Polymerization of C6-C14 α-olefin monomers and polymers thereof

Abstract

The present disclosure provides a process. In one embodiment, the process comprises the step of contacting one or more C6-C14α-olefin monomers with a bis-biphenylphenoxy catalyst under polymerization conditions. The process comprises the step of forming a polymer composed of one or more C6-C14α-olefin monomers having an absolute weight average molecular weight (Mw) greater than 1,300,000 g / mol and an Mw / Mn ratio of 1.3 to 3.0.

Description

Background Technology

[0001] Olefin polymers, such as polyhexene and / or polyoctene, are produced using various catalyst systems. The selection of these catalyst systems used in the polymerization process of olefin polymers is an important factor contributing to the characteristics and properties of these olefin polymers.

[0002] Polyhexene and polyoctene are manufactured for a wide variety of articles. The polymerization process varies in several aspects, allowing for the production of a wide range of resulting polyoctene and polyhexene resins with different physical properties, providing various resins suitable for use in different applications. The monomer (hexene or octene) and optionally one or more comonomers are present in a liquid diluent, such as an alkane or isoalkane, such as isobutane. Hydrogen may also be added to the polymerization reactor. The catalyst system for producing the olefinic polymer is typically selected from chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or post-metallocene) catalyst systems. The reactants and catalyst system in the diluent are circulated at the polymerization temperature around the reactor to produce a homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, containing one or more unreacted optional comonomers along with the polymer product dissolved in the diluent, is removed from the polymerization reactor. When the reaction mixture is removed from the reactor, it may be treated to remove the polyethylene product from the diluent and unreacted reactants, whereby the diluent and unreacted reactants are typically recycled back into the polymerization reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced.

[0003] Although efforts are underway to develop catalyst systems suitable for olefin polymerization, such as the polymerization of polyoctene or polyhexene, the industry recognizes the need for catalyst systems with increased catalytic efficiency capable of producing olefinic polymers (particularly polyhexene and polyoctene) with high molecular weight (greater than 1,000,000 g / mol) and a narrow molecular weight distribution (MDD less than 3.0).

[0004] The present disclosure provides a process. In one embodiment, the process comprises one or more C6-C under polymerization conditions. 14 The process includes the step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst. The process comprises one or more C6-C 14 Composed of α-monomers and an absolute weight-average molecular weight (Mw) greater than 1,300,000 g / mol (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) It includes the step of forming a polymer having

[0005] The present disclosure provides a composition. In one embodiment, the composition comprises one or more C6-C 14 It comprises a polymer composed of α-monomers. The polymer contains a residual amount of zirconium, and the polymer has an absolute weight-average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) has

[0006] definition

[0007] Any references to the periodic table of elements are those published in the literature [CRC Press, Inc., 1990-1991]. References to the groups of elements in this periodic table follow the new notation for group numbering.

[0008] In U.S. patent practice, the contents of any cited patent, patent application, or publication are incorporated by reference in their entirety, particularly with respect to definitions (unless otherwise provided for in this disclosure) and the disclosure of general knowledge of the art (or an equivalent U.S. version thereof is incorporated by reference).

[0009] The numerical ranges disclosed herein include lower and upper limits and include all values ​​therefrom. In the case of a range having explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6 or 7), all sub-ranges between any two explicit values ​​are included (e.g., the range 1 to 7 includes 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0010] Unless otherwise specified, implied from the context, or conventional in the art, all parts and percentages are by weight, and all test methods are in use as of the filing date of this disclosure.

[0011] As used herein, the terms “combination” or “polymer combination” refer to a combination of two or more polymers. Such combinations may be miscible (not phase-separated at the molecular level) or may not be miscible. Such combinations may or may not phase-separate. Such combinations may or may not contain one or more domain configurations as measured by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art.

[0012] The term "composition" refers to a mixture of substances including not only the composition but also reaction products and decomposition products formed from the material of the composition.

[0013] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude any additional components, steps, or procedures, regardless of whether the presence of any additional components, steps, or procedures is specifically disclosed. To avoid doubt, any composition claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or not, unless otherwise stated. In contrast, the term “essentially composed of” excludes any other components, steps, or procedures from any subsequent enumerated categories, except those that are not essential to the feasibility. The term “composed of” excludes any components, steps, or procedures that are not specifically described or listed. Unless otherwise stated, the term “or” refers to the listed elements individually as well as in any combination. Use in the singular includes use in the plural, and vice versa.

[0014] The term "1-hexene" as used herein has the molecular formula C6H 12 It is an unsaturated hydrocarbon α-olefin having, where the unsaturation is located at the alpha position. 1-hexene has the molecular structural formula (A) shown below.

[0015] Structural formula (A)

[0016]

[0017] The "hexene-based polymer" contains more than 50 weight percent (weight%) of polymerized hexene monomers (based on the total amount of polymerizable monomers) and optionally at least one comonomer different from hexene (e.g., C 2-7 α-olefin and / or C 9-12It is a polymer that may contain (selected from α-olefins). Hexene-based polymers include hexene homopolymers and hexene comonomers (meaning units derived from hexene and one or more comonomers). The terms "hexene-based polymer" and "polyhexene" may be used interchangeably.

