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

Abstract

The present disclosure provides a process, in one embodiment, for the production of one or more C6-C 14 The process involves contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst. 14 It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (abs) ) and Mw of 1.3 to 3.0 (abs) / Mn (abs) forming a polymer having the formula:

Description

[Background technology]

[0001] Olefin-based polymers such as polyhexene and / or polyoctene are produced via various catalyst systems. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0002] Polyhexene and polyoctene are produced for a wide range of applications. The polymerization process can be varied in many ways to produce a wide variety of polyoctene and polyhexene resins with varying physical properties that make the various resins suitable for use in a variety of applications. The monomer (hexene or octene) and, optionally, one or more comonomers are present in a liquid diluent, such as an alkane or isoalkane, e.g., isobutane. Hydrogen can also be added to the polymerization reactor. Catalyst systems for producing olefin-based polymer resins are typically selected from chromium-based catalyst systems, Ziegler-Natta catalyst systems, and molecular (either metallocene or post-metallocene) catalyst systems. The diluent and the reactants in the catalyst system are circulated around the reactor at polymerization temperatures, thereby producing a homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, including the polymer product dissolved in the diluent, along with one or more optional unreacted comonomers, is removed from the polymerization reactor. The reaction mixture upon removal from the reactor may be treated to remove the polymer product from the diluent and unreacted reactants, which are typically recycled into the polymerization reactor. Alternatively, the reaction mixture may be sent to a second polymerization reactor connected in series with the first polymerization reactor, where a second polymer fraction may be produced.

[0003] Despite continuing efforts in developing catalyst systems suitable for olefin polymerization, such as polyoctene or polyhexene polymerization, the art recognizes a need for catalyst systems with improved catalytic efficiency capable of producing olefin-based polymers (particularly polyhexene and polyoctene) with high molecular weights (greater than 1,000,000 g / mol) and narrow molecular weight distributions (MWD less than 3.0). Summary of the Invention

[0004] The present disclosure provides a process, in one embodiment, for the production of one or more C6-C 14 The process involves contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst. 14 It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (abs) ) and Mw of 1.3 to 3.0 (abs) / Mn (abs) forming a polymer having the formula:

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

[0006] definition Any references to the Periodic Table of the Elements are to the table as published in 1990-1991 by CRC Press, Inc. References to element groups in this table are to the new notation for numbering groups.

[0007] For purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent United States version thereof is so incorporated by reference), particularly with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0008] Numerical ranges disclosed herein include all values, inclusive, between and including the lower and upper limits. Ranges containing explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7) also include all subranges between any two explicit values ​​(e.g., the 1 to 7 range above includes subranges of 1 to 2, 2 to 65, 73 to 75, 6, etc.).

[0009] Unless otherwise stated, implied from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0010] As used herein, the terms "blend" or "polymer blend" refer to a blend of two or more polymers. Such blends may or may not be miscible (not phase separated at the molecular level). Such blends may or may not be phase separated. Such blends may or may not contain one or more domain configurations as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art.

[0011] The term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0012] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or not, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes any other component, step, or procedure from the scope of any succeeding description, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not expressly delineated or listed. The term "or," unless otherwise stated, refers to the listed members individually as well as in any combination. The use of the singular includes the use of the plural, and vice versa.

[0013] As used herein, the term "1-hexene" has the molecular formula CH 12 1-Hexene is an unsaturated hydrocarbon α-olefin having the structure (A), where the unsaturation is in the alpha position. 1-Hexene has the molecular structure (A) shown below.

[0014] [ka]

[0015] A "hexene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized hexene monomer (based on the total amount of polymerizable monomers), and optionally at least one comonomer different from hexene (C 2-7 α-olefin and / or C 9-12 Hexene-based polymers, which may contain, for example, those selected from α-olefins, include hexene homopolymers and hexene copolymers (meaning units derived from hexene and one or more comonomers). The terms "hexene-based polymer" and "polyhexene" may be used interchangeably.

