Syndiotactic propylene-based ethylene-propylene copolymer

Abstract

Provided is a syndiotactic polypropylene-based ethylene-propylene copolymer comprising: a) 5-15% by weight ethylene and 85-95% by weight propylene; b) 60-90% rr triads; c) a Mw(LS) of 10-250 kg / mol; and d) no substantial melting peaks with a peak heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of the filing date of U.S. Provisional Patent Application No. 63 / 276,012, entitled “SYNDIOTACTIC PROPYLENE-BASED ETHYLENE-PROPYLENE COPOLYMERS,” filed November 5, 2021, the disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates to syndiotactic rich propylene-based ethylene-propylene copolymers. [Background technology]

[0003] Generally, olefin polymers and oligomers ("polyolefins" or "polyolefin polymers"), particularly polyalphaolefin polymers containing propylene or other C3 or higher alpha olefin monomers, contain hydrocarbyl groups pendant from the polymer backbone. The pendant hydrocarbyl groups may be arranged in a determined stereochemical configuration relative to the polymer backbone. These configurations include atactic, isotactic and / or syndiotactic configurations.

[0004] Tacticity can be related to the degree of crystallinity that an olefin polymer, particularly a polyalphaolefin polymer, can obtain. As used herein, the tacticity of a polymer reflects the stereochemical regularity of the hydrocarbyl groups pendant to the polymer molecular backbone (i.e., the tacticity of the polymer). In polyalphaolefins, four types of tacticity have been described: atactic, normal isotactic, isotactic stereoblock, and syndiotactic.

[0005] Atactic polyolefins are those in which the hydrocarbyl groups pendant to the polymer molecule backbone are not regularly ordered relative to the backbone. This random or atactic structure is represented by a polymer backbone with alternating methylene and methine carbons, with randomly oriented branches replacing the methine carbons. The methine carbons randomly have R and S configurations, forming adjacent pairs of either similar configurations ("meso" or "m" dyads) or different configurations ("racemic" or "r" dyads).

[0006] Atactic forms of polymers contain approximately equal fractions of meso and racemic dyads. Importantly, atactic polyalphaolefins, particularly atactic polypropylene, can be characterized as being soluble in aliphatic and aromatic solvents at ambient temperature. Atactic polymers are sometimes referred to as amorphous materials because they do not exhibit regular order or repeat unit arrangement in the polymer chain. As amorphous materials, atactic polymers tend to lack molecular lattice structure and may not have a well-defined melting point. Thus, atactic polyalphaolefins are amorphous and typically do not have a measurable melting point, and therefore exhibit little, if any, crystallinity.

[0007] Isotactic polyolefins are characterized as having pendant hydrocarbyl groups spatially aligned to the same side or plane of the polymer backbone. Using isotactic polypropylene as an example, an isotactic structure is typically described as having pendant methyl groups attached to tertiary carbon atoms of successive monomer units on the same side of an imaginary plane through the carbon backbone of the polymer, e.g., the methyl groups are all above or below the plane.

[0008] Isotactic stereoblock morphology of polyolefins can result from "site chirality exchange" and / or "chain end control" mechanisms during the formation of isotactic stereoblock polyalphaolefin polymers. Deviation or inversion of the regularity of the chain structure reduces the degree of isotacticity and therefore the degree of crystallinity that the polymer is capable of.

[0009] Syndiotactic polyalphaolefins are those in which the hydrocarbyl groups pendant to the polymer molecular backbone alternate in a sequential manner from one side or face to the opposite side or face relative to the polymer backbone. The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer and is related to the crystallinity of the polymer.

[0010] The molecular chain backbone of a syndiotactic polymer can be considered to be a copolymer of olefins having alternating stereochemical configurations. Highly syndiotactic polymers can be highly crystalline and therefore have similar defined melting points as their isotactic polymorphs and therefore can be characterized in part by their melting point temperatures.

[0011] The triad tacticity of a polymer is the relative tacticity of a sequence of three adjacent propylene units in a chain consisting of head-to-tail bonds, expressed as a binary combination of m and r sequences. In propylene-based polymers, it is usually expressed as the ratio of the number of units of a particular tacticity to all propylene triads in the polymer.

[0012] Ethylene-propylene copolymers containing a backbone with syndiotactic sequences are softer than PP homopolymers, but have better impact strength, are tougher, and are more durable. Syndiotactic ethylene-propylene copolymers tend to have better stress crack resistance and low temperature toughness than PP homopolymers. Major potential applications include impact modifiers, viscosity modifiers, packaging, textiles, healthcare, pipes, automotive, construction, and electrical applications. Summary of the Invention

[0013] The present disclosure relates to syndiotactic propylene-based ethylene-propylene copolymers comprising: a) 5-15 wt. % ethylene; b) 60-90% rr triads; c) Mw(DRI) from 10-200 kg / mol; and d) no substantial melting peaks with a peak heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min.

[0014] The syndiotactic polypropylene-based ethylene-propylene copolymer (srPP / C2) according to the present disclosure is 13 It exhibits high syndiotacticity as indicated by % rr triads as determined by C NMR. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 shows [PPP] from 13C NMR versus Mw,LS from GPC for the srPP / C2 EP copolymer of the present invention, a commercial EP, and a non-syndiorich EP reference sample, respectively.

[0016] [Diagram 2] Figure 2 shows that inventive sample M8 exhibits good pellet stability after aging in an oven at 40°C and 1 psig for 3 months: the pellets remain well-dispersed individual pellets.

[0017] [Diagram 3] FIG. 3 shows ethylene content (C2 wt%) from FTIR and [EPP] from 13C NMR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0018] [Figure 4] FIG. 4 shows ethylene content (C2 wt%) from FTIR and [EEP] from 13C NMR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0019] [Diagram 5] FIG. 5 shows ethylene content (C2 wt%) from FTIR and [PPP] from 13C NMR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0020] [Figure 6] FIG. 6 shows ethylene content (C2 wt%) from FTIR and [PEP] from 13C NMR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0021] [Figure 7] FIG. 7 shows ethylene content (C2 wt%) from FTIR and [EE] from 13C NMR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0022] [Figure 8] FIG. 8 shows ethylene content (C2 wt%) from FTIR and propylene run # from 13C NMR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0023] [Figure 9]FIG. 9 shows the ethylene content (C2 wt%) from FTIR and glass transition temperature (Tg) from DSC for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure.

[0024] [Figure 10] FIG. 10 shows the g'vis and MW,LS from GPC for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] As used herein, the term "substituted" means that a hydrogen group has been replaced with a heteroatom or a heteroatom-containing group. For example, a "substituted hydrocarbyl" is a radical composed of carbon and hydrogen in which at least one hydrogen has been replaced with a heteroatom or a heteroatom-containing group.

[0026] As used herein, the numbering scheme of the Periodic Table of the Elements is used as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

[0027] For purposes of this disclosure, when a polymer is referred to as comprising an olefin, the olefins present in the polymer are each the polymerized form of an olefin. Similarly, use of the term polymer is meant to encompass homopolymers and copolymers, with copolymers including any polymer having two or more chemically distinct monomers.

[0028] For purposes of this disclosure, the term "polypropylene" as used herein means a polymer that contains propylene as a monomer and may be a homopolypropylene or a copolymer of propylene and an α-olefin comonomer.

[0029] A "catalyst system" is a combination of at least one catalyst compound, at least one activator, optional activating cofactor, and optional support material. The terms "catalyst compound", "catalyst complex", "transition metal complex", "transition metal compound", "precatalyst compound", and "precatalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with the activator and optionally the activating cofactor. When "catalyst system" is used to describe such a pair after activation, it means the activated complex and the activator or other charge balancing moiety. The transition metal compound may be neutral, as in a precatalyst, or a charged species with a counterion, as in an activated catalyst system. For purposes of this disclosure and the claims thereto, when a catalyst system is described as including the neutral stable form of a component, it is well understood by those skilled in the art that the ionic form of the component is the form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize a monomer into a polymer. Additionally, the catalyst compounds and activators represented by formulas herein are intended to encompass both neutral and ionic forms of the catalyst compounds and activators.

[0030] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.

[0031] An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. A "Lewis base" is a neutrally charged ligand that donates one or more electron pairs to a metal ion. Examples of Lewis bases include ethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocycle. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0032] A scavenger is a compound that can be added to promote polymerization by removing impurities. Some scavengers can also act as activators and are sometimes called coactivators. Coactivators that are not scavengers can also be used with activators to form active catalysts. In at least one embodiment, the coactivator can be premixed with the transition metal compound to form an alkylated transition metal compound.

[0033] A noncoordinating anion (NCA) is defined to mean an anion that does not coordinate to the catalyst metal cation or that coordinates to the metal cation but only weakly. The term NCA is also defined to include multi-component NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, which contains an acidic cationic group and a noncoordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with the catalyst to form an activated species by abstraction of an anionic group. A Lewis acid is defined to be a compound or element that can react with an electron donor to form a bond. NCAs coordinate weakly enough that a Lewis base, such as an olefin monomer, can displace it from the catalyst center. Any metal or metalloid capable of forming a compatible weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.

[0034] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also called polydispersity (PDI), is defined as Mw divided by Mn. Unless otherwise stated, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0035] Generally, olefin polymers and oligomers ("polyolefins" or "polyolefin polymers"), particularly polyalphaolefin polymers comprising propylene or other C3 or higher alpha-olefin monomers, contain hydrocarbyl groups pendant from the polymer backbone. The pendant hydrocarbyl groups can be arranged in different stereochemical configurations determined relative to the polymer backbone. These configurations include atactic, isotactic and / or syndiotactic configurations.

[0036] As used herein, the "tacticity" of a polymer reflects the stereochemical regularity of the hydrocarbyl groups pendant to the polymer molecular backbone. Tacticity can be related to the degree of crystallinity that an olefin polymer, particularly a polyalphaolefin polymer, can obtain. Three major types of tacticity have been described in polyalphaolefins: atactic, isotactic, and syndiotactic.

[0037] Atactic polyolefins are those in which the hydrocarbyl groups pendant to the polymer molecule backbone are not regularly ordered relative to the backbone. This random or atactic structure is represented by a polymer backbone with alternating methylene and methine carbons, with randomly oriented branches replacing the methine carbons. The methine carbons randomly have Rectus ("R") and Sinister ("S") configurations, forming adjacent pairs of either similar configurations ("meso" or "m" dyads) or different configurations ("racemic" or "r" dyads).

[0038] Isotactic polyolefins are characterized by having pendant hydrocarbyl groups that are spatially aligned to the same side or plane of the polymer backbone.Using isotactic polypropylene as an example, isotactic structures are typically described as having pendant methyl groups attached to ternary carbon atoms of successive monomer units on the same side of an imaginary plane that runs through the carbon backbone of the polymer, e.g., all methyl groups are above or below the plane.The percentage of m dyads in the chain determines the degree of isotacticity of the polymer and is related to the crystallinity of the polymer.

[0039] Syndiotactic polyolefins are those in which the hydrocarbyl groups pendant to the polymer molecular backbone alternate in a sequential order from one side or face to the opposite side or face relative to the polymer backbone. The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer and is related to the crystallinity of the polymer.

[0040] The molecular chain backbone of a syndiotactic polymer can be considered to be a copolymer of olefins having alternating stereochemical configurations. Highly syndiotactic polymers can be highly crystalline and therefore have similar defined melting points as their isotactic polymorphs and therefore can be characterized in part by their melting point temperatures.

[0041] The triad tacticity of a polymer is the relative tacticity of a sequence of three adjacent propylene units, a chain consisting of head-to-tail bonds, expressed as a binary combination of m and r sequences. In propylene-based polymers, it is usually expressed as the ratio of the number of units of a particular tacticity to the total number of propylene triads in the polymer. For example, a rr triad indicates three adjacent propylene units, and the stereochemistry of the propylene units alternates (e.g., RSR, SRS).

[0042] According to one embodiment, the syndiotactic rich propylene copolymer of the present disclosure comprises: a) 5 to 15% by mass of ethylene and 85 to 95% by mass of propylene; b) 60-90% rr triads; c) Mw(LS) of 10 to 250 kg / mol; d) comprises an ethylene-propylene copolymer having no substantial melting peak and a peak heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min.

[0043] In some embodiments, the syndiotactic rich ethylene-propylene copolymers produced in the present disclosure have syndiotactic stereoregular propylene crystallinity. The term "stereoregular" as used in the present disclosure means that the predominant number of propylene residues in the polypropylene segments in the polymer chain, i.e., greater than 50%, have the same 1,2 insertion, excluding any other monomers such as ethylene, and the stereochemical orientation of the pendant methyl groups is the same, either meso or racemic.

[0044] The tacticity of ethylene-propylene copolymers, including the concentrations of isotactic and syndiotactic dyads ([m] and [r]) and triads ([mm], [mr], and [rr]), is 13 The molecular weight distribution is determined by C NMR. The symbols "m" or "r" represent the stereochemistry of the pairs of successive propylene groups, with "m" referring to meso and "r" referring to racemic. The calculations involved in characterizing polymers by NMR are described in Polymer Conformation and Configuration by F. A. Bovey (Academic Press, New York 1969) and Polymer Sequence Determination, 13C-NMR Method by J. Randall (Academic Press, New York, 1977).

[0045] The "rr triad tacticity index" of a polymer is a measure of the relative syndiotacticity of a sequence of three adjacent propylene units linked in a head-to-tail configuration. More specifically, in the present invention, the rr triad tacticity index (also called the "rr fraction") of a polypropylene copolymer is expressed as the ratio of the number of units of racemic tacticity to the total number of methyl triads in the copolymer.

number

[0046] The areas PP+EP(mm), PP+EP(mr), and PP+EP(rr) are defined as follows: [Table 1]

[0047] This triad tacticity calculation does not take into account sequences, chain ends, or regional defects present within these regions.

[0048] Similarly, the m dyad and r dyad can be calculated as follows, where mm, mr, and rr are defined above:

number

[0049] The propylene copolymers produced in the present disclosure include 13 The rr triad tacticity index of the three propylene units can be 55% or more, 60% or more, 65% or more, 70% or more, as measured by C NMR. In some embodiments, the syndiotactic rich ethylene-propylene copolymers can range from 60-90% rr triads, 65-90% rr triads, 70-90% rr triads, 75-90% rr triads, and 75-85% rr triads. In other embodiments, the copolymers can range from 65-85% rr triads, and 75-85% rr triads.