[0018] The term "1-octene" as used herein is an unsaturated hydrocarbon α-olefin having the molecular formula C8H16, where the unsaturation is located at the alpha position. 1-octene has the molecular structural formula (B) shown below.

[0019] Structural formula (B)

[0020]

[0021] The term "isomer of octene" as used herein has the molecular formula C8H 16 It is an unsaturated hydrocarbon having, and the unsaturation (double bond) does not exist at the alpha position. In other words, the term "isomer of octene" is any octene other than 1-octene. Non-limiting examples of isomers of octene include cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene, and combinations thereof, as well as cis-4-octene, trans-4-octene, branched octene isomers, and combinations thereof.

[0022] The "octene-based polymer" contains more than 50 weight percent (weight%) of polymerized octene monomer (based on the total amount of polymerizable monomers) and optionally at least one comonomer different from octene (e.g., C 2-7 α-olefin and / or C 9-12 It is a polymer that may contain (selected from α-olefins). Octene-based polymers include octene homopolymers and octene copolymers (meaning units derived from octene and one or more comonomers). The terms "octene-based polymer" and "polyoctene" may be used interchangeably.

[0023] "Polymer" is a compound prepared by polymerizing identical or different types of monomers that provide a plurality of and / or repeating "units" or "mer units" constituting the polymer in a polymerized form. Accordingly, the general term polymer encompasses the term homopolymer, which is generally used to refer to a polymer prepared from only one type of monomer, and the term copolymer, which is generally used to refer to a polymer prepared from at least two types of monomers. It also encompasses all forms of copolymers, e.g., random, block, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" each refer to the copolymers described above prepared by polymerizing ethylene or octene and one or more additional polymerizable α-olefin monomers. Polymers are generally referred to as “made of one or more specified monomers,” “based on” a specified monomer or monomer type, or “containing” a specified monomer content, but note that in this context, the term “monomer” is understood to refer to the polymerized residual portion of a specified monomer and not to an unpolymerized species. Generally, polymers herein are referred to as being based on a “unit,” which is the polymerized form of the corresponding monomer.

[0024] Test method

[0025] Gel Permeation Chromatography (GPC)

[0026] The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column compartment was set to 150°C. The columns used were four Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns and a 20-µm preposition column. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparging. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / min.

[0027] Calibration of the GPC column set was performed using 21 polystyrene standards with a narrow molecular weight distribution arranged in six "cocktail" mixtures with molecular weights ranging from 580 to 8,400,000 and spaced at least 10 apart between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 ml of solvent for molecular weights greater than 1,000,000 and at 0.05 grams in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes while gently stirring. A fifth-order polynomial was used to fit each polyethylene-equivalent calibration point.

[0028] The total plate count of the GPC column set was determined using decane (prepared with 0.04 g in 50 ml of TCB and dissolved with gentle stirring for 20 minutes). The plate count (Equation 2) and symmetry (Equation 3) were measured for a 200 microliter injection according to the following equations:

[0029] (Equation 2)

[0030] In the above formula, RV is the volume of residence in milliliters, the peak width is in milliliters, the maximum peak is the maximum height of the peak, and the ½ height is the height of the peak maximum value.

[0031] (Equation 3)

[0032] In the above formula, RV is the retention volume in milliliters, the peak width is in milliliters, the maximum peak is the maximum position of the peak, the 1 / 10 height is the 1 / 10 height of the peak maximum, the back peak refers to the peak tail at a retention volume later than the maximum peak, and the forward peak refers to the forward peak at a retention volume earlier than the maximum peak. The number of stages of the chromatography system must be greater than 18,000, and the symmetry must be between 0.98 and 1.22.

[0033] The sample was prepared semi-automatically using PolymerChar's "Instrument Control" software, with a target weight of 2 mg / ml, and a solvent (containing 200 ppm BHT) was added to a diaphragm-stoppered vial pre-sparged with nitrogen via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours under "low-speed" shaking.

[0034] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4 to 6, using the PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data acquisition point (i), and the polystyrene equivalent molecular weight obtained from the narrow standard correction curve for said point (i) from Equation 1.

[0035] (Equation 4)

[0036] (Equation 5)

[0037] (Equation 6)

[0038] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. Using this flow marker (FM), the RV (RV) of the decane peak within a narrow standard correction was calculated. (보정된 FM) The RV of each decane peak in the sample for ) (RV (FM 샘플) By aligning the pump flow rate (flow rate) for each sample (공칭) ) was linearly corrected. Subsequently, any change in the Deccan marker peak over time linearly shifted the flow rate over the entire run (flow rate (유효) It is assumed to be related to ). To enable the highest accuracy of the RV measurement of the flow marker peak, the peak of the flow marker concentration chromatogram is fitted to a quadratic equation using a least-squares fitting routine. Subsequently, the actual peak location is found using the first derivative of the quadratic equation. After calibrating the system based on the flow marker peak, the effective flow rate (for narrow standard correction) is calculated as in Equation 7. Processing of the flow marker peak was performed using PolymerChar GPCOne™ software. Acceptable flow correction ensures that the effective flow rate is within ±1% of the nominal flow rate.