[0016] As used herein, the term "1-octene" refers to an unsaturated hydrocarbon α-olefin having the molecular formula CH, where the unsaturation is in the alpha position. 1-octene has the molecular structure (B) as shown below.

[0017] [ka]

[0018] As used herein, the term "octene isomers" refers to isomers of the molecular formula CH 16 where the unsaturation (double bond) is not in the alpha position. In other words, the term "octene isomer" refers to any octene except 1-octene. Non-limiting examples of octene isomers 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.

[0019] An "octene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized octene monomer (based on the total amount of polymerizable monomers), and optionally at least one comonomer different from octene (C 2-7 α-olefin and / or C 9-12 The octene-based polymer may contain, for example, an α-olefin. 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.

[0020] A "polymer" is a compound prepared by polymerizing monomers, whether of the same or different types, that provide multiple and / or repeating "units" or "mer units" that, in polymerized form, constitute the polymer. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer prepared from only one type of monomer, and the term copolymer, which is commonly used to refer to a polymer prepared from at least two types of monomer. It also encompasses all forms of copolymers, e.g., random, block, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" refer to the aforementioned copolymers prepared from polymerizing ethylene or octene with one or more additional polymerizable α-olefin monomers, respectively. While polymers are often referred to as "made of" one or more specific monomers, "based on" a particular monomer or monomer type, "containing" a particular monomer content, etc., it should be noted that in this context, the term "monomer" is understood to refer to the polymerized residue of a particular monomer, and not to the unpolymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomers.

[0021] Test Method Gel Permeation Chromatography (GPC) 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-um precolumn. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0022] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights, arranged in six "cocktail" mixtures with at least 10-fold spacing between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. A third-order polynomial was used to fit each polystyrene equivalent calibration point.

[0023] Total plate counts for the GPC column set were performed using decane (prepared at 0.04 g in 50 mL of TCB and dissolved for 20 minutes with gentle stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured with a 200-microliter injection according to the following equations:

[0024]

number

[0025]

number

[0026] Samples were prepared in a semi-automated fashion using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged septa-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0027] Mn (GPC) , Mw (GPC) and Mz (GPC) The calculation was based on GPC results using the PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polystyrene equivalent molecular weight obtained from a narrow standard calibration curve at point (i) in Equation 1, according to Equations 4-6, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph.

[0028]

number

[0029]

number

[0030] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by RV-matching the respective decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow rate marker peaks, a least-squares fitting routine is used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) is calculated as shown in Equation 7. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. An acceptable flow correction is to have the effective flow be within + / - 1% of the apparent flow. flow rate (有効) = flow rate (見かけ) * (RV (FM較正済み) / RV (FM試料) ) (Formula 7)

[0031] Triple Detector GPC (TDGPC) The chromatographic system, analytical conditions, column set, column calibration and calculation and distribution of conventional molecular weight moments were performed according to the methods described in Gel Permeation Chromatography (GPC).

[0032] For the determination of viscometer and light scattering detector offsets from the IR5 detector, a systematic approach for the determination of multiple detector offsets was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)) using PolymerChar GPCOne™ software to optimize triple detector log (MW and IV) results from broad homopolymer polyethylene standards (Mw / Mn>3) against narrow standard column calibration results from a narrow standard calibration curve.

[0033] Molecular weight data were obtained using PolymerChar GPCOne™ software in a manner consistent with that published by 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 injected concentration used in determining the molecular weight was obtained from the mass detector area and mass detector constant derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards of known weight average molecular weight. Calculated molecular weights (using GPCOne™) were obtained using the light scattering constant and refractive index concentration coefficient, dn / dc, of 0.104, derived from one or more of the polyethylene standards described below. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) should be determined from a linear polyethylene standard with 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, by using published values ​​of suitable linear standards. A viscometer constant (obtained using GPCOne™) is calculated, relating the specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. Chromatographic concentrations are assumed to be low enough to preclude addressing second viral coefficient effects (concentration effects on molecular weight).

