molecular sieves before use.

[0259] The product characteristics are as follows:

[0260] 1 H NMR

[0261] Unless otherwise specified, data are collected at room temperature using a Bruker NMR spectrometer with a 5 mm probe. 1 H NMR data, this spectrometer operates at 400 or 500 MHz. 1 H frequency operation. Use 30. Data were recorded using RF pulses with a rotation angle, 8 scans, and a 5-second delay between pulses. Samples were prepared using approximately 5–10 mg of the compound dissolved in approximately 1 mL of a suitable deuterated solvent, as listed in the experimental examples. The residual protons of the sample relative to the reference solvent were 7.15, 7.24, 5.32, 5.98, and 2.10, respectively, for D5-benzene, chloroform, D-dichloromethane, D-1,1,2,2-tetrachloroethane, and C6D5CD2H. Unless otherwise specified, NMR spectral data of the polymer were recorded in a 5 or 10 mm probe on the spectrometer at 120 °C using a solution of approximately 20 mg of the polymer and 1 mL of d2-1,1,2,2-tetrachloroethane. Unless otherwise specified, a 30% NMR solution was used. Data is recorded using RF pulses at the slewing angle, with 120 scans and a 5-second delay between pulses.

[0262] Unless otherwise specified, all reactions were carried out in a glovebox purged with inert N2. All anhydrous solvents were purchased from Fisher Chemical and degassed and dried on molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried on molecular sieves before use. n-Butyllithium (2.5M hexane solution), methyl magnesium bromide (3.0M diethyl ether solution), dichloromethylsilane (Me(H)SiCl2) and dichlorophenylsilane (Ph(H)SiCl2) were purchased from Sigma-Aldrich, and hafnium tetrachloride (HfCl4) 99+% was purchased from Strem Chemicals and used as is. Lithium-n-propylcyclopentadiene was obtained from Boulder Scientific.

[0263] Example of carrier preparation:

[0264] Silica support (sMAO): Silica (Grace Davison D948, 40.7 g) was calcined at 600 °C and then slurried in 200 mL of toluene. MAO (71.4 g in 30 wt% toluene solution, 351.1 mmol of Al) was slowly added to the slurry. The slurry was then heated to 80 °C and stirred for 1 hour. The slurry was filtered, washed three times with 70 mL of toluene, and once with pentane. The solid was vacuum dried overnight to obtain 60.7 g of free-flowing white solid.

[0265] Alternatively, a fluorinated support can be used as a support. A fluorinated support can be prepared as follows:

[0266] Fluorinated silica support (F-sMAO): 1.18 g of (NH4)2SiF6 dissolved in 7.00 g of water in a 20 ml glass vial. 50 g of silica (Grace Davison D948) and 200 g of toluene in 250 ml Celstil. TM Mixing was performed. An aqueous solution of (NH4)2SiF6 was added to the toluene slurry via a syringe under vigorous stirring. The mixture was stirred at room temperature for 2.5 hours. The emulsion slurry was filtered through 500 ml of Optichem disposable polyethylene glass frit (40 μm), washed three times with 200 g of pentane, and then air-dried overnight to obtain a white, free-flowing solid. The solid was transferred to a tube furnace and heated to 200 °C under a constant nitrogen flow (temperature program: 25 °C / h to 150 °C; hold at 150 °C for 4 hours; 50 °C / h to 200 °C; hold at 200 °C for 4 hours; cool to room temperature). 46 g of fluorinated silica was collected after calcination. Calculated F-loading: 0.8 mmol / g (F-loading = mmol F / g added raw silica).

[0267] MAO (37.6 g, 30% wt toluene solution) was added together with 100 mL of toluene into a 250 mL Celstir flask. 29.9 g of fluorinated silica prepared in the previous step was added to the slurry in increments of 5 g. The reaction was stirred at room temperature for 10 minutes, then heated to 100 °C and held for 3 hours. The solid was filtered, washed twice with 80 mL of toluene, twice with pentane, and dried under vacuum overnight. 39.6 g of free-flowing white solid was collected.

[0268] Examples of the preparation of supported catalysts:

[0269] Silica-supported catalyst

[0270] In a 20 ml glass vial, combine sMAO (0.495 g) and toluene (3.0 g). Transfer the catalyst (18.8 g) represented by formula (I) or formula (II) to a separate vial using a pipette. Add 1.0 g of toluene solution (mol) to a glass vial. Cap the vial with a Teflon-lined cap and rotate at high speed for approximately 90 minutes at room temperature. Filter the resulting slurry through 18 mL of polyethylene glass frit (10 microns) and rinse with toluene (2 mol) solution. Rinse with 3g, then rinse with pentane (3g) Wash three times with 1.4 g of the sample. Dry the collected solid under vacuum for approximately 40 minutes. Recover the supported catalyst. Calculate the catalyst loading: 38 mol / g (catalyst loading = (mol catalyst / gram of added sMAO).

[0271] Fluorinated silica supported catalyst

[0272] In a 20 ml glass vial, combine F-sMAO (0.493 g) and toluene (0.493 g). Add the catalyst (18.8 g) represented by formula (I) or formula (II). A 1.0 g toluene solution (mol) was added to a glass vial via pipette. The remaining steps of the preparation were essentially the same as those described above for the silica-supported catalyst. The catalyst supported on fluorinated silica was collected. The catalyst loading was calculated: 38 mol / g.

[0273]

[0274] Synthesis of bis(n-propylcyclopentadiene)methylsilane Me(H)Si(n-PrCpH)2: Pure Me(H)SiCl2 (20.0 g, 173.9 mmol) was dissolved in 300 mL of THF and cooled to -25 °C. Solid lithium-n-propylcyclopentadiene (40.08 g, 351.2 mmol) was slowly added over 10–15 minutes. The resulting mixture was stirred at room temperature for 18 hours. The volatiles in the reaction mixture were removed under vacuum and further ground with hexane. The crude material was then extracted into hexane, and the solvent was removed to give a deep orange-yellow Me(H)Si(n-PrCpH)2 oil along with 0.5 equivalents of hexane, in a yield of 50.08 g (95.5%).