[0039] flux (유효) = Flow rate (공칭) * (RV (보정된 FM) / RV (FM 샘플) ) (Equation 7)

[0040] Triple Detector GPC (TDGPC)

[0041] The chromatography system, running conditions, column set, column calibration, and calculation of typical molecular weight moments and distributions were performed according to the method described in gel permeation chromatography (GPC).

[0042] To determine the viscometer and light scattering detector offsets from the IR5 detector, the triple detector log (MW and IV) results from wide homopolymer polyethylene standards (Mw / Mn > 3) are optimized for the narrow standard column correction results from the narrow standard correction curve using PolymerChar GPCOne™ software by performing a systematic approach for determining multiple detector offsets in the same manner as disclosed in the literature [Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992))].

[0043] Absolute molecular weight data were obtained using PolymerChar GPCOne™ software in the same manner as disclosed in the literature [Zimm (Zimm, bH, j. Chem. Phys., 16, 1099 (1948))] and [Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987))]. The total injection concentration used for molecular weight determination was obtained from the mass detector area and mass detector constant derived from one of the suitable linear polyethylene homopolymers or polyethylene standards of known weight-average molecular weight. The calculated molecular weight (using GPCOne™) was obtained using the light scattering constant derived from one or more polyethylene standards mentioned below and a refractive index concentration factor dn / dc of 0.104. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) should be determined from a linear polyethylene standard having a molecular weight of approximately 120,000 g / mol. Viscometer calibration (determined using GPCOne™) can be achieved using the method described by the manufacturer, or alternatively, using the published values ​​of a suitable linear standard. Calculate the viscometer constant (obtained using GPCOne™) by relating the injected mass and specific viscosity area (DV) for the calibration standard to its intrinsic viscosity. The chromatographic concentration is assumed to be sufficiently low to eliminate the presented second-order virial factor effect (concentration effect on molecular weight).

[0044] Absolute weight average molecular weight (MW) (절대)) is obtained from the value obtained by dividing the integrated chromatogram area of ​​the light scattering region (LS) (factored by the light scattering constant) by the mass constant and the mass recovered from the mass detector (IR5) area (using GPCOne™). The molecular weight and intrinsic viscosity responses are linearly extrapolated at the chromatographic end where the signal for noise decreases (using GPCOne™). Each of the other moments, Mn (절대) , and Mz (절대) It is calculated according to the following equations 8 to 9.

[0045] (Equation 8)

[0046] (Equation 9)

[0047] Residual amount of catalyst metal. The "residual amount" of catalyst metal (Ti, hf, zr, and Ge) is 0 ppm, or greater than 0 ppm and less than 300 ppm, and was determined by a material balance based on the amount of added catalyst and the polymer formed during the reaction. The results are recorded in parts per million (ppm). Specific details for implementing the invention

[0048] The present disclosure provides a process. In one embodiment, the process comprises one or more C6-C under polymerization conditions. 14 The process includes the step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst. The process comprises one or more C6-C 14 The method includes the step of forming a polymer composed of α-olefin monomers, wherein the polymer has an absolute weight average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) has

[0049] This process involves one or more C6-C under polymerization conditions 14The method comprises the step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst. As used herein, "polymerization conditions" refer to temperature, pressure, reactant concentration, solvent selection, chain transfer agent (CTA), reactant mixing / addition parameters, and the reaction between reagents and the resulting product, namely one or more C6-C 14 Other conditions within the polymerization reactor that promote the formation of a polymer composed of α-olefin monomers. Polymerization may be carried out in a batch or continuous process in tubular reactors, stirred autoclaves, continuous stirred tank reactors, gas phase polymerization reactors, slurry phase polymerization reactors, loop reactors, isothermal reactors, fluidized bed gas phase reactors, and combinations thereof.

[0050] Under polymerization conditions, one or more C6-C 14 The α-olefin monomer is contacted with a bis-biphenylphenoxy catalyst (or interchangeably referred to as "BBP"). The bis-biphenylphenoxy catalyst is a metal-ligand complex having the structure shown in the following chemical formula (I):

[0051] [Chemical Formula (I)]

[0052]

[0053] In the above formula,

[0054] M is a metal selected from zirconium or hafnium, and said metal is in a formal oxidation state of +2, +3, or +4;

[0055] n is an integer from 0 to 3, and when n is 0, X does not exist;

[0056] Each X is independently a monodentate ligand of a neutral, monovalent, or divalent anion; or two Xs are taken together to form a bidentate ligand of a neutral, monovalent, or divalent anion; and X and n are selected in such a way that the metal-ligand complex of formula (I) is generally neutral;

[0057] Each Z is independently O, S, N(C1C40 )hydrocarbyl, or P(C1-C 40 It is hydrocarbil;