[0050] The copolymerization between monomers "E" and "P" in the presence of catalyst "M" can be represented by the following reaction scheme and rate equation: 11 is the rate of "E" insertion after "E", and R 12 is the rate of "P" insertion after "E", and R 21 is the rate of "E" insertion after "P", and R 22 is the rate of "P" insertion after "P", and k 11 , k 12 , k 21 , and k 22 are the corresponding rate constants. The reaction scheme and reaction rate equations are shown below.

number

[0051] The reactivity ratios r1 and r2 are:

number

[0052] The product r1 × r2 provides information about how the different monomers are distributed along the polymer chain. Below are examples of alternating, random and block copolymers, showing how the product r1 × r2 relates to each:

number

[0053] r1 and r2 also represent the reactivity of ethylene and propylene in the copolymer, respectively, and are used to describe the properties of the catalyst system. The product of r1 and r2, r1r2, represents the distribution of monomers in the backbone of the copolymer. 13Monomer content and sequence distribution for ethylene-propylene copolymers were determined using C NMR using a procedure adapted from JC Randall's paper: Polymer Reviews, 1989, vol. 29(2), pp.201-317. This paper includes measurements and calculations for 1,2 propylene addition triad sequence distributions, referred to as EEE, EEP, PEP, EPE, EPP and PPP, and reported as mole fractions. Propylene content in mole %, run number, average sequence length, and dyad / triad distribution were all calculated according to the methods established in the paper.

[0054] For propylene-ethylene copolymers, the reactivity ratio (r1r2) is defined as: r1r2=4×(EE×PP) / (EP) 2 (where EE, PP and EP are dyads where E=ethylene, P=propylene).

[0055] The calculation of propylene run# (also called P run# and P run length) is based on the formula P run# = ([EPE] + 0.5 x [EPP]) x 100, where [EPE], [EPP] are the triad molar concentrations, E is ethylene, and P is propylene.

[0056] The present disclosure includes syndiotactic rich ethylene-propylene copolymers where r1r2 is less than 8, less than 6, less than 4, less than 2, or at least less than 1.4.

[0057] In some embodiments, 13 The syndiotactic ethylene-propylene copolymer according to any one of claims 1 to 3, wherein the relationship between [EPP] from C NMR and C2 mass% from FTIR is 1.9833 × C2 mass% - 0.0818 < [EPP] < 1.3333 × C2 mass% + 0.09.

[0058] In some embodiments, the syndiotactic ethylene-propylene copolymer is 13The relationship between [EEP] from C NMR and C2 mass% from FTIR is 0.2931 × C2 mass% - 0.0187 < [EEP] < 0.303 × C2 mass% - 0.0045.

[0059] In some embodiments, the syndiotactic ethylene-propylene copolymer is 13 The relationship between [PPP] from C NMR and C2 mass% from FTIR is -2.8 × C2 mass% + 0.878 < [PPP] < -2.8154 × C2 mass% + 1.0451.

[0060] In some embodiments, the syndiotactic ethylene-propylene copolymer is 13 The relationship between [PEP] from C NMR and C2 mass% from FTIR is 0.8923 × C2 mass% − 0.0021 < [PEP] < 0.9333 × C2 mass% + 0.03.

[0061] In some embodiments, the syndiotactic ethylene-propylene copolymer is 13 [EEE] from C NMR is less than 0.008.

[0062] In some embodiments, the syndiotactic ethylene-propylene copolymer is 13 The relationship between [EE] from C NMR and C2 mass% from FTIR is 0.2 × C2 mass% − 0.016 < [EE] < 0.1292 × C2 mass% + 0.0082.

[0063] In some embodiments, the syndiotactic ethylene-propylene copolymer is 13 The relationship between propylene run# from C NMR and C2 mass% from FTIR is 110.67×C2 mass%−4.7<[P run#]<97.143×C2 mass%+4.7286.

[0064] In some embodiments, for the syndiotactic ethylene-propylene copolymer, the relationship between Tg from DSC and C2 mass % from FTIR is -190×C2 mass % - 9.15 < Tg < -175×C2 mass % + 1.725.

[0065] In some embodiments, for the syndiotactic ethylene-propylene copolymer, g’ from GPC vis and the relationship with MW,LS is g’ vis > 2E-06×MW,LS + 0.9703.

[0066] In some embodiments, the syndiotactic-rich ethylene-propylene copolymer can be in the range of 5 to 15% by mass of ethylene, or 5 to 12% by mass of ethylene, or 5 to 10% by mass of ethylene.

[0067] In some embodiments, Mw(LS) can be in the range of 10 to 250 kg / mol, or 20 to 200 kg / mol, or 30 to 150 kg / mol, or 30 to 120 kg / mol, or 30 to 100 kg / mol. In some embodiments, the MWD (or PDI) of the syndiotactic-rich ethylene-propylene copolymer can be in the range of 1.2 to 5.0, or 1.2 to 2.5, or 1.2 to 2.0, or 1.4 to 2.0.

[0068] The present disclosure includes a syndiotactic-rich ethylene-propylene copolymer having an MFR measured at 2.16 kg and 230 °C of 0.1 to 550 g / 10 min. The MFR measured at 2.16 kg and 230 °C can be in the range of 1 to 450 g / 10 min, or 5 to 300 g / 10 min, or 10 to 200 g / 10 min, or 20 to 100 g / 10 min. Alternatively, the MFR of the syndiotactic-rich ethylene-propylene copolymer is at least 1 g / 10 min, or at least 2 g / 10 min, or at least 10 g / 10 min.

[0069] In some embodiments, the syndiotactic polypropylene-ethylene copolymer has a complex viscosity (at 0.1 rad / s and 190 °C) of about 50,000 Pa·s or less, such as from about 300 Pa·s to about 50,000 Pa·s, such as from about 400 Pa·s to about 40,000 Pa·s, or from about 500 Pa·s to about 10,000 Pa·s, or from about 500 Pa·s to about 10,000 Pa·s. The complex viscosity can be measured by dynamic frequency sweep (DFS) measurement. The complex viscosity can be determined by a small amplitude oscillatory shear (SAOS) test at 190 °C using a TA Instruments model ARES-G2 rheometer. The test specimen can be compression molded using a heat press at 190 °C. The test specimen can have a diameter of 25 mm and a thickness of about 2 mm. The test specimen is loaded into a rheometer preheated to 190 °C and trimmed to a measurement gap of 1.5 mm. The loaded and trimmed test specimen is equilibrated at the test temperature of 190 °C for 5 minutes before testing. The test angular frequency is from 0.01 to 628 rad / s.

[0070] In some embodiments, the syndiotactic-rich ethylene-propylene copolymer has a glass transition temperature of 20 °C or less, or 10 °C or less, or 0 °C or less, or -5 °C or less, or -10 °C or less. In another embodiment, the syndiotactic ethylene-propylene copolymer has a T g from -4.8158 < C2 mass % < -0.5714 × T g + 0.9857, where T g (°C) is from DSC and the ethylene content (C2 mass %) is from FTIR.

[0071] In some embodiments, the syndiotactic rich ethylene-propylene copolymers do not exhibit a substantial melting peak, with the heat of fusion of the peak being 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min. In some embodiments, the syndiotactic rich ethylene-propylene copolymers do not exhibit an endothermic peak during the second heating cycle of a DSC measurement at a scan rate of 10° C. / min. Alternatively, the syndiotactic rich ethylene-propylene copolymers do not have a melting peak during the second heating cycle of a DSC measurement according to the procedures described herein.

[0072] In an embodiment where the syndiotactic rich ethylene-propylene copolymer is a blended polymer, the rr triad tacticity index of the first polymer component can be 70% or less, 65% or less, or even 60% or less. The rr triad tacticity index of the second polymer component can be 70% or more, 75% or more, or even 80% or more.

[0073] In embodiments where the syndiotactic rich ethylene-propylene copolymer is a blended polymer, the ethylene content of the first syndiotactic rich ethylene-propylene copolymer component may be less than 10% by weight, alternatively less than 7%, alternatively less than 5%, alternatively less than 3% by weight based on the total weight of the first polymer component. The ethylene content of the second syndiotactic rich ethylene-propylene copolymer component may be greater than 5%, alternatively greater than 7%, alternatively greater than 10%, alternatively greater than 15%, alternatively greater than 20%, with an upper limit of 25% by weight based on the total weight of the second polymer component.

[0074] In embodiments, the weight average molecular weight of the first copolymer component is greater than the weight average molecular weight of the second copolymer component. In embodiments, the weight average molecular weight of the first copolymer component is greater than about 150,000 g / mol, or greater than about 200,000 g / mol, or greater than about 250,000 g / mol. Alternatively, the weight average molecular weight of the second copolymer component is less than about 150,000 g / mol, or less than about 100,000 g / mol, or between about 50,000 g / mol and about 20,000 g / mol.

[0075] The syndiotactic rich ethylene-propylene copolymer according to various embodiments may be a blend of at least two syndiotactic rich ethylene-propylene copolymers. In one embodiment of the invention, the blend has a bimodal molecular weight distribution or a broad molecular weight distribution with MWD>3.0. The blend can also have a bimodal composition distribution or a broad composition distribution. Alternatively, one component has an ethylene content in the range of 0.2-5 wt.% and a Mw in the range of 100,000-400,000 g / mol, and one component has an ethylene content in the range of 2-15 wt.% and a Mw in the range of 10,000-150,000 g / mol.

[0076] Syndiotactic rich ethylene-propylene copolymers are produced in a process in which the molar ratio of ethylene feed to propylene feed is from about 0.01 to about 0.2, from about 0.02 to 0.15, from about 0.03 to 0.1.

[0077] catalyst The syndiotactic rich ethylene-propylene copolymers of the present disclosure can be produced by any suitable catalyst known in the art. The catalyst compounds described in this disclosure are used to polymerize olefin monomers, including propylene and ethylene, to form syndiotactic rich copolymers. As used in this disclosure, the terms "hydrocarbyl radical", "hydrocarbyl", and "hydrocarbyl group" are used interchangeably throughout this disclosure. Similarly, the terms "group", "radical" and "substituent" are also used interchangeably throughout this disclosure. For purposes of this disclosure, a "hydrocarbyl radical" is defined to be a C1-C100 radical, which may be linear, branched, or cyclic. If cyclic, the hydrocarbyl radical may be aromatic or non-aromatic. A "hydrocarbyl radical" is defined to include substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, and germylcarbyl radicals, as these terms are defined below. A substituted hydrocarbyl radical is one in which at least one hydrogen atom is substituted with at least one functional group, e.g., NR * 2, OR * , SeR * , TeR * , P.R. * 2. AsR * 2. SbR * 2. S.R. * , B.R. * 2. SiR * 3. GeR * 3. SnR * 3. PbR * 3, or at least one non-hydrocarbon atom or group, such as -O-, -S-, -Se-, -Te-, -N(R * )-, =N-, -P(R * )-, =P-, -As(R * )-, =As-, -Sb(R * )-, =Sb-, -B(R * )-, =B-, -Si(R * )2-, -Ge(R *)2-, -Sn(R * )2-, -Pb(R * )2-, etc., are radicals inserted into the hydrocarbyl radical, where R * are independently hydrocarbyl or halocarbyl radicals, and two or more R * may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0078] Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms are replaced with at least one halogen (eg, F, Cl, Br, I) or halogen-containing group (eg, CF3).

[0079] A substituted halocarbyl radical is one in which at least one halocarbyl hydrogen or halogen atom is substituted with at least one functional group, e.g., NR * 2, OR * , SeR * , TeR * , P.R. * 2. AsR * 2. SbR * 2. S.R. * , B.R. * 2. SiR * 3. GeR * 3. SnR * 3. PbR * 3, or at least one non-carbon atom or group, such as -O-, -S-, -Se-, -Te-, -N(R * )-, =N-, -P(R * )-, =P-, -As(R * )-, =As-, -Sb(R * )-, =Sb-, -B(R * )-, =B-, -Si(R * )2-, -Ge(R * )2-, -Sn(R * )2-, -Pb(R * )2-, etc. are radicals inserted into the halocarbyl radical, where R *are independently hydrocarbyl or halocarbyl radicals, provided that at least one halogen atom remains on the original halocarbyl radical. * may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0080] Hydrocarbylsilyl groups, also called silylcarbyl groups (also called hydrocarbylsilyl groups), are groups in which one or more hydrocarbyl hydrogen atoms are bonded to at least one SiR * 3-containing group or at least one -Si(R * )2- is a radical inserted into a hydrocarbyl radical, where R * are independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R * may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. The silylcarbyl radicals can be attached via a silicon atom or a carbon atom.

[0081] A substituted silylcarbyl radical is one in which at least one hydrogen atom is substituted with at least one functional group, e.g., NR * 2, OR * , SeR * , TeR * , P.R. * 2. AsR * 2. SbR * 2. S.R. * , B.R. * 2. GeR * 3. SnR * 3. PbR * 3, or at least one non-hydrocarbon atom or group, such as -O-, -S-, -Se-, -Te-, -N(R * )-, =N-, -P(R * )-, =P-, -As(R * )-, =As-, -Sb(R * )-, =Sb-, -B(R * )-, =B-, -Ge(R * )2-, -Sn(R* )2-, -Pb(R * )2-, etc. are silylcarbyl radicals inserted in silylcarbyl radicals, where R * are independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R * may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0082] A germylcarbyl radical, also called a germylcarbyl group (also called a hydrocarbylgermyl group), is a group in which one or more hydrocarbyl hydrogen atoms are bonded to at least one GeR * 3-containing group or at least one -Ge(R * )2- is a radical inserted into a hydrocarbyl radical, where R * are independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R * may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. The germylcarbyl radical can be attached via a germanium atom or a carbon atom.