[0275] Synthesis of bis(n-propylcyclopentadiene)methylsilane lithium Me(H)Si(n-PrCp)2Li2: Pure Me(H)Si(n-PrCpH)2 0.5 g of hexane (58.08 g, 166.1 mmol) was dissolved in 400 mL of THF and cooled to -25 °C. A hexane solution of n-butyllithium (134.2 mL, 335.5 mmol, 2.02 equivalents) was added over 45–60 minutes. The resulting mixture was gradually warmed to room temperature and stirred continuously for 18 hours. Volatile substances in the reaction mixture were removed under vacuum and milled with hexane to evaporate trace amounts of THF. The crude material was thoroughly washed with hexane to remove any soluble impurities and dried under vacuum to give a grayish-white solid, Me(H)Si(n-PrCp)₂Li₂, in a yield of 44.8 g (99.8%).

[0276] Synthesis of racemic-meta-methylsilyl-bis(n-propylcyclopentadiene)hafnium dichloride, Me(H)Si(n-PrCp)₂HfCl₂: Solid Me(H)Si(n-PrCp)₂Li₂ (49.52 g, 183.2 mmol) was slurried in 600 mL of diethyl ether and cooled to -25 °C. Solid HfCl₄ (58.584 g, 183.2 mmol) was added over 15–20 minutes. The resulting mixture was stirred at room temperature for 48 hours. Insoluble matter was filtered through a diatomaceous earth filter, and volatiles were removed under vacuum to obtain a yellow-red oily substance of Me(H)Si(n-PrCp)₂HfCl₂, yielding 87.2 g (94.1%). Due to the asymmetric chemical environment of the silicon center, the final material… 1 1H NMR spectra revealed a variety of meso / racemic isomers.

[0277] Catalyst 1: Synthesis of meso-racemic-methylsilyl-bis(n-propylcyclopentadienyl)dimethylhafnium, Me(H)Si(n-PrCp)2HfMe2: Pure Me(H)Si(n-PrCp)2HfCl2 (87.188 g, 172.4 mmol) was dissolved in 600 mL of diethyl ether and cooled to -25 °C. An ether solution of MeMgBr (116.1 mL, 348.2 mmol) was added over 45–60 minutes. The resulting mixture was gradually brought to room temperature and continuously stirred for 18 hours. Volatiles were removed under vacuum and the mixture was ground with hexane. The crude material was extracted into hexane and the solvent removed to give a dark brownish-yellow Me(H)Si(n-PrCp)2HfMe2, in a yield of 72.3 g (90.2%). Due to the asymmetric chemical environment at the chiral silicon atoms, the final material… 1 1H NMR spectra revealed a variety of meso / racemic isomers.

[0278] Synthesis of bis(n-propylcyclopentadiene)phenylsilane, Ph(H)Si(n-PrCpH)2: Pure Ph(H)SiCl2 (2.0 g, 11.29 mmol) was dissolved in 20 mL of THF and cooled to -25 °C. Solid lithium-n-propylcyclopentadiene (2.60 g, 22.81 mmol) was slowly added over 3–5 minutes. The resulting mixture was stirred overnight at room temperature to ensure complete reaction. The volatiles in the reaction mixture were removed under vacuum and further ground with hexane. The crude material was then extracted into hexane, and the solvent was removed to give a viscous, orange-yellow oil, Ph(H)Si(n-PrCpH)2, in a yield of 3.41 g (94.3%).

[0279] Synthesis of lithium bis(n-propylcyclopentadiene)phenylsilane Ph(H)Si(n-PrCp)₂Li₂: Pure Ph(H)Si(n-PrCpH)₂ (3.41 g, 10.64 mmol) was dissolved in 30 mL of THF and cooled to -25 °C. A hexane solution of n-butyllithium (8.6 mL, 21.5 mmol, 2.02 equivalents) was added over 5–10 minutes. The resulting mixture was gradually warmed to room temperature and continuously stirred for 18 hours. Volatile substances in the reaction mixture were removed under vacuum, and the mixture was milled with pentane to evaporate trace amounts of THF. The crude material was thoroughly washed with pentane to remove any soluble impurities and dried under vacuum to give a grayish-white solid of Ph(H)Si(n-PrCp)₂Li₂ in yield of 3.68 g, with trace amounts of pentane (100%).

[0280] Synthesis of racemic-meta-phenylsilyl-bis(n-propylcyclopentadiene) hafnium dichloride, Ph(H)Si(n-PrCp)₂HfCl₂: Solid Ph(H)Si(n-PrCp)₂Li₂ (3.68 g, 11.1 mmol) was slurried in 60 mL of diethyl ether and cooled to -25 °C. Solid HfCl₄ (3.54 g, 11.1 mmol) was added over 3–5 minutes. The resulting mixture was stirred at room temperature for 18 hours. Insoluble matter was filtered through diatomaceous earth, and volatiles were removed under vacuum to obtain a pale yellow semi-solid Ph(H)Si(n-PrCp)₂HfCl₂ in yield of 5.91 g (93.8%). Due to the asymmetric chemical environment of the silicon center, the final material… 1 H NMR spectra revealed a variety of racemic isomers, both exonucleo and racemic.

[0281] Catalyst 2: Synthesis of racemic-meta-phenylsilyl-bis(n-propylcyclopentadiene)dimethylhafnium, Ph(H)Si(n-PrCp)2HfMe2: Pure Ph(H)Si(n-PrCp)2HfCl2 (5.91 g, 10.4 mmol) was dissolved in 60 mL of diethyl ether and cooled to -25 °C. An ether solution of MeMgBr (7.0 mL, 21.1 mmol) was added over 5–10 minutes. The resulting mixture was gradually brought to room temperature and stirred continuously for 18 hours. Volatiles were removed under vacuum and the mixture was ground with pentane. The crude material was extracted into pentane and the solvent removed to obtain a dark brownish-yellow Ph(H)Si(n-PrCp)2HfMe2 oil, yield 4.88 g (89.1%). Due to the asymmetric chemical environment at the chiral silicon atoms, the final material… 1 1H NMR spectra revealed a variety of racemic / mesomeric isomers.