[0058] O is O (oxygen atom);

[0059] L is (C1-C 40 )hydrocarbylene or (C1-C 40 )heterohydrocarbylene, and (C1-C 40 ) Hydrocarbylene has a portion comprising a linker framework of 1-carbon to 10-carbon atoms connecting two Z groups of chemical formula (I) (to which L is bonded), or (C1-C 40 )Heterohydrocarbylene has a portion comprising a 1-atom to 10-atom linker framework connecting two Z groups of chemical formula (I), (C1-C 40 Each of the 1 to 10 atoms of the 1-atom to 10-atom linker framework of heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O)2, Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and independently each R C is (C1-C 30 )hydrocarbyl or (C1-C 30 It is a heterohydrocarbil;

[0060] Each R 1-16 (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, Ge(R C )3, P(R C )2, N(R C )2, OR C , SR C , NO2, CN, CF3, R C S(O), R C S(O)2, (R C )2C=N, R C C(O)O, R C OC(O), RC C(O)N(R), (R C )2NC(O), halogen atoms, hydrogen atoms, and combinations thereof are selected from.

[0061] A bis-biphenylphenoxy catalyst having the structure of chemical formula (I) can be catalytically active by contacting or combining a metal-ligand complex with an activating co-catalyst.

[0062] Non-limiting examples of activating co-catalysts suitable for use herein include alkyl aluminum; polymeric or oligomeric alumonic acids (also known as aluminoxan); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Combinations of one or more of the aforementioned activating co-catalysts and techniques are also considered. The term "alkyl aluminum" means monoalkyl aluminum dihydride or monoalkylaluminum dihalide, dialkyl aluminum hydride or dialkyl aluminum halide, or trialkylaluminum. Examples of polymeric or oligomeric alumonic acids include methylaluminum, triisobutylaluminum-modified methylaluminum, and isobutylaluminum.

[0063] Non-limiting examples of suitable Lewis acid activators (co-catalysts) are 1 to 3 (C1-C) described herein. 20 It comprises a Group 13 metal compound containing a )hydrocarbyl substituent. In one embodiment, the Group 13 metal compound is tri((C1-C 20 )hydrocarbyl)-substituted-aluminum, tri((C1-C 20 )hydrocarbyl)-boron compound, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane or tris(pentafluorophenyl)borane. In some embodiments, the activating co-catalyst is tetrakis((C1-C 20)hydrocarbyl borate or tri((C1-C 20 )hydrocarbyl)aluminum tetrakis((C1-C 20 )hydrocarbyl)borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to ((C1-C 20 )hydrocarbyl N(H)3 + or N(H)4 + It refers to nitrogen cations, and each (C1-C 20 Hydrocarbyl may be the same or different when two or more are present.

[0064] Non-limiting examples of neutral Lewis acid activator (co-catalyst) combinations include tri((C1-C4)alkyl)aluminum and tri((C6-C4) halides. 18 It includes a mixture comprising a combination of aryl)boron compounds, in particular tris(pentafluorophenyl)borane. Other embodiments are a combination of such neutral Lewis acid mixtures with polymeric or oligomeric alumonic acids, and a combination of a single neutral Lewis acid, in particular tris(pentafluorophenyl)borane, with polymeric or oligomeric alumonic acids. The ratio of moles of (metal-ligand complex):(tris(pentafluorophenylborane):(alumonic acid) [e.g., (group 4 metal-ligand complex):tris(pentafluorophenylborane):(alumonic acid)] is 1:1:1 to 1:10:100, and in other embodiments, 1:1:1.5 to 1:5:30.

[0065] A bis-biphenylphenoxy catalyst having the structure of formula (I) can be activated by a combination with one or more co-catalysts, e.g., a cation-forming co-catalyst, a strong Lewis acid, or a combination thereof, to form an active catalyst composition. Suitable activating co-catalysts include polymeric or oligomeric aluminoxanes, particularly methyl aluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable co-catalysts include modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-) amine (i.e., [HNMe(C 18 H 37 )2][B(C6F5)4]), and combinations of both, but are not limited thereto.

[0066] One or more of the aforementioned activation co-catalysts may be used in combination with one another. In one embodiment, the co-catalyst is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate and an oligomeric or polymeric alumonic acid compound. The ratio of the total moles of one or more metal-ligand complexes of Formula (I) to the total moles of one or more activation co-catalysts is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, and in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When alumonic acid is used alone as an activation co-catalyst, the moles of alumonic acid used are preferably at least 100 times the moles of the metal-ligand complexes of Formula (I). When tris(pentafluorophenyl)borane is used alone as an activation co-catalyst, in some other embodiments, the mole ratio of tris(pentafluorophenyl)borane used to the total mole ratio of one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activation co-catalyst is generally used in a molar amount approximately equivalent to the total molar amount of one or more metal-ligand complexes of formula (I).

[0067] In one embodiment, a bis-biphenylphenoxy catalyst having the structure of formula (I) comprises a metal M which is zirconium.