[0083] A substituted germylcarbyl radical is one in which at least one hydrogen atom is substituted with at least one functional group, e.g., NR * 2, OR * , SeR * , TeR * , P.R. * 2. AsR * 2. SbR * 2. S.R. * , B.R. * 2. GeR * 3. SnR * 3. PbR * 3, or at least one non-hydrocarbon atom or group, such as -O-, -S-, -Se-, -Te-, -N(R * )-, =N-, -P(R * )-, =P-, -As(R * )-, =As-, -Sb(R *)-, =Sb-, -B(R * )-, =B-, -Ge(R * )2-, -Sn(R * )2-, -Pb(R * )2-, etc. are germylcarbyl radicals inserted in germylcarbyl radicals, where R * are independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R * may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0084] A "polar radical" (or "polar group") is a group in which a heteroatom functional group is directly attached to the indicated atom or atoms. Polar radicals include heteroatoms from Groups 1-17 of the Periodic Table (excluding carbon and hydrogen) alone or bonded to other elements by covalent or other interactions such as ionic bonds, van der Waals forces, or hydrogen bonds. Examples of heteroatom-containing functional groups include carboxylic acids, acid halides, carboxylic esters, carboxylates, carboxylic anhydrides, aldehydes and their chalcogen (group 14) analogs, alcohols and phenols, ethers, peroxides and hydroperoxides, carboxylic acid amides, hydrazides and imides, amidines and other nitrogen analogs of amides, nitriles, amines and imines, azos, nitros, other nitrogen compounds, sulfur acids, selenates, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, aluminates. Examples of polar groups include NR * 2, OR * , SeR * , TeR * , P.R. * 2. AsR * 2. SbR * 2. S.R. * , B.R. * 2. SnR * 3. PbR * 3, where R *are independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl radical as defined above, and two R * may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0085] When the terms "substituted or unsubstituted cyclopentadienyl ligands", "substituted or unsubstituted indenyl ligands", and "substituted or unsubstituted tetrahydroindenyl ligands" are used, the substitutions on the foregoing ligands can be hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl. Substitutions can also be made within the ring to give heterocyclopentadienyl ligands, heteroindenyl ligands, or heterotetrahydroindenyl ligands, each of which may or may not be further substituted.

[0086] The hydrocarbyl radicals are independently methyl, ethyl, ethenyl, as well as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosen ... Cosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecyn ... The radicals may be selected from the isomers of octadecinyl, nonadecinyl, eicosinyl, heneicosinyl, docosinyl, tricosinyl, tetracosinyl, pentacosinyl, hexacosinyl, heptacosinyl, octacosinyl, nonacosinyl, triacontinyl, butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, and decadienyl. Also included are isomers of saturated, partially unsaturated, and aromatic cyclic and polycyclic structures, in which the radicals may be further subjected to the above types of substitution. Examples include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, benzyl, methylbenzyl, naphthyl, anthracenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl, norbornyl, norbornenyl, adamantyl, etc. For purposes of this disclosure, when a radical is recited, it refers to that radical type and all other radicals that are formed when that radical type is subjected to substitution as defined above.The recited alkyl, alkenyl and alkynyl radicals include all isomers, including cyclic isomers where appropriate, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and similar substituted cyclopropyls), pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and similar substituted cyclobutyls and cyclopropyls), butenyl includes the E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl (as well as cyclobutenyl and cyclopropenyl). Substituted cyclic compounds include all isomeric forms, for example, methylphenyl includes ortho-methylphenyl, meta-methylphenyl and para-methylphenyl, and dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0087] Examples of cyclopentadienyl and indenyl ligands as anionic ligands are shown below. The ring numbering scheme is also shown. When the cyclopentadienyl ligand has one bridging substituent, the bridging substituent is at the 1 position. When the cyclopentadienyl ligand has two bridging substituents, the bridging substituents are at the 1 and 2 positions. When the fluorenyl ligand has a bridging substituent, the bridging substituent is at the 9 position. When the dibenzo[b,h]fluorene has a bridging substituent, the bridging substituent is at the 12 position. [ka]

[0088] A similar numbering and naming scheme is used for heterocyclopentapentalenyl, heterofluorenyl, etc., as shown below. Each structure shown is drawn as the anion.

[0089] Non-limiting examples of heterocyclopentapentalenyls include the following, where Q is a heteroatom O, S, Se, or Te, or a heteroatom group NR ** , P.R. ** , AsR ** , or SbR ** R ** is hydrogen or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl substituent. When the heterocyclopentapentalenyl ligand has a bridging substituent, the bridging substituent is at the 7-position. [ka]

[0090] Non-limiting examples of heterofluorenyls where Z represents the heteroatom N or P include: When the heterofluorenyl ligand bears a bridging substituent, the bridging substituent is at the 9-position. [ka]

[0091] A "ring heteroatom" is a heteroatom that is located within a cyclic ring structure. A "heteroatom substituent" is a heteroatom-containing group that is directly attached to a ring structure via a heteroatom. A "bridging heteroatom substituent" is a heteroatom or heteroatom group that is directly attached to two different ring structures via a heteroatom. The terms "ring heteroatom", "heteroatom substituent", and "bridging heteroatom substituent" are set forth below, where Z and R' are as defined above. [ka]

[0092] A "ring carbon atom" is a carbon atom that is part of a cyclic ring structure. For example, an indenyl ligand has 9 ring carbon atoms and a cyclopentadienyl ligand has 5 ring carbon atoms.

[0093] Transition metal compounds have symmetry elements and belong to symmetry groups. These elements and groups are well established and can be found in Chemical Applications of Group Theory (2nd Edition), by F. Albert Cotton, Wiley-Interscience, 1971. s A compound with symmetry has mirror planes. For example, the following structure has a zirconium center, a carbon bridge, and a C bisect cyclopentadienyl and fluorenyl ligands: s It has a plane of symmetry. [ka]

[0094] Symmetrical substituents have a transition C s A substituent that maintains symmetry. For example, t-butyl groups substituted at the 2- and 7-positions of a fluorenyl ligand can be symmetrical substituents.

[0095] pseudo-C s Symmetrical compounds are similar except that bridging groups, labile ligands, and similarly sized distant substituents on cyclopentadienyl or fluorenyl ligands are not included in determining the symmetry of the compound. These compounds are truly C s Although not symmetric, C for olefin polymerization s It is believed to have a symmetric active site. Thus, for example, compounds with MeEtSi or MePhSi bridging ligands are C-peptide-like compounds, taking into account the appropriate remaining ligand structure. s Similarly, for example, a compound having one Me labile ligand and one Cl labile ligand is considered to have a pseudo-C s It is believed to have a plane of symmetry. s Non-limiting examples of symmetrical compounds are shown below: [ka]

[0096] pseudo-Cs Compounds with symmetry can also have different substituents on non-labile ligands (i.e., cyclopentadienyl or fluorenyl ligands) if the substituents are far from the active site. Substituents of this type, called pseudo-symmetrical substituents, are typically adjacent to the bridging group and do not differ substantially in size from one another. Typically, the difference in size of these substituents is within two non-hydrogen atoms of each other. Thus, a cyclopentadienyl substituted with methyl and ethyl at the 2-position and 5-position, respectively, or a cyclopentadienyl substituted with methyl at the 2-position and unsubstituted at the 5-position, or a fluorenyl substituted with hexyl and octyl at the 1-position and 8-position, respectively, are pseudo-C s It is believed to have symmetry.

[0097] Generally, catalysts that can make syndiotactic polypropylene and react with hydrogen to terminate growing polymer chains are useful catalysts for producing the syndiotactic polypropylene homopolymers and syndiotactic propylene-rich ethylene-propylene copolymers described in this disclosure.

[0098] Catalysts useful for producing syndiotactic polypropylene homopolymer and syndiotactic propylene-rich ethylene-propylene copolymer include C s Or pseudo-C s A metallocene compound (pre-catalyst) having a structure represented by the symmetrical formula (1) is mentioned. [ka] During the ceremony, M is zirconium or hafnium; L 1is an unsubstituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand, or a substituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand having one or more symmetric or pseudosymmetric substituents, each substituent group being independently a radical group which is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, and optionally two or more adjacent substituents may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic substituent;

[0099] L 2 is a cyclopentadienyl ring or a substituted cyclopentadienyl ring having one or more symmetric or pseudo-symmetric substituents at the 2- and 5-positions of the ring, each substituent group being independently a radical group which is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl; G is a bridging group; Each X is independently a hydrido radical, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl, or both X's are linked and bonded to a metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both can be taken together as an olefin, diolefin or aryne ligand, or both X's can be independently a halogen, alkoxide, aryloxide, amide, phosphide or other monovalent anionic ligand, or both X's can also be linked to form a dianionic chelating ligand.

[0100] In some embodiments of Formula (1), L 1is fluorenyl or a substituted fluorenyl, such as fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 2,7-diphenylfluorenyl, 2,7-dichlorofluorenyl, 2,7-dibromofluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, 3,6-diphenylfluorenyl, 3,6-dichlorofluorenyl, 3,6-dibromofluorenyl, 2,7-di-tert-butylfluorenyl, or 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl. Most preferably, it is 2,7-di-tert-butylfluorenyl or fluorenyl. In some embodiments, L 2 is cyclopentadienyl. In some embodiments, G is methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, diphenylsilylene, di(4-triethylsilylphenyl)silylene, ethylene, or di(para-triethylsilylphenyl)methylene, most preferably dimethylmethylene, diphenylmethylene, or di(para-triethylsilylphenyl)methylene. In some embodiments, each X is independently hydrocarbyl or halo, such as methyl, benzyl, fluoro, or chloro. In some embodiments, M is preferably zirconium. In alternative embodiments, M is hafnium.

[0101] C that can be used s Or pseudo-C s A subset of the metallocene compounds (pre-catalysts) represented by formula (1) that have symmetry are represented by formula (1a): [ka] In the formula, M, G, and X are defined as in formula (1), Each R a and R bare independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, or a polar radical, and optionally two or more adjacent substituents may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic substituent, with the proviso that each R a is the same, and each R b are the same, and the compound is C s Symmetric or pseudo-C s Allowing for symmetry, Each R c are independently symmetric or pseudosymmetric substituents relative to one another and are selected from hydrogen or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl radical; Each R d are symmetric or pseudosymmetric substituents relative to one another and are independently selected from hydrogen or hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl radicals.

[0102] In some embodiments of Formula (1a), each R d , R a and R c is hydrogen, and each R b is hydrogen, hydrocarbyl, halogen, silylcarbyl, or a polar radical, such as hydrogen, methyl, ethyl, propyl, butyl, phenyl, mesityl, fluoro, chloro, bromo, dimethylamido, diethylamido or methoxy, such as hydrogen or butyl, such as hydrogen or tert-butyl, such as tert-butyl.

[0103] In another embodiment of formula (1a), each R d , R b and R c is hydrogen, and each R a is independently hydrogen, hydrocarbyl, halogen, or silylcarbyl, such as hydrogen, methyl, ethyl, propyl, butyl, fluoro, chloro, or bromo, such as hydrogen or butyl, such as hydrogen or tert-butyl, such as hydrogen.

[0104] Additionally, in other embodiments of formula (1a), each R d and R c is hydrogen, and each R a and R b are linked together to form a fused, saturated, six-membered carbocyclic ring, each such fused ring being optionally substituted with four methyl substituents. Such a ligand structure is shown in formula (1b): [ka]

[0105] Additionally, in another embodiment of formula (1a), R c and R d is hydrogen, and each R a and R b are independently hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl or phenyl, for example, R a is hydrogen and R b is hydrogen, methyl, ethyl, propyl, or butyl, or R b is hydrogen and R a is hydrogen, methyl, ethyl, propyl, or butyl. In some embodiments, R a is hydrogen and R b is tert-butyl or hydrogen. G may be methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, diphenylsilylene, di(4-triethylsilylphenyl)silylene, ethylene, di(para-triethylsilylphenyl)methylene, such as diphenylmethylene, dimethylmethylene, diphenylsilylene and dimethylsilylene, such as diphenylmethylene. Each X is independently hydrocarbyl or halo, such as methyl, benzyl, fluoro or chloro, such as methyl or chloro. In some embodiments, M is zirconium. In other embodiments, M is hafnium.

[0106] In some preferred embodiments of the present invention, for the metallocene compounds of formula (1), (1a) and / or (1b), M is zirconium.

[0107] In some preferred embodiments of the present invention, for the metallocene compounds of formula (1), (1a) and / or (1b), X is methyl.

[0108] In some embodiments of Formula (1a), each R d , R a and R c is hydrogen, and each R b is methyl, ethyl, propyl, butyl, and most preferably tert-butyl.

[0109] In some preferred embodiments of the present invention, for the metallocene compounds of formula (1a) and / or (1b), G is di(para-triethylsilylphenyl)methylene.

[0110] Examples of precatalysts represented by formula (1) include diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, methylene-(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, ethylene-(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, Lid, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, methylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, diphenylsilylene-(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, ethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, di(para-triethylsilylphenyl)methylene(2,7-Di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, methylene-(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, ethylene-(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride Examples of such dimethylsilylene-(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl include diphenylsilylene-(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, ... In some embodiments, the pre-catalyst represented by formula (1) is selected from the group consisting of diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, di(para-triethylsilylphenyl)methylene(2,7-di-tertbutylfluorenyl)(cyclopentadienyl)hafnium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, and di(para-triethylsilylphenyl)methylene(2,7-di-tertbutylfluorenyl)(cyclopentadienyl)zirconium dimethyl. In some embodiments, zirconium-based catalysts of formulas 1, 1a and 1b are preferred, such as diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, or di(para-triethylsilylphenyl)methylene(2,7-di-tertbutylfluorenyl)(cyclopentadienyl)zirconium dimethyl.

[0111] Catalysts capable of producing syndiotactic polypropylene homopolymer and syndiotactic propylene-rich ethylene-propylene copolymer include C s Or pseudo-C s Also included are metallocene compounds (pre-catalysts) having a structure represented by the symmetrical formula (2): [ka] During the ceremony, M is hafnium, zirconium or titanium; L 1 is an unsubstituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand, or a substituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand having one or more symmetric or pseudosymmetric substituents, each substituent group being independently a radical group which is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, and optionally two or more adjacent substituents may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic substituent; G is a bridging group; J is a heteroatom from group 15, such as N or P, e.g. N; R' is a radical group that is hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl; L' is a neutral Lewis base; w represents the number of L's attached to M, where w is 0, 1, or 2; and optionally, any L' and any X may be bonded to each other; Each X is independently a hydride radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halocarbyl radical, a substituted halocarbyl radical, a silylcarbyl radical, a substituted silylcarbyl radical, a germylcarbyl radical, or a substituted germylcarbyl radical, or both X's are linked and attached to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both together are an olefin, diolefin, or aryne ligand, or both X's may independently be halogens, alkoxides, aryloxides, amides, phosphides, or other monovalent anionic ligands, or both X's may be linked to form a dianionic chelating ligand.