[0282] Synthesize trimethylsilylmethylcyclopentadiene, (Me3SiCH2)CpH. Dissolve pure trimethylsilylmethyltrifluoromethanesulfonate (25.0 g, 105.8 mmol) in 300 mL of diethyl ether and cool to -25 °C. Slowly add solid potassium cyclopentadiene (11.14 g, 106.9 mmol) to the solution over 10–15 minutes. Stir the resulting mixture overnight at room temperature. Filter out the insoluble material. Carefully remove the volatiles from the reaction mixture under dynamic vacuum to avoid evaporating volatile trimethylsilylmethylcyclopentadiene (Me3Si)CH2CpH. Weigh the reaction flask (250 mL round-bottom flask) and the glass feed containing diatomaceous earth to calculate the yield of the extracted product. Then extract the crude material into pentane (3... It can be used directly in 50 mL of solution without further purification. Based on the above calculation method, the yield is calculated to be 15.47 g (95.2%). Record the raw material... 1 ¹H NMR spectroscopy is used to ensure product formation.1 H NMR (400 MHz, C6D6): δ-0.05 (9H, s, Si-C H 3), 1.77 (2H, d, J) HH =1.2 Hz, Me3Si-C H 2), 2.83 (1H, sex, J) HH =1.5 Hz, Cp-C H ), 5.80-6.49 (4H, m, Cp-C H ) ppm.

[0283] Trimethylsilylmethylcyclopentadiene lithium, Me3SiCH2CpLi, was synthesized. A hexane solution of n-butyllithium (41.5 mL, 103.8 mmol, 2.5 M) was added dropwise to a pre-cooled solution of Me3SiCH2CpLi (15.47 g, 101.7 mmol) in pentane and diethyl ether (200 mL) at -25 °C for 40–50 min. The resulting mixture was gradually brought to room temperature and then stirred continuously overnight. All volatiles in the reaction mixture were removed under vacuum, and the crude material was then thoroughly washed with pentane. Vacuum-dried Me3SiCH2CpLi material was obtained as a colorless crystalline solid in a yield of 13.6 g (84.6%). 1 H NMR (400 MHz, THF-) d 8): δ-0.09 (9H, s, Si-C) H 3), 1.84 (2H, s, Me3Si-C) H 2), 5.36 (2H, t, J) HH =2.6 Hz, Cp-C H ), 5.47 (2H, t, J HH =2.6 Hz, Cp-C H ) ppm.

[0284] Synthesized bis(trimethylsilylmethylcyclopentadiene)methylsilane, Me(H)Si(Me3SiCH2CpH)2. Solid Me3SiCH2CpLi (5.51 g, 34.9 mmol) was added to a pre-cooled THF (100 mL) solution of Me(H)SiCl2 (2.01 g, 17.4 mmol) at -25 °C. The resulting mixture was stirred overnight at room temperature. All volatiles in the reaction mixture were removed under vacuum and the mixture was ground with pentane. The crude material was then extracted into pentane, followed by solvent removal under vacuum, yielding a concentrated yellow viscous oil of Me(H)Si(Me3SiCH2CpH)2, 5.9 g (97.4%). 1H NMR (400 MHz, C6D6): δ0.02-(-)0.10 (21H, m, Si-C H 3 and Si-C H 3), 1.79-1.86 (4H, m, Me3Si-C H 2), 3.31-3.69 (2H, broad multi-peaked, Cp-C H ), 4.25 (1H, bs, Si- H ), 6.03-6.89 (6H, m, Cp-C H ) ppm.

[0285] Synthesize lithium bis(trimethylsilylmethylcyclopentadiene)methylsilane, Me(H)Si(Me3SiCH2Cp)2Li2. A hexane solution of n-butyllithium (13.72 mL, 34.3 mmol, 2.5 M) was added dropwise to a pre-cooled solution of Me(H)Si(Me3SiCH2CpH)2 (5.9 g, 17.0 mmol) in 100 mL of THF over 25–30 minutes at -25 °C. The resulting mixture was gradually warmed to room temperature and then stirred continuously overnight. All volatiles in the reaction mixture were removed under vacuum, and the mixture was ground with pentane. The crude material was thoroughly washed with pentane to remove any soluble impurities and dried under vacuum to give a colorless crystalline solid of Me(H)Si(Me3SiCH2Cp)2Li2, 3.2 g (52.3%). 1 H NMR (400 MHz, THF-) d 8): δ-0.05-(-)0.06 (18H, m, Si-C H 3), 0.22-0.32 (3H, m, Si-C) H 3), 1.90 (4H, s, Me3Si-C) H 2), 4.89-4.99 (1H,m,Si- H ), 5.51-5.60 (2H,m,Cp-C H ), 5.66-5.74 (2H, m, Cp-C H ), 5.82-5.86 (2H,m,Cp-C H ) ppm.