[0068] This process involves one or more C6-C 14 A step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst of formula (I) under polymerization conditions and one or more C6-C 14 It includes the step of forming a polymer composed of α-olefin monomers. The polymer is C6-C 14 A homopolymer of one monomer selected from α-olefins (hereinafter, "C6-C 14 α-olefin homopolymer"), C6-C 14A copolymer having two monomers selected from α-olefins (hereinafter, "C6-C 14 α-olefin copolymer"), or C6-C 14 A terpolymer having three monomers selected from α-olefins (hereinafter, "C6-C 14 It may be an α-olefin terpolymer"). A polymer (i.e., C6-C 14 α-olefin homopolymer, C6-C 14 α-olefin copolymer, or C6-C 14 The α-olefin terpolymer has an absolute weight-average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) has

[0069] polymer (i.e., C6-C 14 α-olefin homopolymer, C6-C 14 α-olefin copolymer, or C6-C 14 The α-olefin terpolymer contains residual amounts of zirconium or hafnium, or zirconium in amounts greater than 0 ppm to 300 ppm, and contains little to no titanium, or contains titanium in amounts of 0 ppm to less than 10 ppm.

[0070] In one embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the following structural formula (V):

[0071] [Chemical Formula (V)]

[0072]

[0073] In the above formula, Ge is germanium, Me is a methyl group, tBu is a t-butyl group, and iPr is an isopropyl group. This process involves one or more C6-C 14 A step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst of formula (V) under polymerization conditions and a polymer (i.e., C6-C 14 α-olefin homopolymer, C6-C 14α-olefin copolymer, or C6-C 14 It includes the step of forming an α-olefin terpolymer. A polymer (i.e., C6-C 14 α-olefin homopolymer, C6-C 14 α-olefin copolymer, or C6-C 14 α-olefin terpolymers) have one, some, or all of the following characteristics:

[0074] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0075] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0076] (Iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0077] (Iv) Residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm.

[0078] In one embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the following structural formula (VI):

[0079] [Structural Formula (VI)]

[0080]

[0081] In the above formula, Me is a methyl group and tBu is a t-butyl group. This process comprises one or more C6-C 14 The steps include contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst of formula (VI) under polymerization conditions and forming an octene polymer having one, some, or all of the following characteristics:

[0082] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0083] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0084] (iii) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm (hereinafter, Polymer 1 ).

[0085] In one embodiment, zirconium is one or more C6-C excluding titanium and / or hafnium. 14 Polymer composed of α-olefins ( Polymer 1 It exists among ).

[0086] In one embodiment, the process comprises the step of contacting one or more C6-C8α-olefin monomers under polymerization conditions with a bis-biphenylphenoxy catalyst having formula (I), formula (V), or formula (VI). The process comprises the step of forming a polymer composed of one or more C6-C8α-olefin monomers. The polymer composed of one or more C6-C8α-olefin monomers is a hexene homopolymer, a heptene homopolymer, an octene homopolymer, a hexene / heptene copolymer, a hexene / octene copolymer, a heptene / octene copolymer, or a hexene / heptene / octene terpolymer. The polymer composed of one or more C6-C8α-olefin monomers has one, some, or all of the following characteristics:

[0087] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0088] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0089] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0090] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm (hereinafter, Polymer 2 ).

[0091] In one embodiment, zirconium and / or germanium is a polymer composed of one or more C6-C8α-olefins excluding titanium ( Polymer 2 It exists in ). In additional embodiments, a polymer composed of one or more C6-C8α-olefins ( Polymer 2 ) contains a residual amount of zirconium (and optionally a residual amount of germanium) and additionally contains 0 ppm to less than 10 ppm of titanium.

[0092] In one embodiment, the process comprises the step of contacting an octene monomer with a bis-biphenylphenoxy catalyst having formula (I), or formula (V), or formula (VI) under polymerization conditions. The process comprises the step of forming an octene homopolymer. The octene homopolymer has one, some, or all of the following characteristics:

[0093] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0094] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0095] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0096] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm (hereinafter, Polymer 3 ).

[0097] In one embodiment, zirconium and / or germanium is an octene homopolymer of titanium excluding titanium or less than 0 ppm to 10 ppm ( Polymer 3 It exists among ).

[0098] In one embodiment, the process comprises the step of contacting an octene monomer with a bis-biphenylphenoxy catalyst having formula (I), or formula (V), or formula (VI) under polymerization conditions. The process comprises the step of forming a hexene homopolymer. The hexene homopolymer has one, some, or all of the following characteristics:

[0099] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0100] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대); and / or

[0101] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0102] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm (hereinafter, Polymer 4 ).

[0103] In one embodiment, germanium and / or zirconium is present in a hexene homopolymer of titanium (polymer 4) excluding titanium or in an amount of 0 ppm to less than 10 ppm.

[0104] 2. Composition

[0105] The present disclosure provides a composition. In one embodiment, the composition comprises one or more C6-C 14 α-olefin monomer (i.e., C6-C 14 α-olefin homopolymer, C6-C 14 α-copolymer, or C6-C 14 It includes a polymer composed of an α-olefin terpolymer. One or more C6-C 14 A polymer composed of α-olefin monomers has one, some, or all of the following characteristics:

[0106] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0107] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0108] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0109] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm ( Polymer 1 ).