[0112] In some embodiments of formula (2), L 1is fluorenyl or a substituted fluorenyl, such as fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 2,7-diphenylfluorenyl, 2,7-dichlorofluorenyl, 2,7-dibromofluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, 3,6-diphenylfluorenyl, 3,6-dichlorofluorenyl, 3,6-dibromofluorenyl, or 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl. In some embodiments, G is methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, methylphenylsilylene, diphenylsilylene, di(4-triethylsilylphenyl)silylene, ethylene, such as diphenylmethylene, diphenylsilylene, methylphenylsilylene, and dimethylsilylene, such as dimethylsilylene. In some embodiments, J is nitrogen. In some embodiments, R' is hydrocarbyl or halocarbyl, such as C3-C20 hydrocarbyl, such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, benzyl, phenyl and all isomers of substituted phenyl (including cyclic and polycyclic), such as tert-butyl, neopentyl, benzyl, phenyl, diisopropylphenyl, adamantyl, norbornyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl, such as tert-butyl, adamant-1-yl, norborn-2-yl, cyclohexyl, cyclooctyl, and cyclododecyl. In some embodiments, X is hydrocarbyl or halo, such as methyl, benzyl, fluoro, or chloro, such as methyl or chloro. In some embodiments, w is 0 (L' is absent) and M is zirconium or titanium.

[0113] In some embodiments, the catalyst of formula (2) is: [ka]

[0114] Catalysts useful for producing syndiotactic polypropylene homopolymer and syndiotactic propylene-rich ethylene-propylene copolymer include C s Or pseudo-C s Also included are metallocene compounds (pre-catalysts) having a structure represented by the symmetrical formula (3): [ka] During the ceremony, M is hafnium or zirconium; L 3 is a cyclopentadienyl ring optionally substituted at the 4-position of the ring, the substituents being selected from radical groups which are hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl; L 4 is a substituted cyclopentadienyl ring having symmetric or pseudosymmetric substituents at the 3- and 5-positions of the ring, each substituent group being independently a radical group which is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl; G' and G" are bridging groups;

[0115] Each X is independently a hydrido radical, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, or both X's are linked and attached to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both together are an olefin, diolefin, or aryne ligand, or both X's may independently be halogen, alkoxide, aryloxide, amide, phosphide, or other monovalent anionic ligand, or both X's may be linked to form a dianionic chelating ligand.

[0116] In formula (3), L 3is cyclopentadienyl or a hydrocarbyl or silylcarbyl substituted cyclopentadienyl having a substitution at the 4-position of the cyclopentadienyl ring, such as cyclopentadienyl, 4-methylcyclopentadienyl, 4-ethylcyclopentadienyl, 4-propylcyclopentadienyl, 4-butylcyclopentadienyl, 4-pentylcyclopentadienyl, 4-hexylcyclopentadienyl, 4-heptylcyclopentadienyl, 3-octylcyclopentadienyl, or 4 -trimethylsilylcyclopentadienyl, such as cyclopentadienyl, 4-isopropylcyclopentadienyl, 4-tert-butylcyclopentadienyl, 4-(2,2-dimethylpent-3-yl)cyclopentadienyl, 4-(2,2-dimethylbut-3-yl)cyclopentadienyl, or 4-trimethylsilylcyclopentadienyl, such as cyclopentadienyl, 4-isopropylcyclopentadienyl, or 4-trimethylsilylcyclopentadienyl. In some embodiments, L 4is a hydrocarbyl or silylcarbyl substituted cyclopentadienyl having substitutions at the 3- and 5-positions of the cyclopentadienyl ring, such as 3,5-dimethylcyclopentadienyl, 3,5-diethylcyclopentadienyl, 3,5-dipropylcyclopentadienyl, 3,5-dibutylcyclopentadienyl, 3,5-dipentylcyclopentadienyl, 3,5-dihexylcyclopentadienyl, 3,5-dibenzylcyclopentadienyl, or 3,5-bis(trimethylsilyl)cyclopentadienyl, such as 3,5-dimethylcyclopentadienyl, 3,5-diisopropylcyclopentadienyl, cyclopentadienyl, 3,5-di-tert-butylcyclopentadienyl, 3,5-dicyclopentylcyclopentadienyl, 3,5-dipent-3-ylcyclopentadienyl, 3,5-dicyclohexylcyclopentadienyl, 3,5-dibenzylcyclopentadienyl, or 3,5-bis(trimethylsilyl)cyclopentadienyl, for example 3,5-dimethylcyclopentadienyl, 3,5-diisopropylcyclopentadienyl, 3,5-di-tert-butylcyclopentadienyl, 3,5-dibenzylcyclopentadienyl, or 3,5-bis(trimethylsilyl)cyclopentadienyl. In some embodiments, each G' and G" is methylene, dimethylmethylene, dimethylsilylene, such as dimethylmethylene or dimethylsilylene, such as dimethylsilylene. In some embodiments, each X is hydrocarbyl or halo, such as methyl, benzyl, fluoro or chloro, such as methyl or chloro. In some embodiments, M is zirconium. In alternative embodiments, M is hafnium.

[0117] C s Or pseudo-C s A subset of metallocene compounds (pre-catalysts) represented by formula (3) that may be used, including those having symmetry, is represented by formula (3a): [ka] In the formula, M, G', G" and X are defined as in formula (3), R eis selected from hydrogen or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl radical; Each R f and R g is selected from hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, with the proviso that each R f and R g is the compound C s Symmetric or pseudo-C s It is chosen to allow for symmetry.

[0118] In some embodiments of Formula (3a), each R f and R g is independently a hydrocarbyl or silylcarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or trimethylsilyl, such as methyl, isopropyl, tert-butyl, cyclopentyl, pent-3-yl, cyclohexyl, benzyl, or trimethylsilyl, such as methyl, isopropyl, tert-butyl, benzyl, or trimethylsilyl. In some embodiments, R e is hydrogen, hydrocarbyl or silylcarbyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or trimethylsilyl, for example hydrogen, isopropyl, tert-butyl, 2,2-dimethylpent-3-yl, 2,2-dimethylbut-3-yl, or trimethylsilyl, for example hydrogen, isopropyl or trimethylsilyl.

[0119] In some embodiments, the catalyst of formula (3) is: [ka]

[0120] In some embodiments of formula 1, 1a, 1b, 2, 3, or 3a, G, G′, and G″ are R * 2C, R * 2Si, R * 2Ge, R* 2CCR * 2. R * C=CR * , R * 2CSiR * 2. R * 2SiSiR * 2. R * B, R * 2C-BR * , R * N,R * P, O, S, and Se, where each R * are independently hydrogen, C1 to C 20 containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituents, and optionally two or more adjacent R * may be linked to form a substituted or unsubstituted saturated, partially unsaturated cyclic or polycyclic substituent. In some embodiments, G, G', and G" are R * 2C, R * 2Si, R * 2Ge, R * 2CCR * 2. R * B, R * N,R * P, O, S, and Se, where each R * are independently hydrogen, C1 to C 20 containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituents, and optionally two or more adjacent R * may be linked to form a substituted or unsubstituted saturated, partially unsaturated cyclic or polycyclic substituent. In some embodiments, G, G', and G" are independently selected from R * 2C, R * 2Si and R * 2CCR * 2, where each R * are independently hydrogen, C1 to C 20 containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituents, and optionally two or more adjacent R *may be linked to form a substituted or unsubstituted saturated, partially unsaturated cyclic or polycyclic substituent.

[0121] Catalysts capable of producing the syndiotactic polypropylene polymers and syndiotactic propylene-rich ethylene-propylene copolymers described herein can include compounds (precatalysts) having a structure represented by formula (4) having C2 symmetry: [ka] During the ceremony, M is zirconium or titanium; O is oxygen, N is nitrogen; R 1 is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl, for example R 1 is a halocarbyl, R 2 is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl, for example R 2 is a hydrocarbyl having 3 or more carbon atoms or a silylcarbyl having 3 or more carbon atoms; R 3 , R 4 and R 5 Each of R is independently hydrogen or hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, for example, R 3 , R 4 and R 5 is hydrogen, Each X is independently a hydrido radical, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, or both X's are linked and attached to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both together are an olefin, diolefin, or aryne ligand, or both X's may independently be halogen, alkoxide, aryloxide, amide, phosphide, or other monovalent anionic ligand, or both X's may be linked to form a dianionic chelating ligand.

[0122] In some embodiments of formula (4), R 1 is a hydrocarbyl or halocarbyl radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, perfluorophenyl, trifluorophenyl, difluorophenyl, or fluorophenyl, such as phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, perfluorophenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-difluorophenyl, or 4-fluorophenyl, such as perfluorophenyl. In some embodiments, R 2 is a hydrocarbyl or silylcarbyl radical, e.g., C 12 Hydrocarbyl or C3-C 12 Silylcarbyl, such as propyl, butyl, pentyl, hexyl, heptyl, octyl, cumyl, or trimethylsilyl, such as isopropyl, tert-butyl, cumyl, or trimethylsilyl, such as tert-butyl or trimethylsilyl. In some embodiments, R 3 , R 4 , and R 5is independently hydrogen or a hydrocarbyl radical. In some embodiments, each X is hydrocarbyl or halo, such as methyl, benzyl, fluoro or chloro, such as methyl or chloro. In some embodiments, M is titanium.

[0123] In some embodiments, the catalyst compound of formula (4) is: [ka]

[0124] Activators and Catalyst Activation The terms "cocatalyst" and "activator" are used interchangeably in this disclosure and are defined as any compound capable of activating any one of the above precatalyst compounds by converting the neutral precatalyst compound into a catalytically active cationic compound. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, ionizing activators that can be neutral (Lewis acid activators) or ionic (ionic activators), and conventional cocatalysts. Activators can include alumoxane compounds, modified alumoxane compounds, or ionizing anion precursor compounds that abstract reactive σ-bonded metal ligands to render the metal complex cationic and provide a charge-balancing non-coordinating or weakly coordinating anion.

[0125] Alumoxane activators are utilized as activators in the catalyst systems described in this disclosure. Alumoxanes are generally represented by the formula -Al(R 1 )-O-subunits, where R 1is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. Visually clear methylalumoxane may be used. Cloudy or gelled alumoxane may be filtered to produce a clear solution, or clear alumoxane may be decanted from the cloudy solution. A useful alumoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A and protected by U.S. Pat. No. 5,041,584). Another useful alumoxane is solid polymethylaluminoxane such as those described in US Pat. Nos. 9,340,630, 8,404,880, and 8,975,209.

[0126] When the activator is an alumoxane (modified or unmodified), at least one embodiment typically selects a maximum amount of activator of up to 5000-fold molar excess Al / M over the catalyst compound (per metal catalytic site). The minimum molar ratio of activator to catalyst compound is 1:1. Alternative suitable ranges include 1:1 to 500:1, alternatively 1:1 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 50:1.

[0127] In alternative embodiments, little or no alumoxane is used in the polymerization processes described herein, for example, the alumoxane is present at 0 mole %, or the alumoxane is present at a molar ratio of aluminum to transition metal of the catalyst compound of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0128] Lewis acid activators include triphenyl boron, tris-perfluorophenyl boron, and tris-perfluorophenyl aluminum, but exclude the class of activators called alumoxanes. Ionic activators include dimethylanilinium tetrakisperfluorophenyl borate, triphenyl carbonium tetrakisperfluorophenyl borate, and dimethylanilinium tetrakisperfluorophenyl aluminate. Lewis acid activators and ionic activators are referred to as stoichiometric activators because a relatively low molar ratio of activator to transition metal compound is required, compared to alumoxane activators, which require a large excess of activator relative to the transition metal compound.

[0129] Neutral or ionic activators such as tri(n-butyl)ammonium tetrakis(pentafluorophenylborate), trisperfluorophenyl boron, trisperfluoronaphthyl boron, polyhalogenated heteroborane anions, boric acid, or combinations thereof can also be used.

[0130] Stoichiometric activators (sometimes used in combination with coactivators) can be used in making the syndiotactic polypropylene homopolymers and syndiotactic propylene-rich ethylene-propylene copolymers described in this disclosure.

[0131] For example, trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, Activators such as N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate (where alkyl is methyl, ethyl, propyl, n-butyl, iso-butyl or t-butyl) are used.

[0132] In at least one embodiment, the activator is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium ... and one or more of the following: tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropylium tetrakis(perfluoronaphthyl)borate, di(hydrogenated tallow)methylammonium tetrakis(perfluorophenyl)borate, di(hydrogenated tallow)methylammonium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, and dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate. Further useful activators include: N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate], N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N,N-di(octadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(hexadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(tetradecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(dodecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N-Octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-Octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-Octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-Octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-Hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-Hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-Hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate] is an example.

[0133] Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent groups are each independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy and halide. For example, the three substituent groups are independently selected from halogen, monocyclic or polycyclic (including halo-substituted) aryl, alkyl and alkenyl compounds, and mixtures thereof, and can be, for example, alkenyl groups having 1-20 carbon atoms, alkyl groups having 1-20 carbon atoms, alkoxy groups having 1-20 carbon atoms, and aryl groups (including substituted aryl) having 3-20 carbon atoms. In some embodiments, the three substituent groups are alkyl, phenyl, naphthyl or mixtures thereof having 1-4 carbon groups. In some embodiments, the three substituent groups are halogenated, such as fluorinated aryl groups. In some embodiments, the neutral stoichiometric activator is tris(perfluorophenyl)boron or tris(perfluoronaphthyl)boron.

[0134] Ionic stoichiometric activator compounds may contain an active proton or some other cation that is associated but not coordinated or only loosely coordinated with the remaining ions of the ionized compound. Such compounds are disclosed in European Publication Nos. EP-A-0570982, EP-A-0520732, EP-A-0495375, EP-B1-0500944, EP-A-0277003 and EP-A-0277004, as well as U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741 and 5,206,197. Nos. 5,241,025, 5,384,299 and 5,502,124, U.S. Patent Application Publication No. 2021079537, WO 2021 / 086467, U.S. Patent Application Publication Nos. 2019 / 0330169, 2019 / 0330392, and U.S. Patent No. 5,972,823, all of which are incorporated by reference into this disclosure.