[0286] Racemic methylsilylbis(trimethylsilylmethylcyclopentadiene) hafnium dichloride, Me(H)Si(Me3SiCH2Cp)2HfCl2, was synthesized. Solid HfCl4 (2.818 g, 8.81 mmol) was added to a pre-cooled ether (50 mL) solution of Me(H)Si(Me3SiCH2Cp)2Li2 (3.16 g, 8.81 mmol) at -25 °C. The resulting mixture was stirred overnight at room temperature. Insoluble substances were filtered off, and volatiles in the filtrate were removed under vacuum. The resulting substance was dried under vacuum to give a yellow crystalline solid of Me(H)Si(Me3SiCH2Cp)2HfCl2, in yield of 4.9 g (93.6%). Due to the asymmetric chemical environment of the silicon centers, the final material... 1 H NMR spectra revealed a variety of racemic isomers, both exonucleo and racemic. 1 H NMR (400MHz, CD2Cl2): δ-0.02-(-)0.04(18H,m,Si-C H 3), 0.62-0.80 (3H, m, Si-C) H 3), 2.08-2.21 (4H, m, Me3Si-C H 2), 5.00-5.11 (1H, m, Si- H ), 5.15-5.41 (2H,m,Cp-C H ), 5.64-5.90 (2H, m, Cp-C) H ), 6.18-6.37 (2H, m, Cp-C H ) ppm.

[0287] Catalyst 3: Synthesis of racemic methylsilyl-bis(trimethylsilylmethylcyclopentadiene)dimethylhafnium, Me(H)Si(Me3SiCH2Cp)2HfMe2. At -25°C, an ether solution of MeMgBr (5.6 mL, 16.66 mmol) was added dropwise to a pre-cooled ether solution of Me(H)Si(Me3SiCH2Cp)2HfCl2 (4.9 g, 8.3 mmol) over 10–15 minutes. The resulting mixture was stirred overnight at room temperature to ensure complete reaction. Insoluble matter was filtered through a diatomaceous earth-filled glass frit. All volatiles in the filtrate were removed under vacuum, and the crude material was then extracted into pentane. The solvent was removed under vacuum to give a viscous yellow substance of Me(H)Si(Me3SiCH2Cp)2HfMe2, 4.0 g (87.1%) yield. Due to the asymmetric chemical environment of the silicon center, the final material… 1 H NMR spectra revealed a variety of racemic isomers, both exonucleo and racemic. 1H NMR (400 MHz, C6D6): δ-0.17-(-)0.25 (6H,m, Hf-C H 3), 0.02-0.05 (18H, m, Si-C H 3), 0.18-0.26(3H,m,Si-C) H 3), 2.04-2.12(4H,m,Me3Si-C H 2), 4.68-4.79 (1H,m,Si- H ), 4.98-5.60 (4H, m, Cp-C) H ), 6.22-6.30 (2H, m, Cp-C) H ) ppm.

[0288] Bis(trimethylsilylmethylcyclopentadiene)phenylsilane, Ph(H)Si(Me3SiCH2CpH)2, was synthesized. Solid Me3SiCH2CpLi (746 mg, 4.72 mmol) was added to a pre-chilled THF (15 mL) solution of Ph(H)SiCl2 (418 mg, 2.36 mmol) at -25 °C. The resulting mixture was stirred overnight at room temperature. All volatiles in the reaction mixture were removed under vacuum and the mixture was ground with pentane. The crude material was then extracted into pentane, followed by solvent removal under vacuum to give a deep yellow, viscous, oily Ph(H)Si(Me3SiCH2CpH)2 in 610 mg (64.0%). 1 H NMR (400MHz, C6D6): δ-0.07-0.02 (18H, m, Si-C H 3), 1.78 (4H, broad bimodal, Me3Si-C) H 2), 3.03 (1H, broad bimodal, Cp-C H ), 3.80 (1H, broad bimodal, Cp-C H ), 4.56 (1H, broad bimodal, Si- H ), 5.58-6.98 (6H, broad multi-peak, Cp-C H ), 7.17-7.21 (3H, m, Ar-C) H ), 7.57 (2H, broad bimodal, Ar-C) H ) ppm.

[0289] Synthesis of lithium bis(trimethylsilylmethylcyclopentadiene)phenylsilane, Ph(H)Si(Me3SiCH2Cp)2Li2. A hexane solution of n-butyllithium (1.18 mL, 2.95 mmol, 2.5 M) was added dropwise to a pre-cooled solution of Ph(H)Si(Me3SiCH2Cp)2 (593 mg, 1.46 mmol) in 10 mL of THF at -25 °C for 2–3 minutes. The resulting mixture was gradually warmed to room temperature and then stirred continuously overnight. All volatiles in the reaction mixture were removed under vacuum and the mixture was ground with pentane. The crude material was thoroughly washed with pentane to remove any soluble impurities and dried under vacuum to give a colorless crystalline solid Ph(H)Si(Me3SiCH2Cp)2Li2 in a yield of 350 mg (57.0%). 1 H NMR (400 MHz, THF- d 8):δ-0.04 (18H, s, Si-C) H 3), 1.90-1.92 (4H, m, Me3Si-C H 2), 5.34-5.42 (1H, m, Si- H ), 5.52-5.64 (2H, m, Cp-C H ), 5.81-5.87 (2H, m, Cp-C H ), 5.93-5.97 (2H, m, Cp-C H ), 7.03-7.14 (3H, m, Ar-C H ), 7.58-7.67 (2H, m, Ar-C) H ) ppm.

[0290] Racemic phenylsilyl-bis(trimethylsilylmethylcyclopentadiene) hafnium dichloride, Ph(H)Si(Me3SiCH2Cp)2HfCl2, was synthesized. Solid HfCl4 (213 mg, 0.67 mmol) was added to a pre-cooled ether (10 mL) solution of Ph(H)Si(Me3SiCH2Cp)2Li2 (280 mg, 0.67 mmol) at -25 °C. The resulting mixture was stirred overnight at room temperature. Insoluble substances were filtered off, and volatiles in the filtrate were removed under vacuum. The resulting material was dried under vacuum to give a yellow crystalline solid Ph(H)Si(Me3SiCH2Cp)2HfCl2, with a yield of 366 g (83.2%). Due to the asymmetric chemical environment at the silicon bridge atoms, the final material… 1 H NMR spectra revealed a variety of racemic isomers, both exonucleo and racemic. 1 H NMR (400 MHz, CD2Cl2): δ-0.04-0.05 (18H, m, Si-CH 3), 1.97-2.25 (4H, m, Me3Si-C H 2), 5.05-5.30 (1H, m, Si- H ), 5.42-6.43 (6H, m, Cp-C) H ), 7.48-7.61 (3H, m, Ar-C) H ), 7.82-7.98 (2H, m, Ar-C) H ) ppm.