[0110] In one embodiment, germanium and / or zirconium is one or more C6-C excluding titanium and / or hafnium. 14 Polymer composed of α-olefins ( Polymer 1 It exists in ). In additional embodiments, one or more C6-C 14 Polymer composed of α-olefins ( Polymer 1 ) contains a residual amount of zirconium (and optionally a residual amount of germanium) and 0 ppm to less than 10 ppm of titanium.

[0111] In one embodiment, the composition comprises one or more C6-C 14 It includes a polymer composed of α-olefin monomers. One or more C6-C 14The polymer composed of α-olefin monomers is a hexene homopolymer, a heptene homopolymer, an octene homopolymer, a hexene / heptene copolymer, a hexene / octene copolymer, a heptene / octene copolymer, or a hexene / heptene / octene terpolymer. One or more C6-C 14 A polymer composed of α-olefin monomers contains a residual amount of germanium and has one, some, or all of the following characteristics:

[0112] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0113] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0114] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0115] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm ( Polymer 2 ).

[0116] In one embodiment, germanium and / or zirconium is a polymer composed of one or more C6-C8α-olefins, excluding titanium and / or hafnium ( Polymer 2 It exists in ). In additional embodiments, a polymer composed of one or more C6-C8α-olefins ( Polymer 2 ) contains a residual amount of zirconium (and optionally a residual amount of germanium) and 0 ppm to less than 10 ppm of titanium.

[0117] In one embodiment, the composition comprises an octene homopolymer. The octene homopolymer has one, some, or all of the following characteristics:

[0118] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0119] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0120] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0121] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm ( Polymer 3 ).

[0122] In one embodiment, zirconium is an octene homopolymer (excluding titanium) Polymer 3 It exists in ). In additional embodiments, octene homopolymer ( Polymer 3 ) contains a residual amount of zirconium (and optionally a residual amount of germanium) and 0 ppm to less than 10 ppm of titanium.

[0123] In one embodiment, the composition comprises a hexene homopolymer. The hexene homopolymer has one, some, or all of the following characteristics:

[0124] (i) Mw of greater than 1,300,000 g / mol to 12,000,000 g / mol, or 1,400,000 g / mol to 10,000,000 g / mol, or 1,400,000 g / mol to 9,000,000 g / mol, or 1,500,000 g / mol to 8,000,000 g / mol (절대) ; and / or

[0125] (ii) Mw of 1.3 to 3.0, or 1.4 to 2.9, or 1.5 to 2.8, or 2.1 to 2.7, or 2.2 to 2.6 (절대) / Mn (절대) ; and / or

[0126] (iii) residual amount of germanium, or greater than 0 ppm or 1 ppm to less than 300 ppm, or 10 ppm to 200 ppm, or 12 ppm to 150 ppm, or 14 ppm to 130 ppm, or 14 ppm to 125 ppm of germanium; and / or

[0127] (iv) residual amount of zirconium, or greater than 0 ppm or less than 1 ppm to 300 ppm, or 10 ppm to 200 ppm, or 15 ppm to 180 ppm, or 20 ppm to 170 ppm, or 30 ppm to 160 ppm ( Polymer 4 ).

[0128] In one embodiment, zirconium is an octene homopolymer (excluding titanium) Polymer 4 It exists in ). In additional embodiments, a hexene homopolymer ( Polymer 4 ) contains a residual amount of zirconium (and optionally a residual amount of germanium) and 0 ppm to less than 10 ppm of titanium.

[0129] Now, some embodiments of the present disclosure will be described in detail in the following examples, in an exemplary rather than limiting manner.

[0130] Examples

[0131] The catalyst used in the comparative sample (CS) is provided in Table 1 below. The catalyst used in the example (IE) is provided in Table 2 below.

[0132] [Table 1]

[0133]

[0134] [Table 2]

[0135]

[0136] A. Polymerization of 1-hexene and 1-octene

[0137] For Comparative Sample 1 (CS1), polymerization was carried out with Ziegler-Natta catalyst (ZN) in a 40 mL vial filled with 4 mL of 1-octene, 8 mL of solvent (Isopar E), 4 μmol of catalyst (ZN), and 5 equivalents of Et3Al (as an activator) at a temperature of 23 to 25 °C for a period of 12 hours. Subsequently, the solvent was removed under vacuum.

[0138] For Comparative Sample 2 (CS2), polymerization is carried out with a CGC catalyst (as shown in Table 1) in a 40 mL vial filled with 4 mL of 1-octene, 8 mL of solvent (Isopar E), 4 μmol of catalyst, and 1.2 equivalents of RIBS-2 at a temperature of 23 to 25 °C for a period of 12 hours. Subsequently, the solvent is removed under vacuum.