[0034] Absolute weight average molecular weight (Mw (Abs) ) is obtained (using GPCOne™) by dividing the light scattering (LS) area integrated chromatogram (factored by the light scattering constant) by the mass recovered from the mass constant and the mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated (using GPCOne™) at the chromatographic end where the signal to noise is low. The other respective moments, Mn (Abs) and Mz (Abs) is calculated according to steps 8-9 below:

[0035]

number

[0036] Residual Amount of Catalytic Metals. The "residual amount" of catalytic metals (Ti, Hf, Zr, and Ge) is 0 ppm or greater than 0 ppm to less than 300 ppm, as determined by mass balance based on catalyst added and the amount of polymer formed during the reaction. Results are reported in parts per million (ppm). DETAILED DESCRIPTION OF THE INVENTION

[0037] The present disclosure provides a process, in one embodiment, for the production of one or more C6-C 14 The process involves contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst. 14 It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (Abs) ) and Mw of 1.3 to 3.0 (Abs) / Mn (Abs) forming a polymer having the formula:

[0038] This process involves the polymerization of one or more C6-C 14 The term "polymerization conditions" as used herein refers to the temperature, pressure, reactant concentration, solvent selection, chain transfer agent (CTA), reactant mixing / addition parameters, and the resulting product, i.e., one or more C6-C 14 Other conditions within the polymerization reactor promote the reaction between the α-olefin monomers to form a polymer. Polymerization can be carried out in a batch or continuous process in a tubular reactor, stirred autoclave, continuous stirred tank reactor, gas phase polymerization reactor, slurry phase polymerization reactor, loop reactor, isothermal reactor, fluidized bed gas phase reactor, and combinations thereof.

[0039] 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"), which is a metal-ligand complex having the structure shown in formula (I) below.

[0040] [ka] During the ceremony, M is a metal selected from zirconium or hafnium, the metal being in the +2, +3 or +4 formal oxidation state; n is an integer of 0 to 3, and when n is 0, X does not exist; each X is independently a monodentate ligand which is neutral, monoanionic or dianionic, or two X together form a bidentate ligand which is neutral, monoanionic or dianionic, and X and n are selected such that the metal-ligand complex of formula (I) as a whole is neutral; Each Z is independently O, S, N(C-C 40 ) hydrocarbyl or P(C-C 40 ) hydrocarbyl, O is O (oxygen atom), L is (C1-C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, (C1-C 40 ) Hydrocarbylene has a moiety that includes a linker skeleton of 1 carbon atom to 10 carbon atoms that connects the two Z groups (to which L is attached) in formula (I), or (C1-C 40 ) Heterohydrocarbylene has a moiety containing a linker skeleton of 1 atom to 10 atoms connecting the two Z groups in formula (I), (C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R C )2, Ge(R C )2, P(R C) or N(R C ), where each R C independently represents a group selected from the group consisting of (C - C 30 ) hydrocarbyl or (C-C 30 ) heterohydrocarbyl, Each R 1-16 is (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(R C )3, Ge(R C )3, P(R C )2, N(R C )2, OR C , S.R. 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), a halogen atom, a hydrogen atom or a combination thereof.

[0041] The bis-biphenylphenoxy catalyst having the structure of formula (I) can be made catalytically active by contacting the metal-ligand complex with an activating cocatalyst or by combining the metal-ligand complex with an activating cocatalyst.

[0042] Non-limiting examples of activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); 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 foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0043] Non-limiting examples of suitable Lewis acid activators (cocatalysts) include those having one to three (C-C 20 In one embodiment, the Group 13 metal compound includes a tri((C-C) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C-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, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tetrakis((C-C 20 ) hydrocarbyl borate or tri((C1-C 20 )hydrocarbyl)ammonium tetrakis((C1-C 20 )hydrocarbyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a ((C-C 20 ) Hydrocarbyl N(H)3+ or N(H)4 + means a nitrogen cation, each (C1-C 20 ) Hydrocarbyls, when present in two or more, may be the same or different.