[0291] Catalyst 4: Synthesis of racemic phenylsilyl-bis(trimethylsilylmethylcyclopentadiene)dimethylhafnium, Ph(H)Si(Me3SiCH2Cp)2HfMe2. At -25°C, an ether solution of MeMgBr (0.4 mL, 1.13 mmol) was added dropwise to a pre-cooled ether solution of Ph(H)Si(Me3SiCH2Cp)2HfCl2 (366 mg, 0.56 mmol) over 2–3 minutes. The resulting mixture was stirred overnight at room temperature to ensure complete reaction. Insoluble matter was filtered through a diatomaceous earth-filled pipette filter pad. All volatiles in the filtrate were removed under vacuum, and the crude material was then extracted into pentane. The solvent was removed under vacuum to give a viscous yellow substance, Ph(H)Si(Me3SiCH2Cp)2HfMe2, in a yield of 280 mg (81.3%). Due to the asymmetric chemical environment at the silicon bridge atoms, the final material… 1 H NMR spectra revealed a variety of racemic isomers, both exonucleo and racemic. 1 H NMR (400 MHz, C6D6): δ-0.34-(-)0.15 (6H, m, Hf-C H 3), 0.01-0.08 (18H, m, Si-C H 3), 1.85-2.21 (4H, m, Me3Si-C H 2), 4.96-5.07 (1H, m, Si- H ), 5.21-5.82 (4H, m, Cp-C H ), 6.18-6.39 (2H, m, Cp-C H ), 7.13-7.15 (1H, m, Ar-C) H ), 7.18-7.26 (2H, m, Ar-C) H ), 7.71-7.94 (2H, m, Ar-C) H ) ppm.

[0292] Synthesized chloromethyl (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)silane, Me(H)Si(Me4CpH)Cl. Pure Me(H)SiCl2 (5.0 g, 43.5 mmol) was dissolved in 60 mL of THF and cooled to -25 °C. Solid Me4Cp-Li (5.57 g, 43.5 mmol) was added to the mixture, and the resulting mixture was stirred overnight at room temperature. All volatiles in the reaction mixture were removed under vacuum, and the mixture was ground with pentane. The crude material was then extracted into pentane, followed by solvent removal under vacuum to give a deep yellow Me(H)Si(Me4CpH)Cl oil, yielding 8.4 g (96.7%). 1 H NMR (400 MHz, C6D6): δ-0.15 (0.7H, d, J HH =3.7 Hz, Si-C H 3), -0.06 (2.3H, d, J) HH =2.9 Hz, Si-C H 3), 1.68 (2H, s, Cp-C) H 3), 1.70 (2H, s, Cp-C) H 3), 1.81 (4H, s, Cp-C) H 3), 1.94 (1H, s, Cp-C) H 3), 1.97 (3H, s, Cp-C) H 3), 2.79 (0.4H, bs, Cp-C) H ), 2.96 (0.6H, bs, Cp-C H ), 4.03-4.06 (0.2H, m, Si- H ), 4.89 (0.8H, bs, Si- H ) ppm.

[0293] Synthesized methyl(2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)((trimethylsilyl)methylcyclopentadien)silane, Me(H)Si(Me4CpH)(Me3SiCH2CpH). Solid Me3SiCH2CpLi (500 mg, 3.2 mmol) was added to a pre-cooled ether solution of Me(H)Si(Me4CpH)Cl (632 mg, 3.2 mmol) at -25 °C. The resulting mixture was stirred overnight at room temperature to ensure complete reaction. The volatiles in the reaction mixture were removed under vacuum and ground together with pentane. The crude material was extracted into pentane, and then the solvent was removed under vacuum to give a deep yellow Me(H)Si(Me4CpH)(Me3SiCH2CpH) oil in a yield of 590 mg (56.8%). 1H NMR (400 MHz, C6D6): δ-0.04 (1.3H, s, Si-C H 3), -0.01 (1.7H, s, Si-C) H 3), 0.04 (9H, s, Si-C) H 3), 1.80 (3H, s, Cp-C) H 3), 1.82 (3H, s, Cp-C) H 3), 1.91 (3H, s, Cp-C) H 3), 1.94 (2H, s, Me3Si-C) H 2), 1.97 (3H, s, Cp-C) H 3), 3.25 (1H, bs, Cp-C) H ), 3.64 (1H, bs, Cp-C) H ), 4.67-4.72 (1H, m, Si- H ), 6.01-6.79 (3H, m, Cp-C) H ) ppm.

[0294] Synthesis of lithium methylsilyl-(tetramethylcyclopentadiene)(trimethylsilylmethylcyclopentadiene), Me(H)Si(Me4Cp)(Me3SiCH2Cp)Li2. A hexane solution of n-butyllithium (1.5 mL, 3.68 mmol, 2.5 M) was added dropwise over 2–3 minutes at -25 °C to a pre-cooled solution of Me(H)Si(Me4Cp)(Me3SiCH2Cp) (576 mg, 1.82 mmol) in 10 mL of THF. The resulting mixture was gradually warmed to room temperature and then stirred continuously overnight. All volatiles in the reaction mixture were removed under vacuum, and the mixture was ground together with pentane. The crude material was thoroughly washed with pentane to remove any soluble impurities and dried under vacuum to give a colorless crystalline solid of Me(H)Si(Me4Cp)(Me3SiCH2Cp)Li2 in a yield of 590 mg (98.7%). 1 H NMR (400 MHz, THF-) d 8): δ-0.10 (9H, s, Si-C) H 3), 0.36 (3H, d, J) HH =3.5 Hz, Si-C H 3), 1.69 (2H, bs, Me3Si-C) H 2), 1.86 (6H, s, Cp-C) H 3), 2.04 (6H, s, Cp-C) H 3), 4.96 (1H, q, J) SiH=3.9 Hz, Si- H ), 5.48 (1H, t, J HH =2.3 Hz, Cp-C H ), 5.60 (1H, t, J HH =2.0 Hz, Cp-C H ), 5.68 (1H, t, J HH =2.3Hz, Cp-C H ) ppm.