[0135] Ionic catalysts can be prepared by reacting a transition metal compound with an activator, such as B(C6F6)3, which upon reaction with a hydrolyzable ligand (X') of the transition metal compound forms ([B(C6F5)3(X')] - ) which stabilizes the cationic transition metal species produced by the reaction. The catalysts can be prepared using activator components that are ionic compounds or compositions. However, activator preparations utilizing neutral compounds are also contemplated.

[0136] Compounds useful as activator components in the preparation of the ionic catalyst system used in the present method can include a cation, which can be a Bronsted acid capable of donating a proton, and a relatively large (bulky) compatible non-coordinating anion capable of stabilizing the active catalyst species formed when the two compounds are combined, which anion is sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated substrates, or other neutral Lewis bases such as ethers, nitriles, etc. Two classes of compatible non-coordinating anions have been disclosed in EPA 277,003 and EPA 277,004 published in 1988: 1) anionic coordination complexes containing multiple lipophilic groups covalently coordinated to and shielding a central charge-carrying metal or metalloid core, and 2) anions containing multiple boron atoms such as carboranes, metallacarboranes and boranes.

[0137] In at least one embodiment, the ionic stoichiometric activator comprises a cationic component and an anionic component and has the following formula: (L ** -H) d + (A d- ) It can be expressed by In the formula, L ** is a neutral Lewis base, H is hydrogen, (L ** -H) + is a Brønsted acid, and A d- is a non-coordinating anion having a charge d-, where d is an integer from 1 to 3.

[0138] Cationic component ((L ** -H) d + ) can include a Bronsted acid, such as a proton or a protonated Lewis base, or a reducible Lewis acid that can protonate or abstract a moiety, such as an alkyl or aryl, from the pre-catalyst after alkylation.

[0139] Activated cation (L ** -H) d+ may be a Bronsted acid capable of donating a proton to the alkylated transition metal catalyst precursor resulting in a transition metal cation, including ammonium, oxonium, phosphonium, silylium, and mixtures thereof, such as ammonium from methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromoN,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphonium from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, sulfonium from thioethers such as diethylthioether and tetrahydrothiophene, and mixtures thereof. The activated cation (L ** -H) d + may be moieties such as silver, tropylium, carbenium, ferrocenium, and mixtures such as carbonium and ferrocenium, e.g., triphenylcarbonium. d- is expressed by the formula [M k+ Q n ] d- Wherein k is an integer from 1 to 3, n is an integer from 2 to 6, nk=d, M is an element selected from Group 13 of the Periodic Table of Elements, such as boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl radical, with Q having up to 20 carbon atoms, provided that in no more than one occurrence, Q is a halide. For example, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group, such as each Q is a pentafluoryl aryl group. Suitable A d-Examples also include diboron compounds such as those disclosed in U.S. Pat. No. 5,447,895, the entirety of which is incorporated by reference into this disclosure.

[0140] In some embodiments, boron compounds that may be used as non-coordinating anion activators in combination with activating cofactors in the preparation of the catalysts of the present disclosure include trisubstituted ammonium salts, such as trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N, N-Dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-Diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-Dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, Trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, Triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, Tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, tripropylammonium tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, as well as dialkylammonium salts such as di-(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, and dicyclohexylammonium tetrakis(pentafluorophenyl)borate, as well as other salts such as tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tropylium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, benzene(diazonium)tetraphenylborate, tropylium tetrakis(pentafluorophenyl)borate, fluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropylium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylphosphonium tetrakis(perfluoronaphthyl)borate, triethylsilylium tetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropylium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium tetrakis(perfluorobiphenyl)borate, triethyl These are silylium tetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0141] In some embodiments, a non-coordinating anion activator (L ** -H) d + (A d-) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

[0142] The catalyst precursor can also be activated with a cocatalyst or activator comprising a non-coordinating anion containing a non-metalloid-containing cyclopentadienide ion as described in US Patent Application Publication No. 2002 / 0058765(A1), and the present disclosure requires the addition of an activating cofactor to the catalyst precursor. A "compatible" non-coordinating anion is one that does not decompose neutrally when the initially formed complex decomposes. Furthermore, the anion does not transfer an anion substituent or fragment to the cation causing the formation of a neutral transition metal compound and neutral by-products from the anion. Exemplary non-coordinating anions useful according to the present disclosure are those that are compatible and stabilize the transition metal complex cation in the sense of balancing its ionic charge to +1, and still retain sufficient propensity to allow displacement by ethylenically or acetylenically unsaturated monomers during polymerization. These types of cocatalysts may be used with scavengers such as, but not limited to, tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, triethylaluminum, or trimethylaluminum.

[0143] The disclosed method can also use cocatalyst or activator compounds that are initially neutral Lewis acids but form cationic metal complexes and non-coordinating anions, or zwitterionic complexes, upon reaction with alkylated transition metal compounds. The alkylated metallocene compounds are formed from the reaction of the catalyst precursor with an activating cofactor. For example, tris(pentafluorophenyl)boron or aluminum acts to abstract hydrocarbyl ligands to produce the disclosed cationic transition metal complexes and stabilizing non-coordinating anions (see EP-A-0427697 and EP-A-0520732 for a description of similar Group 4 metallocene compounds). See also the methods and compounds of EP-A-0495375. For the formation of zwitterionic complexes using similar Group 4 compounds, see U.S. Pat. Nos. 5,624,878, 5,486,632, and 5,527,929.

[0144] Further neutral Lewis acids are known in the art and are suitable for abstracting formal anionic ligands, see in particular the review article by EY-X. Chen and TJ Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships", Chem. Rev., 100, 1391-1434 (2000).

[0145] When the cation of the non-coordinating anion activator is a Bronsted acid, such as a proton or a protonated Lewis base (excluding water), or a reducible Lewis acid, such as a ferrocenium or silver cation, or an alkali or alkaline earth metal cation, such as a cation of sodium, magnesium, or lithium, the molar ratio of catalyst precursor to activator can be any ratio. Combinations of the described activator compounds can also be used for activation.

[0146] When an ionic or neutral stoichiometric activator (such as NCA) is used, the molar ratio of catalyst precursor to activator is 1:10 to 1:1, 1:10 to 10:1, 1:10 to 2:1, 1:10 to 3:1, 1:10 to 5:1, 1:2 to 1.2:1, 1:2 to 10:1, 1:2 to 2:1, 1:2 to 3:1, 1:2 to 5:1, 1:3 to 1.2:1, 1:3 to 10:1, 1:3 to 2:1, 1:3 to 3:1, 1:3 to 5:1, 1:5 to 1:1, 1:5 to 10:1, 1:5 to 2:1, 1:5 to 3:1, 1:5 to 5:1, 1:1 to 1:1.2. The molar ratio of catalyst precursor to activating cofactor is 1:500-1:1, 1:100-100:1, 1:75-75:1, 1:50-50:1, 1:25-25:1, 1:15-15:1, 1:10-10:1, 1:5-5:1, 1:2-2:1, 1:100-1:1, 1:75-1:1, 1:50-1:1, 1:25-1:1, 1:15-1:1, 1:10-1:1, 1:5-1:1, 1:2-1:1, 1:10-2:1.

[0147] In some embodiments, the activator and activator / coactivator combinations include dimethylanilinium tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron, or a mixture of trialkylaluminum and dimethylanilinium tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron. In some embodiments, a scavenger compound is used in conjunction with the activator. Exemplary aluminum or boron alkyl moieties useful as scavengers are of the general formula R x J'Z'2, where J' is aluminum or boron, and R x is as defined above, and each Z′ is independently R x or halogens (Cl, Br, I), alkoxides (OR x) and different monovalent anionic ligands. Aluminum alkyls can include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, trimethylaluminum, and the like. Boron alkyls can include triethylboron. The scavenging compounds can be alumoxanes and modified alumoxanes, including methylalumoxane and modified methylalumoxane.

[0148] In some embodiments, the precatalyst and / or activator are combined with an alkylaluminum compound, such as a trialkylaluminum compound, prior to entering the reactor. For example, the alkylaluminum compound can be represented by the formula: RAl, where each R is independently C1-C 20 The alkyl groups, for example, the R groups are independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, pentyl, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isooctyl, n-octyl, nonyl, isononyl, n-nonyl, decyl, isodecyl, n-decyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl, and n-dodecyl, such as isobutyl, n-octyl, n-hexyl, and n-dodecyl. In some embodiments, the alkyl aluminum compound is selected from tri-isobutyl aluminum, tri-n-octylaluminum, tri-n-hexyl aluminum, and tri-n-dodecyl aluminum.

[0149] Chain Transfer Agents The polymerization process of the present disclosure may include polymerization in the presence of a chain transfer or chain shuttling agent.

[0150] Chain transfer agents include alkylaluminum compounds represented by the formula: RAl, where each R is independently a C1-C 18and R is an alkyl group, for example, each R is independently selected from methyl, ethyl, n-propyl, isopropyl, iso-butyl, n-butyl, t-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and their iso analogs.

[0151] In this process, hydrogen can also be used as a useful chain transfer agent in the reaction. In some embodiments, alternative chain transfer agents can be used in the process described in the present disclosure to reduce the need for hydrogen when it is not present or is used in limited amounts. In some embodiments, the chain transfer agent includes diethyl zinc and trialkyl aluminum, such as triisobutyl aluminum, tri-n-octyl aluminum, triethyl aluminum, etc., or mixtures thereof.

[0152] In some embodiments, the chain transfer agent can be used in a molar ratio of chain transfer agent to transition metal compound of from 1:1 to 150:1. In at least one embodiment, the molar ratio of chain transfer agent to transition metal compound can be greater than 5:1, or greater than 10:1, or greater than 20. Similarly, the molar ratio of chain transfer agent to transition metal compound can be less than 120:1, or less than 100:1, or less than 80:1.

[0153] Polymerization Process Syndiotactic rich ethylene-propylene copolymers can be made by contacting ethylene and propylene with at least one catalyst in any manner known in the art. Any homogeneous, bulk, solution (including supercritical) phase, slurry and gas phase polymerization process known in the art can be used. Such processes can be run in batch, semi-batch or continuous mode. Such processes can also be run in a single reactor or in a system with multiple reactors in series and / or parallel configuration. Homogeneous polymerization processes are preferred. A homogeneous polymerization process is defined as a process in which at least 90% by weight of the product is soluble in the reaction medium at the polymerization conditions. The monomer itself can also be used as a solvent / diluent in a bulk polymerization process. A bulk process is typically a process in which the monomer concentration in all feeds to the reactor is 70% by volume or greater. Alternatively, neither solvent nor diluent is present or added to the reaction medium (except for small amounts used as carriers for the catalyst system or other additives, or amounts typically found with the monomer (e.g., propane in propylene)).

[0154] Suitable diluents / solvents for polymerization include non-coordinating inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; normal paraffinic solvents (such as Norpar solvents available from ExxonMobil Chemical Company, Houston, Texas) or isoparaffinic solvents (such as Isopar solvents available from ExxonMobil Chemical Company, Houston, Texas) (Isopar™); cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and alkyl-substituted aromatic compounds such as toluene and / or xylene and / or ethylbenzene; perhalogenated hydrocarbons such as perfluorinated C 4~10Alkanes, chlorobenzene. Mixtures of any of the aforementioned hydrocarbon solvents can also be used. Suitable solvents also include liquid olefins that can act as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents, 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, are used as the solvent. In another embodiment, the solvent is not aromatic, and preferably aromatics are present in the solvent at less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0% by weight, based on the weight of the solvent.

[0155] The preferred polymerization can be carried out at any temperature and / or pressure suitable to obtain the desired polymer. Typical temperatures and / or pressures include temperatures ranging from about 50°C to about 200°C, about 55°C to about 150°C, about 58°C to about 120°C, preferably about 60°C to about 110°C, preferably about 60°C to about 90°C, and pressures ranging from about 0.35MPa to about 14MPa, preferably about 2MPa to about 13MPa, preferably about 4MPa to about 13MPa, preferably about 7MPa to about 12MPa, preferably about 9MPa to about 11.5MPa, preferably about 9MPa to about 11MPa. In some catalyst systems, the syndiotacticity of the ethylene-propylene copolymer varies with the polymerization temperature, and the selection of the temperature can be determined by the desired level of syndiotacticity of the ethylene-propylene copolymer. In one embodiment, the polymerization is carried out at a temperature of 60°C or higher with an upper temperature limit of 120°C, and a pressure of 9.5MPa or higher.

[0156] In one embodiment, the polymerization is carried out at a polymerization temperature equal to or greater than TP1, where TP1 = 0.9 x EXP (-0.005 x rr). Preferably, the polymerization temperature is at least TP2, where TP2 = 1.15 x EXP (-0.006 x rr). TP1 and TP2 are in °C, and rr is 13 is the triad tacticity index of syndiotactic ethylene-propylene copolymers measured using C NMR.

[0157] In some embodiments, hydrogen is present in the polymerization reactor at a partial 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 some embodiments, hydrogen is not added to the polymerization reactor, i.e., hydrogen is not added to the reactor, although it may be present from other sources, such as a hydrogen generating catalyst. Alternatively, the hydrogen concentration is 10,000 ppm or less in the feed, preferably 5,000 ppm or less.

[0158] The catalyst typically has a catalytic activity of greater than 10,000 kg of polymer per kg of catalyst, greater than 20,000 kg of polymer per kg of catalyst, greater than 50,000 kg of polymer per kg of catalyst, or greater than 100,000 kg of polymer per kg of catalyst when the polymerization is carried out in a continuous process. Similarly, the conversion of the olefin monomer is at least 10%, preferably greater than 20%, preferably greater than 30%, preferably greater than 50%, and preferably greater than 80%, based on the polymer yield and the mass of monomer entering the reaction zone.