[0139] For Comparative Sample 3 (CS3), polymerization was carried out with a metallocene 1 catalyst (as shown in Table 1) in a 40 mL vial filled with 6 mL of 1-octene, 12 mL of solvent (Isopar E), 2 μmol of catalyst, 1.2 equivalents of RIBS-2, and 10 equivalents of MMAO 3A at a temperature of 23 to 25 °C for a period of 12 hours. Subsequently, the solvent and unreacted octene isomers were removed under vacuum.

[0140] For Comparative Sample 4 (CS4), polymerization was carried out at a temperature of 23°C to 25°C for a period of 12 hours using a metallocene 2 catalyst (as shown in Table 1) in a vial filled with 6 mL of 1-octene, 12 mL of solvent (Isopar E), 2 μmol of catalyst, 1.2 equivalents of RIBS-2, and 10 equivalents of MMAO 3A. Subsequently, the solvent and unreacted octene isomers were removed under vacuum.

[0141] In the case of Invention Examples 1 to 4 (IE1 to 4), 6 mL of 1-octene and 12 mL of Isopar-E (in Isopar-E), 4 μmol of catalyst, and 1.2 equivalents of RIBS-2 (R2N(H)Me B(C6F5)4 as an activator, where R is a hydrogenated tallow alkyl (C 14-18 Polymerization is carried out with a bis-biphenylphenoxy catalyst (BBP1) in a 40 mL vial filled with alkyl (CAS No. 200644-82-2) at a temperature of 23°C to 25°C for a period of 12 hours. Subsequently, the solvent is removed under vacuum.

[0142] In the case of Invention Example 5 (IE5), 8 mL of 1-octene and 12 mL of Isopar-E, 4 μmol of catalyst, and 1.2 equivalents of RIBS-2 (R2N(H)Me B(C6F5)4 as an activator, where R is a hydrogenated tallow alkyl (C 14-18 Polymerization is carried out with a bis-biphenylphenoxy catalyst (BBP1) in a 40 mL vial filled with alkyl (CAS No. 200644-82-2) at a temperature of 23°C to 25°C for a period of 12 hours. Subsequently, the solvent and unreacted hexene isomers are removed under vacuum.

[0143] In the case of Invention Examples 6 to 7 (IE6 to 7), 8 mL of 1-octene and 12 mL of Isopar-E (Isopar E), 4 μmol of catalyst, and 1.2 equivalents of RIBS-2 (R2N(H)Me B(C6F5)4 as an activator, where R is a hydrogenated tallow alkyl (C 14-18 Polymerization is carried out with a bis-biphenylphenoxy catalyst (BBP2) in a 40 mL vial filled with alkyl (CAS No. 200644-82-2) at a temperature of 23°C to 25°C for a period of 12 hours. Subsequently, the solvent and unreacted octene isomer are removed under vacuum.

[0144] The characteristics of the generated octene homopolymer (and hexene homopolymer) are provided in Table 3 below.

[0145] [Table 3]

[0146]

[0147] Table 3 surprisingly indicates that polymerization using a BBP catalyst (BBP 1 or BBP 2) yielded high molecular weight octene or hexene homopolymers (greater than 1,300,000 g / mol) having a narrow molecular weight distribution (Mw / Mn). The obtained Invention Examples IE1 to IE7 do not contain titanium and contain residual zirconium (IE 1 to 5 also contain residual germanium).

[0148] Comparative examples using CGC, metallocene 1, or metallocene 2 obtained significantly lower molecular weights compared to IE1 to IE7. Comparative examples using ZN catalyst obtained a wide molecular weight distribution.

[0149] The present disclosure is not limited to the embodiments and examples included herein, but is particularly intended to include combinations of elements of different embodiments and variations of these embodiments including parts of the embodiments falling within the scope of the following claims.