[0295] Synthesized methylsilyl-(tetramethylcyclopentadiene)(trimethylsilylmethylcyclopentadiene)hafnium dichloride, Me(H)Si(Me4Cp)(Me3SiCH2Cp)HfCl2. Solid HfCl4 (574 mg, 1.8 mmol) was added to a pre-cooled ether solution (10 mL) of Me(H)Si(Me4Cp)(Me3SiCH2Cp)Li2 (590 mg, 1.8 mmol) at -25 °C. The resulting mixture was stirred overnight at room temperature. Insoluble matter was filtered off, and volatiles in the filtrate were removed under vacuum. The crude material was washed with cold pentane to remove soluble impurities. The resulting material was dried under vacuum to give a pale yellow crystalline solid of Me(H)Si(Me4Cp)(Me3SiCH2Cp)HfCl2, in a yield of 480 mg (47.5%). 1 H NMR (400 MHz, CD2Cl2): δ-0.31 (9H, s, Si-C H 3), 0.63 (1.5H, s, Si-C) H 3), 0.64 (1.5H, s, Si-C) H 3), 1.69 (2H, s, Me3Si-C) H 2), 1.73 (3H, s, Cp-C) H 3), 1.76 (5H, overlapping single peaks, Cp-C H 3), 1.81 (4H, overlapping singlet, Cp-C H 3), 4.77-4.81 (1H, m, Si- H ), 4.95-5.05 (2H, m, Cp-C H ), 6.02-6.09 (1H, m, Cp-C) H ) ppm.

[0296] Catalyst 5: Synthesis of methylsilyl-(tetramethylcyclopentadiene)(trimethylsilylmethylcyclopentadiene)dimethylhafnium, Me(H)Si(Me4Cp)(Me3SiCH2Cp)HfMe2. An ether solution of MeMgBr (0.58 mL, 1.73 mmol) was added dropwise to a pre-cooled ether solution of Me(H)Si(Me4Cp)(Me3SiCH2Cp)HfCl2 (480 mg, 0.86 mmol) at -25 °C for 5–10 minutes. The resulting mixture was stirred overnight at room temperature to ensure complete reaction. All volatiles in the reaction mixture were removed under vacuum, and the crude product was then extracted into pentane. The solvent was removed under vacuum to give a viscous yellow substance of Me(H)Si(Me4Cp)(Me3SiCH2Cp)HfMe2 in a yield of 280 mg (62.2%). 1 H NMR (400 MHz, C6D6): δ-0.48-0.43 (6H, m, Hf-C H 3), -0.02 (9H, s, Si-C) H 3), 0.04-0.43 (3H, m, Si-C) H 3), 1.71 (2H, s, Me3Si-C) H 2), 1.82 (3H, s, Cp-C) H 3), 1.97-2.05 (9H, m, Cp-C) H 3), 4.94-5.01 (1H, m, Si- H ), 5.08 (1H, t, J HH =2.3 Hz, Cp-C H ), 5.27 (1H, t, J HH =2.6 Hz, Cp-C H ), 6.27 (1H, m, Cp-C H )ppm.

[0297] Synthesis of methylsilyl-(tetramethylcyclopentadiene)(trimethylsilylmethylcyclopentadiene)zirconium dichloride, 0.5-dimethoxyethane complex, Me(H)Si(Me4Cp)(Me3SiCH2Cp)ZrCl2 0.5 dme. At -25 °C, solid ZrCl4 (dme) (669 mg, 2.1 mmol) was added to a pre-cooled ether solution (30 mL) of Me(H)Si(Me4Cp)(Me3SiCH2Cp)Li2 (680 mg, 2.1 mmol). The resulting mixture was stirred overnight at room temperature. The solvent was removed under vacuum, and then extracted into diethyl ether. The resulting substance was dried under vacuum to give Me(H)Si(Me4Cp)(Me3SiCH2Cp)ZrCl2. A pale yellow crystalline solid with a concentration of 0.5 dme, yield 960 mg (87.6%). 1 H NMR (400 MHz, CD2Cl2): δ-0.02-(-)0.01 (9H, m, Si-C H 3), 0.89-0.92 (3H, m, Si-C) H 3), 1.89-2.06 (14H, m, Me3Si-C H 2 and Cp-C H 3), 3.45 (3H, s, dme-OC) H 3), 3.60(2H, s, dme-C H 2), 5.11-5.13 (1H, m, Si- H ), 5.25-5.65 (2H, m, Cp-C H ), 6.39-6.44 (1H, m, Cp-C) H ) ppm.

[0298] Catalyst 6: Synthesis of methylsilyl-(tetramethylcyclopentadiene)(trimethylsilylmethylcyclopentadiene)dimethylzirconium, Me(H)Si(Me4Cp)(Me3SiCH2Cp)ZrMe2. An ether solution of MeMgBr (1.3 mL, 3.72 mmol) was added dropwise to Me(H)Si(Me4Cp)(Me3SiCH2Cp)ZrCl2 over 5–10 minutes at -25 °C. The mixture was added to a pre-cooled diethyl ether solution at 0.5 dme (960 mg, 1.84 mmol). The resulting mixture was stirred overnight at room temperature to ensure the reaction was complete. All volatiles in the reaction mixture were removed under vacuum, and the crude material was then extracted into pentane. The solvent was removed under vacuum to give a colorless semi-solid Me(H)Si(Me4Cp)(Me3SiCH2Cp)ZrMe2 in a yield of 610 mg (76.1%). 1 H NMR (400 MHz, C6D6): δ-0.30-(-)0.26 (6H, m, Zr-C H 3), 0.03 (9H, s, Si-C)H 3), 0.38-0.42 (3H, m, Si-C) H 3), 1.67-1.69 (3H, m, Cp-C) H 3), 1.77-1.80 (3H, m, Cp-C) H 3), 1.97-2.01 (6H, m, Cp-C) H 3), 2.14-2.16 (2H, broad bimodal, Me3Si-C) H 2), 4.93-5.01 (1H, m, Si- H ), 5.12-5.63 (2H, m, Cp-C H ), 6.38-6.44 (1H, m, Cp-C) H ) ppm.