[0044] A non-limiting example of a neutral Lewis acid activator (cocatalyst) combination is tri((C1-C4) alkyl)aluminum and tri((C6-C 18 (aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include mixtures containing such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane)] is 1:1:1 to 1:10:100, and in other embodiments, 1:1:1.5 to 1:5:30.

[0045] The bisbiphenylphenoxy catalyst having the structure of formula (I) can be activated to form an active catalyst composition by combining one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include modified methylaluminoxane (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.

[0046] One or more of the foregoing activating cocatalysts may be used in combination with one another. In one embodiment, the cocatalyst is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total moles of the one or more metal-ligand complexes of Formula (I) to the total moles of the one or more activating cocatalysts is from 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000; in other embodiments, it is at least 1:1000 and no more than 10:1; and in other embodiments, it is no more than 1:1. When alumoxane is used alone as the activating cocatalyst, preferably the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of Formula (I).

[0047] In one embodiment, the bis-biphenylphenoxy catalyst having the structure of Formula (I) comprises a metal M that is zirconium.

[0048] The process involves the polymerization of one or more C6-C 14 contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst of formula (I) and 14 and forming a polymer comprised of α-olefin monomers, the polymer being C6-C 14 Homopolymers of one monomer selected from α-olefins (hereinafter referred to as "C6-C 14 α-olefin homopolymer), C6-C 14 Copolymers having two monomers selected from α-olefins (hereinafter referred to as "C6-C 14α-olefin copolymer) or C6-C 14 Terpolymers having three monomers selected from α-olefins (hereinafter referred to as "C6-C 14 The polymer (i.e., C6-C α-olefin terpolymer) may be 14 Alpha-olefin homopolymer, C6-C 14 α-olefin copolymer or C6-C 14 α-olefin terpolymers) have an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol. (Abs) ) and Mw of 1.3 to 3.0 (Abs) / Mn (Abs) It has.

[0049] This polymer (i.e., C6-C 14 Alpha-olefin homopolymer, C6-C 14 α-olefin copolymer or C6-C 14 The α-olefin terpolymer) contains residual amounts of zirconium or hafnium, or 0 ppm to 300 ppm of zirconium, and little or no titanium, or 0 ppm to less than 10 ppm of titanium.

[0050] In one embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the following structural formula (V):

[0051] [ka] where Ge is germanium, Me is a methyl group, tBu is a t-butyl group, and iPr is an isopropyl group. This process involves the polymerization of one or more C6-C 14 contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst of formula (V) and forming a polymer (i.e., C6-C 14 Alpha-olefin homopolymer, C6-C 14 α-olefin copolymer or C6-C 14 and forming a C6-C α-olefin terpolymer. 14Alpha-olefin homopolymer, C6-C 14 α-olefin copolymer or C6-C 14 The α-olefin terpolymers have one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 15 ppm and 180 ppm, or between 20 ppm and 170 ppm, or between 30 ppm and 160 ppm.

[0052] In one embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the following structural formula (VI):

[0053] [ka] where Me is a methyl group and tBu is a t-butyl group. This process involves the polymerization of one or more C6-C 14 contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst of formula (VI) and forming an octene polymer having one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) Residual amounts of zirconium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 15 ppm and 180 ppm, or between 20 ppm and 170 ppm, or between 30 ppm and 160 ppm (hereinafter Polymer 1).

[0054] In one embodiment, zirconium is selected from one or more C6-C excluding titanium and / or excluding hafnium. 14 It is present in polymers composed of α-olefins (polymer 1).