Claims

Claim 1 As a process, one or more C6-C under polymerization conditions 14 A step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst; and one or more C6-C 14 Composed of α-olefin monomers and having an absolute weight-average molecular weight (Mw) greater than 1,300,000 g / mol (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A process comprising the step of forming a polymer having Claim 2 In paragraph 1, one or more C6-C 14 A process comprising the step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the following chemical formula: [Chemical Formula (I)] In the above formula, M is a metal selected from zirconium or hafnium, said metal having a formal oxidation state of +2, +3, or +4; n is an integer from 0 to 3, and when n is 0, X is absent; each X is independently a monodentate ligand of a neutral, monovalent anion, or divalent anion; or two Xs are taken together to form a bidentate ligand of a neutral, monovalent anion, or divalent anion; X and n are selected in such a way that the metal-ligand complex of formula (I) is generally neutral; and each Z is independently O, S, N (C1-C 40 )hydrocarbyl, or P(C1-C 40 )hydrocarbyl and; O is O (oxygen atom) and; L is (C1-C 40 )hydrocarbylene or (C1-C 40 )heterohydrocarbylene, and (C1-C 40 ) Hydrocarbylene has a portion comprising a linker framework of 1-carbon to 10-carbon atoms connecting two Z groups of chemical formula (I) (to which L is bonded), or (C1-C 40 )Heterohydrocarbylene has a portion comprising a 1-atom to 10-atom linker backbone connecting two Z groups of chemical formula (I), (C1-C 40 Each of the 1 to 10 atoms of the 1-atom to 10-atom linker framework of heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O)2, Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and independently each R c is (C1-C 30 )hydrocarbyl or (C1-C 30 )heterohydrocarbyl and; each R 1-16 (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, Si(R c )3, Ge(R c )3, P(R C )2, N(R c )2, OR c , SR c , NO2, CN, CF3, R C S(O), R C S(O)2, (R C )2C=N, R C C(O)O, R c OC(O), R c C(O)N(R), (R c )2NC(O), selected from halogen atoms, hydrogen atoms, and combinations thereof. Claim 3 In paragraph 1, one or more C6-C 14 A step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the chemical formula (V) [chemical formula (V)] ; and one or more C6-C 14 Composed of α-olefin monomers and having an absolute weight-average molecular weight (Mw) greater than 1,300,000 g / mol (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A process comprising the step of forming a polymer having a residual amount of zirconium and a residual amount of germanium. Claim 4 In paragraph 1, one or more C6-C 14 A step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the chemical formula (VI) [chemical formula (VI)] ; and one or more C6-C 14 Composed of α-olefin monomers and having an absolute weight-average molecular weight (Mw) greater than 1,300,000 g / mol (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A process comprising the step of forming a polymer having a residual amount of zirconium. Claim 5 In claim 3 or 4, the step of contacting one or more C6-C8α-olefin monomers with a bis-biphenylphenoxy catalyst having formula (V) or formula (VI) under polymerization conditions; and the step of forming a polymer composed of one or more C6-C8α-olefin monomers, wherein the polymer comprises a residual amount of zirconium and has an absolute weight average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A process comprising steps having Claim 6 In claim 5, the step of contacting an octene monomer with a bis-biphenylphenoxy catalyst having formula (V) or formula (VI) under polymerization conditions; and comprising a residual amount of zirconium and an absolute weight average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A process comprising the step of forming an octene homopolymer having Claim 7 In claim 6, the step of contacting an octene monomer with a bis-biphenylphenoxy catalyst having the formula (V) under polymerization conditions; and comprising a residual amount of germanium and an absolute weight average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A process comprising the step of forming an octene homopolymer having Claim 8 As a composition, the composition comprises one or more C6-C 14 A polymer composed of α-olefin monomers and containing boron; and comprising a residual amount of zirconium, wherein the polymer has an absolute weight average molecular weight (Mw) greater than 1,300,000 g / mol. (절대) ) and Mw of 1.3 to 3.0 (절대) / Mn (절대) A composition having Claim 9 In claim 8, the polymer is a composition comprising 0 ppm of titanium. Claim 10 A composition according to claim 8 or 9, wherein the polymer comprises more than 0 ppm to 300 ppm of zirconium. Claim 11 A composition according to claim 8 or 9, wherein the polymer comprises germanium in an amount greater than 0 ppm to 300 ppm. Claim 12 A composition according to claim 8 or 9, wherein the polymer is selected from the group consisting of octene homopolymers and hexene homopolymers. Claim 13 In claim 1, the contact step is a process that takes place at a temperature of 23°C to 25°C. Claim 14 In Paragraph 13, one or more C6-C 14 A process comprising the step of contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst and a boron-containing co-catalyst. Claim 15 In claim 8 or 9, the polymer comprises a bis-biphenylphenoxy metal-ligand complex having the formula (I), [formula (I)] In the above formula, M is zirconium; n is an integer from 0 to 3, and when n is 0, X is absent; each X is independently a monodentate ligand of a neutral, monovalent, or divalent anion; or two Xs are taken together to form a bidentate ligand of a neutral, monovalent, or divalent anion; X and n are selected in such a way that the metal-ligand complex of formula (I) is generally neutral; and each Z is independently O, S, N (C1-C 40 )hydrocarbyl, or P(C1-C 40 )hydrocarbyl; O is O (oxygen atom); L is (C1-C 40 )hydrocarbylene or (C1-C 40 )heterohydrocarbylene, and (C1-C 40 ) Hydrocarbylene has a portion comprising a linker framework of 1-carbon to 10-carbon atoms connecting two Z groups of chemical formula (I) (to which L is bonded), or (C1-C 40 )Heterohydrocarbylene has a portion comprising a 1-atom to 10-atom linker backbone connecting two Z groups of chemical formula (I), (C1-C 40 Each of the 1 to 10 atoms of the 1-atom to 10-atom linker framework of heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O)2, Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and independently each R c is (C1-C 30 )hydrocarbyl or (C1-C 30 )heterohydrocarbyl and; each R 1-16 (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, Si(R c )3, Ge(R c )3, P(R c )2, N(R c )2, OR c , SR c , NO2, CN, CF3, R C S(O), R C S(O)2, (R C )2C=N, R C C(O)O, R c OC(O), R c C(O)N(R), (R C A composition selected from )2NC(O), halogen atoms, hydrogen atoms, and combinations thereof.

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