[0299] Preparation of supported catalysts

[0300] Catalyst 1

[0301] Using Celstir TM 0.8 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. 15.1 mg of methylsilylbis(n-propyl-cyclopentadiene)dimethylhafnium (32.5 mg) was added. mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to obtain 0.71 g of white silica.

[0302] Catalyst 2

[0303] Using Celstir TM 1.0 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. 20.0 mg of phenylsilyl bis(n-propyl-cyclopentadiene)dimethylhafnium (40 mL) was added. mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to obtain 0.93 g of white silica.

[0304] Catalyst 3

[0305] Using Celstir TM 1.0 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. 22.1 mg of methylsilylbis(trimethylsilylmethylenecyclopentadiene)dimethylhafnium (40 mL) was added. mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to obtain 0.91 g of white silica.

[0306] Catalyst 4

[0307] Using Celstir TM 0.76 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. 18.7 mg of phenylsilylbis(trimethylsilylmethylenecyclopentadiene)dimethylhafnium (30.4 mg) was added. mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to obtain 0.70 g of white silica.

[0308] Catalyst 5

[0309] Using Celstir TM 1.0 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. 20.9 mg of methylsilyl(trimethylsilylmethyl-cyclopentadiene)(tetramethyl-cyclopentadiene)dimethylhafnium (40 mL) was added. mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to obtain 0.90 g of white silica.

[0310] Catalyst 6

[0311] Using Celstir TM 1.0 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. 17.4 mg of methylsilyl(trimethylsilylmethyl-cyclopentadiene)(tetramethyl-cyclopentadiene)dimethylzirconium (40 mL) was added. mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to give 0.81 g of pale yellow silica.

[0312] Preparation of mixed catalyst supports

[0313] Supported catalyst: Mixed catalyst system 1

[0314] Using Celstir TM 1.0 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. Methylsilyl(trimethylsilylmethyl-cyclopentadiene)(tetramethyl-cyclopentadiene)dimethylhafnium, 5, (15.7 mg, 30) mol) and bis(1-methylindanyl)zirconium dichloride (3.8 mg, 10 mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to obtain 0.92 g of pale yellow silica.

[0315] Supported catalyst: Mixed catalyst system 2

[0316] Using Celstir TM 1.0 g of the prepared ES-70 875C SMAO was stirred in 10 mL of toluene in a flask. Methylsilylbis(n-propyl-cyclopentadiene)dimethylhafnium, 1, (12.4 mg, 26.6 mg) mol) and meso-bis(1-ethylindenyl)dimethylzirconium (5.4 mg, 13.3 mg). mol) was added to the slurry and stirred for 3 hours. The mixture was filtered, washed with several 10 mL portions of hexane, and then dried under vacuum to give 0.91 g of pale yellow silica.

[0317] Catalyst activity during polymerization in organosilicon-supported catalyst systems.

[0318] Heat a 2L autoclave to 110°C and purge with N2 for at least 30 minutes. Add dry NaCl (350g; Fisher, S271-10 dehydrated at 180°C with several pump / purge cycles, and finally passed through a 16-mesh sieve before use) and sMAO (5g) to the autoclave at 105°C and stir for 30 minutes. Adjust the temperature to 85°C. Under a N2 pressure of 2 psig, add dry, degassed 1-hexene (2.0 mL) to the reactor using a syringe, then add N2 to the reactor to a pressure of 20 psig. Flow a mixture of H2 and N2 into the reactor (200 SCCM; 10% H2 in N2) while stirring the bed.

[0319] The various catalysts shown in Table 1 or the catalyst systems in Table 2 were injected into a reactor containing ethylene at a pressure of 220 psig; ethylene flow was permitted during operation to maintain a constant pressure in the reactor. For each sample, 1-hexene was added to the reactor at a ratio to the ethylene flow rate (0.1 g / g). Hydrogen was added to the reactor at a ratio to the ethylene flow rate (0.5 mg / g). The hydrogen to ethylene ratio was measured by online GC analysis. Polymerization was stopped after 1 hour by venting the reactor, cooling to room temperature, and then exposing it to air. Salts were removed by washing twice with water; the polymer was separated by filtration, briefly washed with acetone, and dried in air for at least two days.

[0320] Table 1: Slurry-phase polymerization of ethylene and 1-heptene

[0321]

[0322] The data in Table 1 are based on the average of several measurements. As shown in Table 1, I is (n-propyl CP)₂Hf(Me)₂, and II is Me₂Si(n-propyl CP)₂Hf(Me)₂. I and II are known catalysts that provide polyethylene copolymers with a hexene comonomer content of 9.3 wt%–10.86 wt%. In contrast, catalyst 1 of the present invention provides a high molecular weight polyethylene copolymer in which the hexene comonomer content is about 15 wt% (15.66 wt%). Furthermore, catalyst 1 provides a MWD value of 2.1. Catalyst 2 provides a high molecular weight polyethylene copolymer in which the hexene comonomer content is about 12 wt% (12.15 wt%) and the MWD value is about 3 (3.09). Compared with the polyethylene copolymer synthesized using catalyst 1, catalyst 4 provides a polyethylene copolymer with a hexene comonomer content of about 15 wt% (15.04 wt%) and an MWD value of about 2.8 (2.81), but with a lower molecular weight. Catalyst 5 provides a high molecular weight polyethylene copolymer in which the content of hexene comonomer is about 12 wt% (12.24 wt%) and the MWD value is about 3.6 (3.57). These catalysts can be used, for example, as catalysts for providing high molecular weight fractions of bimodal polyolefin compositions (e.g., resins) having a broad orthogonal compositional distribution.