[0159] The catalyst and activator may be charged to the reactor separately as a solution, neat liquid, suspension or slurry, or may be activated in-line just before the reactor, or may be preactivated and pumped to the reactor as an activated solution or slurry. In one embodiment, the catalyst and activator may be fed to the polymerization reactor in the form of a dry powder or slurry without the need to prepare a homogenous catalyst solution by dissolving the catalyst in a support solvent.

[0160] The syndiotactic rich ethylene-propylene copolymer may also include at least one other monomer and may be prepared by contacting ethylene, propylene and at least one other monomer with at least one catalyst in any manner known in the art. Suitable other monomers include substituted or unsubstituted C2-C40 alpha olefins, preferably C2-C20 alpha olefins, preferably C2-C12 alpha olefins, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment of the present invention, the monomers include propylene and an optional comonomer comprising one or more of ethylene or C4-C40 olefins, preferably C4-C20 olefins, or preferably C6-C12 olefins. The C4-C40 olefin monomer may be linear, branched, or cyclic. The C4-C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. Exemplary C2-C40 olefin monomers and optional comonomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, preferably norbornene, norbornadiene, and dicyclopentadiene. Preferably, the polymer is a syndiotactic rich ethylene-propylene-hexene terpolymer or a syndiotactic rich ethylene-propylene-octene terpolymer.

[0161] The polymerization can be carried out in multiple reactors in series and parallel configurations. In one embodiment, the copolymer is a reactor blend of a first polymer component and a second polymer component. Thus, the comonomer content of the copolymer can be adjusted by adjusting the comonomer content of the first polymer component, adjusting the comonomer content of the second polymer component, and / or adjusting the ratio of the first polymer component to the second polymer component present in the copolymer.

[0162] The syndiotactic rich ethylene-propylene copolymer according to various embodiments may be a blend of at least two syndiotactic rich ethylene-propylene copolymers. The blend may be prepared using two or more reactors in series or parallel. Preferably, the blend has a bimodal molecular weight distribution or a broad molecular weight distribution with MWD>3.0. The blend may also have a bimodal composition distribution or a broad composition distribution. Preferably, one component has an ethylene content in the range of 0.2-5 wt.% and one component has an ethylene content in the range of 2-15 wt.%. Each of the blend components may be prepared in a different reactor if multiple reactors are used. This is accomplished by operating the reactors at different polymerization conditions and / or using different catalysts in each reactor. The syndiotactic rich ethylene-propylene copolymer blend may also be produced using multiple catalysts in a single reactor. In one embodiment, one component has a Mw in the range of 10,000 to 30,000 g / mol and an ethylene content in the range of 0.2 to 3 wt.%, and one component has a Mw in the range of 30,000 to 200,000 g / mol and an ethylene content in the range of 2 to 10 wt.%.

[0163] In one embodiment, a solution polymerization process is preferred. A solution polymerization process may be used to carry out the polymerization reaction disclosed herein in any suitable manner known to those skilled in the art. In certain embodiments, the polymerization process may be carried out in a continuous polymerization process. The term "batch" refers to a process in which the complete reaction mixture is removed from the polymerization reaction vessel at the end of the polymerization reaction. In contrast, in a continuous polymerization process, one or more reactants are continuously introduced into the reaction vessel and a solution containing the polymer product is simultaneously or nearly simultaneously removed. Solution polymerization refers to a polymerization process in which the polymer produced is soluble in a liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerization is typically homogeneous. Such a system is preferably not turbid, as described in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng. Chem. Res. 29, 2000, 4627.

[0164] In a typical solution process, catalyst components, solvent, monomers and hydrogen (if used) are fed under pressure to one or more reactors. Temperature control in the reactors can generally be obtained by balancing the heat of polymerization and by reactor cooling with reactor jackets or cooling coils to cool the reactor contents, autorefrigeration, pre-cooled feeds, vaporization of the liquid medium (diluent, monomer or solvent), or a combination of all three. Adiabatic reactors with pre-cooled feeds can also be used. Monomers are dissolved / dispersed in a solvent before being fed to the first reactor or dissolved in the reaction mixture. Solvents and monomers are generally purified to remove potential catalyst poisons before entering the reactor. Feedstocks may be heated or cooled before being fed to the first reactor. Additional monomer and solvent may be added to the second reactor, which may be heated or cooled. Catalyst / activators may be fed to the first reactor or split between the two reactors. In solution polymerization, the polymer produced is molten and remains dissolved in the solvent under reactor conditions, forming a polymer solution (also called the effluent).

[0165] The solution polymerization process of the present invention uses a stirred tank reactor system comprising one or more stirred polymerization reactors. In general, the reactors should be operated under conditions that achieve thorough mixing of the reactants. In a multiple reactor system, the first polymerization reactor is preferably operated at a lower temperature. The residence time in each reactor depends on the design and capacity of the reactor. The catalyst / activator may be fed only to the first reactor or split between the two reactors. In alternative embodiments, loop reactors and plug flow reactors can be used in the present invention.

[0166] The polymer solution is then discharged from the reactor as an effluent stream, and the polymerization reaction is typically quenched with a coordinating polar compound to prevent further polymerization. Upon exiting the reactor system, the polymer solution passes through a heat exchanger system on a route and is sent to a devolatilization system and a polymer finishing process. The dilute phase and volatile materials removed downstream of the liquid phase separation can be recycled to become part of the polymerization feed.

[0167] The polymer can be recovered from the effluent of either reactor or the combined effluent by separating the polymer from the other components of the effluent. Conventional separation means can be used. For example, the polymer can be recovered from the effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by heating and vacuum stripping the solvent or other medium with heat or steam. One or more conventional additives, such as antioxidants, can be incorporated into the polymer during the recovery procedure. Other recovery methods, such as by use of a lower critical solution temperature (LCST) followed by devolatilization, are also envisioned.

[0168] In an embodiment, the polymerization is carried out in a solution process 1) at a temperature of 50° C. or more (preferably 60° C. or more, preferably 65° C. or more) with an upper limit of 120° C. or less, alternatively 110° C. or less, alternatively 100° C. or less; 2) at a pressure of from atmospheric pressure to 15 MPa (preferably 1-15 MPa, preferably 2-14 MPa, preferably 4-13 MPa); 3) in an aliphatic hydrocarbon solvent (e.g., 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; preferably, aromatics (such as toluene), based on the weight of the solvent. Preferably, the polymerization is carried out in a solvent at less than 1% by weight, preferably less than 0.5% by weight, preferably 0% by weight), 4) ethylene is present in the polymerization reactor at a concentration of 2 moles / liter or less), 5) the polymerization is preferably carried out in one reaction zone, and 6) the productivity of the catalyst compound is 5,000 kg or more of polymer per kg of catalyst (preferably 10,000 kg or more of polymer per kg of catalyst, e.g., 20,000 kg or more of polymer per kg of catalyst, e.g., 40,000 kg or more of polymer per kg of catalyst, e.g., 50,000 kg or more of polymer per kg of catalyst, e.g., the catalyst efficiency can be from about 10,000 kg of polymer per kg of catalyst to about 500,000 kg of polymer per kg of catalyst).

[0169] The composition of the syndiotactic rich ethylene-propylene copolymer according to various embodiments varies with the feed composition and concentration of monomers in the polymerization reactor. In one embodiment, the molar ratio of ethylene to propylene in the feed is 0.29 or less, preferably 0.25 or less, preferably 0.20 or less, preferably 0.15 or less, preferably 0.10 or less. In another embodiment, the molar ratio of ethylene to propylene in the feed is 0.03 or more, preferably 0.035 or more.

[0170] In a preferred embodiment, the polymerization is carried out in a solution process at a pressure of 9 MPa or more, a temperature of 60° C. or more with an upper temperature limit of 120° C., and a catalyst efficiency of 50,000 kg polymer per kg catalyst to about 600,000 kg polymer per kg catalyst.

[0171] Preferably, the polymerization is carried out in a solution process at a pressure of 9 MPa or greater, a feed molar ratio of ethylene to propylene of 0.03 or greater, and a catalyst efficiency of 50,000 kg polymer / kg catalyst to about 600,000 kg polymer / kg catalyst.

[0172] The syndiotactic ethylene-propylene copolymers can be used in a variety of end uses. Such end uses can be made by methods known in the art. Exemplary end uses are films, film-based products, diaper backsheets, house wraps, wire and cable coating compositions, articles formed by molding techniques such as injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End uses also include products made from the films, such as bags, packaging, and personal care films, pouches, medical products such as medical films and intravenous (IV) bags, and the like. End uses also include thermoplastic polyolefin (TPO) roof sheeting, foams, nonwovens, 3D printing, and recycling solutions. The syndiotactic ethylene-propylene copolymers can also be used as viscosity index modifiers for lubricants.

[0173] Gel Permeation Chromatography with Three Detectors (GPC-3D) Molecular weights (number average (Mn), weight average (Mw), and z-average (Mz)) are determined using an Agilent PL220 high temperature GPC (gel permeation chromatograph) equipped with an online differential refractive index (DRI), light scattering (LS), and viscometer (VIS) detector. It uses three Polymer Laboratories PLgel 10 μm Mixed-B columns for separation at a nominal flow rate of 0.5 ml / min and a nominal injection volume of 300 microliters. The detectors and columns were housed in an oven maintained at 145° C. Details of these detectors and their calibration are described, for example, in Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) by T. Sun, P. Brant, RR Chance, and WW Graessley, which is incorporated herein by reference.

[0174] Solvent for GPC testing was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 micrometer Teflon® filter. The TCB was then degassed with an online degasser before being placed into the GPC. Polymer solutions were prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, and then heating the mixture at 160 °C for approximately 2 hours with continuous stirring. All quantities were measured gravimetrically. Injection concentrations were 1.0-2.0 mg / mL, with lower concentrations used for higher molecular weight samples. The concentration c at each point in the chromatogram was calculated using the baseline-subtracted DRI signal I using the following equation: DRI Calculated from: c=K DRI I DRI / (dn / dc) In the formula, K DRIis a constant determined by calibrating the DRI with a series of monodisperse polystyrene standards having molecular weights ranging from about 600 to 11M, and (dn / dc) is the refractive index increment of the system. For purposes of this invention and the claims thereto, (dn / dc)=0.1048 for all ethylene-propylene copolymers and homopolymers. The units of parameters used throughout this description of the GPC method are: concentration, g / cm 3 the molecular weight is expressed in g / mol, and the intrinsic viscosity is expressed in dL / g.

[0175] The light scattering detector was a high temperature 18 angle Dawn Heleos (Wyatt Technology, Inc.) The molecular weight M at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (MB Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971).

number

number

[0176] g' vis is defined as the ratio of the intrinsic viscosity of a syndiotactic propylene-ethylene copolymer to that of an isotactic rich polypropylene-ethylene copolymer of equal molecular weight and composition, and was calculated using the output of the SEC-DRI-LS-VIS method as follows: Average intrinsic viscosity of the sample [η] avg was calculated by the following formula:

number

[0177] g' vis is defined as follows:

number

[0178] Differential Scanning Calorimetry (DSC) The peak melting point Tm (also called melting point), peak crystallization temperature Tc (also called crystallization temperature), glass transition temperature (Tg), heat of fusion (ΔHf or Hf), and percent crystallinity were determined using the following DSC procedure according to ASTM D3418-03. Differential scanning calorimetry (DSC) data was obtained using a TA Instruments model Q200 instrument. Samples of approximately 5-10 mg mass were sealed in aluminum hermetic sample pans. DSC data was recorded by first gradually heating the sample to 200°C at a rate of 10°C / min. The sample was held at 200°C for 2 minutes, then cooled to -90°C at a rate of 10°C / min, followed by isothermalization for 2 minutes and heating to 200°C at 10°C / min. Both the first cycle thermal event and the second cycle thermal event were recorded. The area under the endothermic peak was measured and used to determine the heat of fusion and percent crystallinity. Percent crystallinity was calculated using the formula [area under melting peak (J / g) / B(J / g)]×100, where B is the heat of fusion of 100% crystalline homopolymer of the major monomeric component. These B values ​​are taken from Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 189 J / g (B) is used for the heat of fusion of 100% crystalline polypropylene, and a value of 290 J / g is used for the heat of fusion of 100% crystalline polyethylene. Melting and crystallization temperatures reported in this disclosure were obtained during the second heating / cooling cycle, unless otherwise noted.

[0179] Carbon NMR The comonomer content and sequence distribution of the polymers can be determined by methods well known to those skilled in the art. 13C nuclear magnetic resonance (NMR). 13 Polymer samples for C NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 at a concentration of 67 mg / mL at 140 °C and samples were analyzed at 125 MHz or higher using a 10 mm cryoprobe using a 90° pulse and gated decoupling for at least 512 accumulations. 13 Recorded at 120° C. using a Bruker NMR spectrometer with C NMR frequencies. Chemical shifts of the solvent 1,1,2,2-tetrachloroethane-d2 were referenced to 74.24 ppm with the main methyl isotactic peak at 21.83 ppm. Calculations involved in the characterization of polymers by NMR follow the work of Bovey, FA (1969) in Polymer Conformation and Configuration, Academic Press, New York, and Randall, J. (1977) in Polymer Sequence Determination, Carbon-13 NMR Method, Academic Press, New York. [Table 2]

[0180] The simultaneous equations are solved using the linest function in Excel with the output being the triad area, assuming the constants are 0. Y is defined as the area of ​​the chemical shift region and X is the triad contribution for each region. This can then be converted to the mole fraction of the triad by dividing the individual areas by the sum, for example, PPP(area) / (PPP+PPE+EPE+PEP+EEP+EEE) from the linest.

[0181] %rr(PP+EP) is calculated using the CH3 area of ​​propylene as follows: [Table 3]

[0182] Chemical shift assignments for ethylene-propylene copolymers are described in "A Review of High Resolution Liquid Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers" by Randall, Polymer Reviews, 29:2,201-5 317 (1989). Copolymer content, molar and mass %, triad sequencing, and dyad calculations are also calculated and described in the methods established by Randall in this paper.

[0183] The calculation of r1r2 is r1r2=4×[EE]×[PP] / [EP] 2 where [EE], [EP], and [PP] are triad molar concentrations, E is ethylene, and P is propylene. The calculation of P run length (also called propylene run# and P run#) is based on the formula P run#=([EPE]+0.5×[EPP])×100, where [EPE], [EPP] are triad molar concentrations, E is ethylene, and P is propylene.