[0323] Figure 1 Figure 100 shows the TREF of the polyethylene copolymer produced by catalyst 1. Figure 1 As shown, catalyst 1 (line 102) provides a multi-peak polyethylene copolymer, which is primarily a low-density polyethylene copolymer (peak 104) and a high-density material with a lower HfP (peak 106). (Wf(%) is weight fraction %).

[0324] Figure 2 Figure 200 shows the 4D GPC of the polyethylene copolymer prepared by supported catalyst 1. Figure 2 As shown, catalyst 1 provides a linear polyethylene copolymer, such as g The average value of (vis) (line 202) is 0.973, as evidenced by this. The comonomer content (line 204) ranges from approximately 12 wt% to approximately 18 wt%, with an average of 15.77 wt%. Line 204 has a positive slope, indicating a higher comonomer content in higher molecular weight polyethylene copolymers. Molar mass determinations are represented by lines (IR) 208, LS 206, and IV 210. LogM is represented by line 212. IR concentration is represented by line 214. LogM(LS) is represented by line 216. Specific viscosity is represented by line 218.

[0325] These data indicate that catalyst 1 provides linear low-density polyethylene copolymers with high comonomer content and narrow MWD.

[0326] Table 2: Polymerization data for mixed catalysts:

[0327]

[0328] As shown in Table 2, mixed catalyst system 1 provides a polyethylene composition having a linear low-density polyethylene copolymer with a high molecular weight fraction having a high comonomer content and an MWD value of approximately 5. Mixed catalyst system 2 provides a polyethylene composition having a linear low-density polyethylene copolymer with a higher comonomer content and a narrower MWD than mixed catalyst system 1.

[0329] In summary, the catalyst compounds of formula (I) or formula (II) and their catalyst systems provide compositions of high comonomer content, linear, high molecular weight polyolefin copolymers and BOCD polyolefin copolymers, which have increased density separation and high comonomer content.

[0330] All documents mentioned herein are incorporated herein by reference, including any priority documents and / or test procedures, provided they do not contradict this document. It will be apparent from the foregoing general description and specific embodiments that, while some embodiments have been shown and described, various modifications may be made without departing from the spirit and scope of this specification. Therefore, this specification should not be limited. Similarly, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a component, element, or group of elements is preceded by the transitional phrase "comprising," it should be understood that the same component or group of elements, with transitional phrases such as "consistently composed of," "composed of," "selected from the group of components," or "is," before listing the component, element, or multiple elements individually, and vice versa.

Claims

1. Catalyst system: Bridged or unbridged metallocene catalyst compounds, wherein the bridged or unbridged metallocene catalyst compounds include one or more of the following: 。 2. The catalyst system of claim 1 further comprises an activator and a support material.

3. The catalyst system of claim 2, wherein the activator comprises one or more of the following substances: N,N-Dimethylphenylamine tetra(perfluorophenyl)borate, N,N-Dimethylphenylamine tetra(perfluoronaphthyl)borate N,N-Dimethylphenylamine tetra(perfluorobiphenyl)borate N,N-Dimethylphenylamine tetra(3,5-bis(trifluoromethyl)phenyl)borate, Triphenylcarbomontetra(perfluoronaphthyl)borate Triphenylcarbium tetra(perfluorobiphenyl) borate, Triphenylcarbium tetra(3,5-bis(trifluoromethyl)phenyl)borate, Triphenylcarbium tetra(perfluorophenyl)borate, Trimethylammonium tetra(perfluoronaphthyl)borate Triethylammonium tetra(perfluoronaphthyl)borate Tripropylammonium tetra(perfluoronaphthyl)borate Tris(n-butyl)ammonium tetra(perfluoronaphthyl)borate, Tris(tert-butyl)ammonium tetra(perfluoronaphthyl)borate, N,N-Diethylphenylamine tetra(perfluoronaphthyl)borate, N,N-Dimethyl-(2,4,6-trimethylphenylammonium)tetra(perfluoronaphthyl)borate, and Tetra(perfluoronaphthyl)borate onium.

4. The catalyst system of claim 2, wherein the activator comprises alkylaluminoxane.

5. The catalyst system of claim 2, wherein the support material is selected from Al2O3, ZrO2, SiO2 and SiO2 / Al2O2.

6. The catalyst system of claim 5, wherein the support material is fluorinated.

7. A method for polymerizing an olefin to prepare at least one polyolefin composition, the method comprising: Contact at least one olefin with the catalyst system of any one of claims 1-6; And obtain polyolefins.

8. The method of claim 7, further comprising an alkylaluminoxane present in a molar ratio of aluminum to a Group 4 metal of the catalyst compound of 100:1 or higher.

9. The method of claim 7, wherein the catalyst system further comprises an activator represented by the following formula: (From) d + (And d- ) Where Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + It is Brønsted acid; A d- It is a noncoordinate anion with charge d-; d is an integer from 1 to 3.

10. The method of claim 7, wherein the catalyst system further comprises an activator represented by the following formula: (From) d + (And d- ) Where A d- It is a noncoordinate anion with charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the following formula: (Ar3C + ), where Ar is an aryl group or surrounded by heteroatoms, C1-C 40 Hydrocarbon group or substituted C1-C 40 Aromatic groups substituted with hydrocarbon groups.

11. The method of claim 7, wherein the method is carried out at a temperature of 0°C to 300°C, a pressure of 0.35 MPa to 10 MPa, and for a time of up to 300 minutes.

12. The method of claim 7, wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

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