[0184] Unless otherwise stated, the ethylene content of ethylene-propylene copolymers was determined using FTIR according to ASTM D3900. The compositions of other polymers were determined by methods well known to those skilled in the art. 13 C NMR can be used to obtain the ethylene content. In the claims of this disclosure, the ethylene content from FTIR is used.

[0185] Small Amplitude Oscillatory Shear (SAOS): Dynamic shear melt rheology data were measured on an Advanced Rheometrics Expansion System (ARES) using parallel plates (diameter = 25 mm) in dynamic mode under nitrogen atmosphere. For all experiments, the rheometer was thermally stabilized at 190 °C for at least 30 minutes before inserting a compression molded sample of the resin (polymer composition) onto the parallel plates. To determine the viscoelastic behavior of the samples, a frequency sweep ranging from 0.01 to 385 rad / s was performed at a temperature of 190 °C under a constant strain of 10%. A nitrogen flow was circulated in the sample oven to minimize chain extension or crosslinking during the experiment. A sinusoidal shear strain is applied to the material. If the strain amplitude is small enough, the material behaves linearly. As one skilled in the art will recognize, the resulting stress may also oscillate sinusoidally at the same frequency, but shifted by a phase angle δ relative to the strain wave. For purely elastic materials, δ=0 degrees (stress is in phase with strain) and for purely viscous materials, δ=90 degrees. For viscoelastic materials, 0<δ<90. Complex viscosity, loss modulus (G") and storage modulus (G') as a function of frequency are provided by small amplitude oscillatory shear testing. Dynamic viscosity is also called complex viscosity or dynamic shear viscosity. The phase or loss angle δ is the arctangent of the ratio of G" (shear loss modulus) to G' (shear storage modulus).

[0186] Melt flow rate (MFR) is measured according to ASTM D1238-13 at 230° C. and 2.16 kg load. High load melt flow rate (MFR HL) is measured according to ASTM D1238 at 230° C. and 21.6 kg load.

[0187] Additional Embodiments The following additional embodiments are contemplated as being within the scope of the present disclosure.

[0188] Embodiment A: A syndiotactic ethylene-propylene copolymer comprising: a) 5-15% by weight ethylene and 85-95% by weight propylene; b) 60-90% rr triads; c) a Mw(LS) from 10 to 250 kg / mol; and d) no substantial melting peaks with a peak heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min.

[0189] Embodiment B: A syndiotactic ethylene-propylene copolymer as described in embodiment A having from 5 to 10% by weight ethylene.

[0190] Embodiment C: A syndiotactic ethylene-propylene copolymer according to embodiment A or B having 75 to 85% rr triads.

[0191] Embodiment D: A syndiotactic ethylene-propylene copolymer according to any one of embodiments A to C, which does not exhibit a melting point in the second heating cycle as measured by differential scanning calorimetry at a scan rate of 10° C. / min.

[0192] Embodiment E: A syndiotactic ethylene-propylene copolymer according to any one of embodiments A to D, having a MFR measured at 2.16 kg and 230° C. of 0.1 to 650 g / 10 min.

[0193] Embodiment F: A syndiotactic ethylene-propylene copolymer of any one of embodiments A through E having a glass transition temperature of 0° C. or less.

[0194] Embodiment G: Mass Average Molecular Weight (M) from Light Scattering W,LS The syndiotactic ethylene-propylene copolymer according to any one of embodiments A to F, wherein the molecular weight of the polymer is from 10 to 120 kg / mol.

[0195] Embodiment H: A syndiotactic ethylene-propylene copolymer according to any one of embodiments A to G, having a molecular weight distribution (Mw, DRI / Mn, DRI) of 1.2 to 2.5.

[0196] Embodiment I: 13 The syndiotactic ethylene-propylene copolymer of any one of embodiments A-H, wherein the relationship between [EPP] from C NMR and C2 wt% from FTIR is 1.9833 x C2 wt% - 0.0818 < [EPP] < 1.3333 x C2 wt% + 0.09.

[0197] Embodiment J: 13 The syndiotactic ethylene-propylene copolymer of any one of embodiments A-I, wherein the relationship between [EEP] from C NMR and C2 wt% from FTIR is 0.2931 x C2 wt% - 0.0187 < [EEP] < 0.303 x C2 wt% - 0.0045.

[0198] Embodiment K: 13 The syndiotactic ethylene-propylene copolymer of any one of embodiments A-J, wherein the relationship between [PPP] from C NMR and C2 mass% from FTIR is -2.8 x C2 mass% + 0.878 < [PPP] < -2.8154 x C2 mass% + 1.0451.

[0199] Embodiment L: 13 The syndiotactic ethylene-propylene copolymer of any one of embodiments A-K, wherein the relationship between [PEP] from C NMR and C2 mass% from FTIR is 0.8923 x C2 mass% - 0.0021 < [PEP] < 0.9333 x C2 mass% + 0.03.

[0200] Embodiment M: 13 The syndiotactic ethylene-propylene copolymer of any one of embodiments A through L, having an [EEE] from C NMR of less than 0.008.

[0201] Embodiment N: 13The syndiotactic ethylene-propylene copolymer according to any one of Embodiments A to M, wherein the relationship between [EE] from 13C NMR and C2 mass% from FTIR is 0.2×C2 mass% - 0.016 < [EE] < 0.1292×C2 mass% + 0.0082.

[0202] Embodiment O: 13 The syndiotactic ethylene-propylene copolymer according to any one of Embodiments A to N, wherein the relationship between the propylene run # from 13C NMR and C2 mass% from FTIR is 110.67×C2 mass% - 4.7 < [P run #] < 97.143×C2 mass% + 4.7286.

[0203] Embodiment P: 13 The syndiotactic ethylene-propylene copolymer according to any one of Embodiments A to O, wherein r1r2 from 13C NMR is less than 8.0.

[0204] Embodiment Q: The syndiotactic ethylene-propylene copolymer according to any one of Embodiments A to P, wherein the relationship between Tg from DSC and C2 mass% from FTIR is -190×C2 mass% - 9.15 < Tg < -175×C2 mass% + 1.725.

[0205] Embodiment R: g' from GPC vis The relationship between vis and MW,LS is g'

[0206] Embodiment S: The syndiotactic ethylene-propylene copolymer according to any one of Embodiments A to R, which exhibits pellet stability after aging at 40°C and 1 psig for 3 months.

[0207] Embodiment T: A method of making a syndiotactic propylene copolymer comprising: contacting, in a homogeneous phase, propylene and ethylene with a catalyst system comprising an activator and a catalyst compound; and obtaining a syndiotactic propylene copolymer comprising: (a) 85-95% by weight propylene based on the weight of the polymer; (b) 60-90% rr triads; (c) a Mw(LS) of 10-250 kg / mol; and (d) no substantial melting peaks and a peak heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min.

[0208] Embodiment U: The method of embodiment T, carried out at a temperature of about 50° C. to about 110° C. and a pressure in the range of about 1 MPa to about 14 MPa.

[0209] Embodiment V: The method of embodiment T, carried out at a temperature of about 50° C. to about 110° C. and a pressure in the range of about 3 MPa to about 14 MPa.

[0210] Embodiment W: The process is carried out at a polymerization temperature equal to or greater than TP1, TP1=0.9×EXP(−0.005×rr), where TP1 is in ° C. and rr is 13 The method of any one of embodiments T through V, wherein the triad tacticity index is measured using C NMR.

[0211] Embodiment X: The method of any one of embodiments T through W, wherein the polymerization is carried out in a solution process at a pressure of 9 MPa or more, a temperature of about 50° C. to about 120° C., and a catalyst efficiency of 50,000 kg or more of polymer per kg of catalyst.

[0212] Embodiment Y: The method of any one of embodiments T through X, wherein the polymerization is carried out in a solution process at a pressure of 9 MPa or greater, a molar ratio of ethylene feed to propylene feed of about 0.01 to about 0.2, and a catalyst efficiency of 50,000 kg of polymer or greater per kg of catalyst.

[0213] Embodiment Z: The catalyst system comprises a catalyst compound represented by formula (1a): [ka] During the ceremony, M is zirconium or hafnium; G is a bridging group; each X is independently a hydrido radical, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl, or both X's are linked and attached to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both together are an olefin, diolefin or aryne ligand, or both X's may independently be halogen, alkoxide, aryloxide, amide, phosphide or other monovalent anionic ligand, or both X's may be linked to form a dianionic chelating ligand; Each R a and R b are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, or a polar radical, and optionally two or more adjacent substituents may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic substituent, with the proviso that each R a is the same, and each R b are the same, and the compound is C s Symmetric or pseudo-C s Allowing for symmetry, Each R c are independently symmetric or pseudosymmetric substituents relative to one another and are selected from hydrogen or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl radical; Each R dThe method of any one of embodiments T through Y, wherein each is a symmetric or pseudosymmetric substituent relative to the other and is independently selected from hydrogen or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl radical.

[0214] Embodiment AA: M is zirconium, X is methyl or chloro, G is di(para-triethylsilylphenyl)methylene or diphenylmethylene, and each R d , R a and R c is hydrogen, and each R b The method of any one of embodiments TZ, wherein is methyl, ethyl, propyl, or butyl.

[0215] Embodiment BB: X is methyl, G is di(para-triethylsilylphenyl)methylene, and each R d , R a and R c is hydrogen, and each R b The method of any one of embodiments T through AA, wherein is tert-butyl.

[0216] Embodiment CC: The activator is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis( The method of any one of embodiments T through BB, wherein the cation exchange reaction is selected from one or more of: tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], di(hydrogenated tallow)methylammonium tetrakis(perfluorophenyl)borate, di(hydrogenated tallow)methylammonium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, and dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate. EXAMPLES

[0217] Syndiotactic ethylene-propylene copolymers were produced in a continuous solution polymerization process. Polymerizations of Examples G1-G20 listed in Table 1 were carried out in a continuous stirred tank reactor system. A 1 liter autoclave reactor was equipped with a stirrer, pressure control, and water cooling / steam heating element with temperature control. The reactor was operated at liquid-filled conditions with the reactor pressure above the boiling point pressure of the reactant mixture to keep the reactants in liquid phase. Isohexane and propylene were pumped to the reactor by Pulsa feed pumps. Ethylene and H2 flowed as gases under their own pressure through a Brooks flow controller. Ethylene, propylene, and H2 feeds were combined into one stream and then mixed with a pre-chilled isohexane stream that had been cooled to at least 0°C. The mixture was then fed to the reactor through a single line. A scavenger solution (tri-n-octylaluminum (TNOA) (25 wt % in hexane, Sigma Aldrich) in isohexane) was also added to the combined solvent and monomer stream just prior to entering the reactor to further reduce any catalyst poisoning. The catalyst solution was fed to the reactor using an ISCO syringe pump through separate lines. Isohexane (used as solvent) and monomers (e.g., ethylene and propylene) were purified over beds of alumina and molecular sieves. Toluene for preparing the catalyst solution was purified by the same technique. The reactor pressure for all examples was approximately 350 psig.

[0218] The polymer made in the reactor exited through a back pressure control valve that reduced the pressure to atmospheric pressure. This caused the unconverted monomers in the solution to evaporate into a vapor phase that was discharged from the top of the gas-liquid separator. The liquid phase, which mainly contained polymer and solvent, was collected for polymer recovery. The collected sample was first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90°C for about 12 hours. The vacuum oven dried sample was weighed to obtain the yield.

[0219] The catalyst was premixed with the activator in toluene at about 1:1 molar ratio. For all of the examples G1-G20, diphenylmethylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (catalyst #1) was used. The catalyst was preactivated with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (activator A). The detailed process conditions and some characterization data are listed in Table 1. The catalyst and TONA feed rates can be adjusted to achieve the target conversion. The chemical structures of catalyst #1 and catalyst #2 are shown below: [ka] [Table 4-1] [Table 4-2] [Table 4-3] [Table 4-4]

[0220] Examples G21-G44 were prepared according to the same procedure used to make Examples G1-G20, except that the catalyst used was di(para-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (Catalyst #2). The catalyst was preactivated with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (Activator A). The detailed process conditions and some characterization data are listed in Table 2. The catalyst and TONA feed rates can be adjusted to achieve the target conversion. [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4] [Table 5-5]

[0221] Examples G45-G59 were prepared according to the same procedure used to make Examples G1-G20, except that the catalyst used was di(para-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (Catalyst #2). This catalyst was preactivated with N,N-dimethylanilinium tetrakis(heptafluoro-2-naphthyl)borate (Activator B). The detailed process conditions and some characterization data are listed in Table 3. Both the catalyst and TONA feed rate can be adjusted to achieve the target conversion. [Table 6-1] [Table 6-2] [Table 6-3]

[0222] Polymerizations of Examples M1-M8 listed in Table 4 were carried out using a solution process in a 28 liter continuous stirred tank reactor (autoclave reactor). The autoclave reactor was equipped with an agitator, pressure control devices, and insulation to prevent heat loss. The reactor temperature was controlled by controlling the catalyst feed rate, and heat removal was achieved by feed cooling. All solvents and monomers were purified over beds of alumina and molecular sieves. The reactor was operated liquid-full at a pressure of 11.03 MPa. Isohexane was used as the solvent. It was fed to the reactor using a turbine pump, and its flow rate was controlled by a downstream mass flow controller. The compressed and liquefied propylene feed was controlled by a mass flow controller. Hydrogen (if used) was fed to the reactor through a thermal mass flow controller. The ethylene feed was also controlled by a mass flow controller. Ethylene, propylene, and hydrogen (if used) were mixed with isohexane vapor at separate addition points via a manifold. A 3 wt % mixture of tri-n-octylaluminum in isohexane was also added to the manifold through a separate line (used as a scavenger), and the combined mixture of monomer, scavenger, and solvent was fed to the reactor through a single line.

[0223] The catalyst used in the polymerization of Examples Nos. M1-M7 was di(para-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (catalyst #2). This catalyst was preactivated with N,N-dimethylanilinium tetrakis(heptafluoro-2-naphthyl)borate (activator B) in about a 1:1 molar ratio in 4 liters of toluene. In Example M8, di(para-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (catalyst #2) was premixed with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (activator A) in about a 1:1 molar ratio in 4 liters of toluene. After the solids had dissolved, the catalyst solution was loaded into an ISCO pump and metered into the reactor with stirring. The catalyst feed rate was controlled along with the monomer feed rate and reaction temperature as shown in Table 4.

[0224] The polymers produced are also listed in Table 4. The reactor product stream was treated with a trace amount of methanol to terminate the polymerization. The mixture was then freed from the solvent in a low pressure flash separation, treated with Irganox™ 1076, and then subjected to a devolatilizing extruder process. The dried polymer was then pelletized. [Table 7-1] [Table 7-2]

[0225] The polymer made in Example M8 was pelletized into spheres (about 26 pellets / gram pellet size). The pellets were subjected to stability testing. The pellet stability testing was carried out in an oven with a ventilator at 40°C and 1 psig pressure for 90 days. Approximately 35 grams of sample was placed in a 100 ml glass beaker with a custom weight on top so that the pressure applied to the top of the pellets was 1 psig. The pellets were poured out of the glass beaker after 90 days, and well-dispersed individual pellets were observed.

[0226] A set of comparative examples are listed in Table 5. Examples C1-C22 were prepared following the same procedure used to make Examples G1-G20, except that (1) diphenylmethylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (catalyst #1) and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (activator A) were used in Examples C1-C6, and (2) di(para-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (catalyst #2) and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (activator A) were used in Examples C7-C20. Detailed process conditions and some characterization data are listed in Table 5. Both the catalyst and TONA feed rate can be adjusted to achieve the target conversion. [Table 8-1] [Table 8-2] [Table 8-3] [Table 8-4]

[0227] Table 6 lists the commercially available Vistamaxx™ polymers available from ExxonMobil Chemical Company as reference materials. Vistamaxx™ polymers are isotactic rich propylene-ethylene copolymers. CV1-CV4 are Vistamaxx™ 3000, Vistamaxx™ 6102, Vistamaxx™ 6502, Vistamaxx™ 3588FL, respectively. [Table 9]

[0228] FIG. 1 shows the linear relationship between the ethylene-propylene copolymers based on syndiotactic polypropylene according to the present disclosure and the non-syndiorich EP Vistamaxx™ reference samples listed in Table 6, respectively. 13 Shows [PPP] from C NMR vs. Mw,LS from GPC. At similar MW, the syndiotactic polypropylene-based ethylene-propylene copolymers according to the present disclosure show higher [PPP] values ​​compared to the reference samples.

[0229] Figure 2 is a photograph of sample M8 immediately after removal from the oven. Sample M8 shows good pellet stability after aging in an oven at 40°C and 1 psig pressure for 90 days. The sample was placed in a beaker with a custom weight on top so that the pressure was 1 psi above atmospheric pressure. After removal from the oven after 90 days, the pellets remained as individual pellets.

[0230] FIG. 3 shows the C2 mass % and β-aminobutyric acid (ABA) data from FTIR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. 13 The two trend lines show the [EPP] from C NMR and the C2 mass% from FTIR for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention. 13 Establish a relationship with [EPP] from C NMR.

[0231] FIG. 4 shows the C2 mass % and β-aminobutyric acid (ABA) data from FTIR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. 13 The two trend lines show the [EEP] from C NMR and the C2 mass% from FTIR for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention. 13 Establish a relationship with [EEP] from C NMR.

[0232] FIG. 5 shows the C2 mass % and β-aminobutyric acid (ABA) data from FTIR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. 13The two trend lines show the [PPP] from C NMR and the C2 mass% from FTIR for the syndiotactic polypropylene-based ethylene-propylene copolymer of the present invention. 13 Establish the relationship with [PPP] from C NMR.

[0233] FIG. 6 shows the ethylene content and ethylene / propylene content from FTIR for syndiotactic polypropylene-based ethylene-propylene copolymers according to the present disclosure. 13 The two trend lines show the ethylene content and [PEP] from FTIR for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention. 13 Establish a relationship with [PEP] from C NMR.

[0234] FIG. 7 shows the C2 mass % and β-aminobutyric acid (ABA) data from FTIR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. 13 The two trend lines show the [EE] from C NMR and the [EE] from FTIR for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention. 13 Establish a relationship with [EE] from C NMR.

[0235] FIG. 8 shows the C2 mass % and β-aminobutyric acid (ABA) data from FTIR for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. 13 The two trend lines show the propylene run# from C NMR and the C2 mass% from FTIR for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention. 13 Establish a relationship with propylene run# from C NMR.

[0236] FIG. 9 shows the C2 mass% from FTIR and the glass transition temperature T from DSC for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. gTwo trend lines establish the relationship between wt% C2 from FTIR and Tg from DSC for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention.

[0237] FIG. 10 shows the g′ from GPC for a syndiotactic polypropylene-based ethylene-propylene copolymer according to the present disclosure. vis and M W,LS The two trend lines show the g' from GPC for the syndiotactic polypropylene-based ethylene-propylene copolymers of the present invention. vis A relationship between the mass average MW from the light scattering from GPC and the molecular weight is established.

[0238] All documents described in this disclosure, including any priority documents and / or test procedures, are incorporated by reference into this disclosure to the extent that they are not inconsistent with this disclosure.As is clear from the above general description and specific embodiments, the form of the present disclosure has been illustrated and described, but various modifications can be made without departing from the spirit and scope of the present disclosure.Therefore, the present disclosure is not intended to be limited thereby.

[0239] For the sake of brevity, only certain ranges are expressly disclosed in this disclosure. However, a range from any lower limit may be combined with any upper limit to describe a range that is not expressly described, and similarly, a range from any lower limit may be combined with any other lower limit to describe a range that is not expressly described, and similarly, a range from any upper limit may be combined with any other upper limit to describe a range that is not expressly described. Furthermore, a range includes every point or individual value between its endpoints, even if not expressly described. Thus, every point or individual value may serve as its own lower limit or upper limit to be combined with any other point or individual value or any other lower limit or upper limit to describe a range that is not expressly described.

[0240] Unless otherwise specified, the phrases "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned herein, unless such steps, elements, or materials do not affect the basic and novel characteristics of the disclosure and further exclude impurities and variations normally associated with the elements and materials used.

[0241] Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements is also contemplated when the composition, element, or list of elements is preceded by the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is," and vice versa.

[0242] The terms "a" and "the," as used in this disclosure, are understood to encompass the plural as well as the singular.

[0243] Various terms are defined above. If a term used in the claims is not defined above, it should be given the broadest definition that one of ordinary skill in the art would give to that term, as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are incorporated by reference in their entirety to the extent such disclosure is not inconsistent with this application and for all jurisdictions where such incorporation is permitted.

[0244] The foregoing description of the disclosure illustrates and describes the disclosure. In addition, the disclosure shows and describes only preferred embodiments, but as stated above, it should be understood that the disclosure can be used in various other combinations, modifications, and environments, and can be changed or modified within the scope of the concepts expressed in the disclosure, commensurate with the teachings above and / or the skill or knowledge of the relevant art. While the above is directed to embodiments of the disclosure, other and further embodiments of the disclosure can be devised without departing from the basic scope of the disclosure, the scope of which is determined by the following claims.

[0245] The above-described embodiments are intended to illustrate the best modes known for carrying out the present invention and are further intended to enable those skilled in the art to utilize the present disclosure in such or other embodiments, with various modifications as required by a particular application or use. Therefore, the present specification is not intended to limit the present disclosure to the forms disclosed herein. Also, the appended claims are intended to be construed to include alternative embodiments.

Claims

1. a) 5 to 15% by weight of ethylene and 85 to 95% by weight of propylene; b) 60-90% rr triads; c) Mw(LS) of 10 to 250 kg / mol; d) Syndiotactic ethylene-propylene copolymers containing no substantial melting peaks with peak heats of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10° C. / min.

2. 2. The syndiotactic ethylene-propylene copolymer of claim 1 having 5 to 10% by weight of ethylene.

3. 2. The syndiotactic ethylene-propylene copolymer of claim 1 having 75 to 85% rr triads.

4. 10. The syndiotactic ethylene-propylene copolymer of claim 1, which exhibits no melting point in the second heating cycle as measured by differential scanning calorimetry at a scan rate of 10°C / min.

5. 2. The syndiotactic ethylene-propylene copolymer according to claim 1, having an MFR measured at 2.16 kg and 230° C. of 0.1 to 650 g / 10 min.

6. 2. The syndiotactic ethylene-propylene copolymer of claim 1, having a glass transition temperature of 0° C. or less.

7. Mass average molecular weight (M Ｗ，ＬＳ 2. The syndiotactic ethylene-propylene copolymer of claim 1, wherein the molecular weight of the polymer is 10 to 120 kg / mol.

8. 2. The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the molecular weight distribution (Mw, DRI / Mn, DRI) is 1.2 to 2.

5.

9. １３ 2. The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the relationship between [EPP] determined by C NMR and C2 mass% determined by FTIR is 1.9833 × C2 mass% −0.0818 < [EPP] < 1.3333 × C2 mass% + 0.

09.

10. １３ 2. The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the relationship between [EEP] from C NMR and C2 mass% from FTIR is 0.2931 × C2 mass% −0.0187 < [EEP] < 0.303 × C2 mass% −0.0045.

11. １３ 2. The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the relationship between [PPP] determined by C NMR and C2 mass% determined by FTIR is −2.8 × C2 mass% + 0.878 < [PPP] < −2.8154 × C2 mass% + 1.0451.

12. １３ 2. The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the relationship between [PEP] from C NMR and C2 mass% from FTIR is 0.8923 × C2 mass% − 0.0021 < [PEP] < 0.9333 × C2 mass% + 0.

03.

13. １３ 2. The syndiotactic ethylene-propylene copolymer of claim 1, having an [EEE] from C NMR of less than 0.

008.

14. １３ The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the relationship between [EE] from C NMR and C2 mass% from FTIR is 0.2 × C2 mass% −0.016 < [EE] < 0.1292 × C2 mass% + 0.0082.

15. １３ 2. The syndiotactic ethylene-propylene copolymer of claim 1, wherein the relationship between propylene run# from C NMR and C2 mass% from FTIR is 110.67 × C2 mass% − 4.7 < [P Run#] < 97.143 × C2 mass% + 4.7286.

16. １３ r from C NMR １ r ２ The syndiotactic ethylene-propylene copolymer of claim 1, wherein the ε is less than 8.

0.

17. 2. The syndiotactic ethylene-propylene copolymer according to claim 1, wherein the relationship between Tg determined by DSC and C2 mass% determined by FTIR is −190×C2 mass%−9.15<Tg<−175×C2 mass%+1.

725.

18. g' from GPC ｖｉｓ The relationship between MW and LS is g' ｖｉｓ 2. The syndiotactic ethylene-propylene copolymer of claim 1, wherein MW,LS is >2E-06 x MW,LS + 0.9703.

19. 10. The syndiotactic ethylene-propylene copolymer of claim 1, which exhibits pellet stability after aging at 40° C. and 1 psig for 3 months.

20. 1. A method for producing a syndiotactic propylene copolymer, the method comprising: contacting propylene and ethylene in a homogeneous phase with a catalyst system comprising an activator and a catalyst compound; and obtaining a syndiotactic propylene copolymer comprising: (a) 85 to 95 weight percent propylene, based on the weight of the polymer; (b) 60 to 90% rr triads; (c) a Mw(LS) of 10 to 250 kg / mol; and (d) no substantial melting peak, the peak having a heat of fusion of 5 J / g or less, as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10°C / min.

21. 21. The method of claim 20, wherein the method is carried out at a temperature of from about 50°C to about 110°C and a pressure in the range of from about 1 MPa to about 14 MPa.

22. 21. The method of claim 20, wherein the method is carried out at a temperature of from about 50° C. to about 110° C. and a pressure ranging from about 3 MPa to about 14 MPa.

23. The process is carried out at a polymerization temperature equal to or greater than TP1, where TP1=0.9×EXP(−0.005×rr), where TP1 is in ° C. and rr is １３ 21. The method of claim 20, wherein the triad tacticity index is measured using C NMR.

24. 21. The method of claim 20, wherein the polymerization is carried out in a solution process at a pressure of 9 MPa or greater, a temperature of about 50°C to about 120°C, and a catalyst efficiency of 50,000 kg or greater of polymer per kg of catalyst.

25. 21. The process of claim 20, wherein the polymerization is conducted in a solution process at a pressure of 9 MPa or greater, a molar ratio of ethylene feed to propylene feed of about 0.01 to about 0.2, and a catalyst efficiency of 50,000 kg or greater of polymer per kg of catalyst.

26. the catalyst system comprises a catalyst compound represented by formula (1a), 【Chemistry 1】 During the ceremony, M is zirconium or hafnium; G is a bridging group; each X is independently a hydrido radical, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, or both X's are linked and attached to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both together are an olefin, diolefin, or aryne ligand, or both X's may independently be a halogen, alkoxide, aryloxide, amide, phosphide, or other monovalent anionic ligand, or both X's may be linked to form a dianionic chelating ligand; Each R ａ and R ｂ are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, or a polar radical, and optionally two or more adjacent substituents may be joined to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent, with the proviso that each R ａ is the same, and each R ｂ are the same, and the compound is C ｓ Symmetric or pseudo-C ｓ Allowing for symmetry, Each R ｃ are independently symmetric or pseudo-symmetric substituents relative to one another and are selected from hydrogen or hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl radicals; Each R ｄ are symmetric or pseudo-symmetric substituents relative to one another and are independently selected from hydrogen or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl radical.

27. M is zirconium, X is methyl or chloro, G is di(para-triethylsilylphenyl)methylene or diphenylmethylene, and each R ｄ , R ａ and R ｃ is hydrogen, and each R ｂ 27. The method of claim 26, wherein is methyl, ethyl, propyl, or butyl.

28. X is methyl, G is di(para-triethylsilylphenyl)methylene, and each R ｄ , R ａ and R ｃ is hydrogen, and each R ｂ The method of claim 27, wherein is tert-butyl.

29. The activator may be N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarben ...perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenyl 21. The method of claim 20, wherein the tetrakis(perfluorophenyl)borate is selected from one or more of tri(perfluorophenyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], di(hydrogenated tallow)methylammonium tetrakis(perfluorophenyl)borate, di(hydrogenated tallow)methylammonium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, and dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate.

Images