[0055] In one embodiment, the process comprises contacting one or more C6-C8 α-olefin monomers with a bis-biphenylphenoxy catalyst having Formula (I), or Formula (V), or (VI) under polymerization conditions. The process comprises forming a polymer comprised of one or more C6-C8 α-olefin monomers. The polymer comprised of one or more C6-C8 α-olefin monomers is a hexene homopolymer, heptene homopolymer, octene homopolymer, hexene / heptene copolymer, hexene / octene copolymer, hexene / octene copolymer, or hexene / heptene / octene terpolymer. The polymer comprised of one or more C6-C8 α-olefin monomers has one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 15 ppm and 180 ppm, or between 20 ppm and 170 ppm, or between 30 ppm and 160 ppm (hereinafter Polymer 2).

[0056] In one embodiment, zirconium and / or germanium are present in a polymer comprised of one or more C6-C8 α-olefins (polymer 2), excluding titanium. In a further embodiment, the one or more C6-C8 α-olefin monomers (polymer 2) contain residual zirconium (and optionally residual germanium) and further contain from 0 ppm to less than 10 ppm titanium.

[0057] In one embodiment, the process comprises contacting octene monomer with a bis-biphenylphenoxy catalyst having formula (I), or formula (V), or (VI) under polymerization conditions. The process comprises forming an octene homopolymer. The octene homopolymer has one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 15 ppm and 180 ppm, or between 20 ppm and 170 ppm, or between 30 ppm and 160 ppm (hereinafter Polymer 3).

[0058] In one embodiment, zirconium and / or germanium are present in the octene homopolymer (Polymer 3) excluding titanium, or from 0 ppm to less than 10 ppm titanium.

[0059] In one embodiment, the process comprises contacting hexene monomer with a bis-biphenylphenoxy catalyst having formula (I) or (VI) of formula (V) under polymerization conditions. The process comprises forming a hexene homopolymer. The hexene homopolymer has one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or greater than 1 ppm but 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; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 15 ppm and 180 ppm, or between 20 ppm and 170 ppm, or between 30 ppm and 160 ppm (hereinafter Polymer 4).

[0060] In one embodiment, germanium and / or zirconium are present in the hexene homopolymer (Polymer 4) excluding titanium, or from 0 ppm to less than 10 ppm titanium.

[0061] 2. Composition The present disclosure provides a composition. In one embodiment, the composition comprises one or more C6-C 14 Polymers composed of α-olefin monomers (i.e., C6-C 14 Alpha-olefin homopolymer, C6-C 14 α-olefin copolymer or C6-C 14 α-olefin terpolymers) containing one or more C6-C 14 Polymers composed of α-olefin monomers have one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or from 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm of zirconium (Polymer 1).

[0062] In one embodiment, germanium and / or zirconium are selected from one or more C6-C excluding titanium and / or excluding hafnium. 14 In a further embodiment, one or more C6-C 14 The α-olefin monomer (Polymer 1) contains residual amounts of zirconium (and optionally residual amounts of germanium) and from 0 ppm to less than 10 ppm of titanium.

[0063] In one embodiment, the composition comprises a polymer comprised of one or more C6-C8 α-olefin monomers. The polymer comprised of one or more C6-C8 α-olefin monomers is a hexene homopolymer, heptene homopolymer, octene homopolymer, hexene / heptene copolymer, hexene / octene copolymer, hexene / octene copolymer, or hexene / heptene / octene terpolymer. The polymer comprised of one or more C6-C8 α-olefin monomers contains a residual amount of germanium and has one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or from 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm of zirconium (Polymer 2).

[0064] In one embodiment, germanium and / or zirconium are present in a polymer comprised of one or more C6-C8 α-olefins (polymer 2) excluding titanium and / or excluding hafnium. In a further embodiment, the one or more C6-C8 α-olefin monomers (polymer 2) contain residual zirconium (and optionally residual germanium) and 0 ppm to less than 10 ppm titanium.

[0065] In one embodiment, the composition comprises an octene homopolymer having one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or from 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm of zirconium (Polymer 3).

[0066] In one embodiment, zirconium is present in the octene homopolymer (Polymer 3) excluding titanium. In a further embodiment, the octene homopolymer (Polymer 3) contains residual amounts of zirconium (and optionally residual amounts of germanium and 0 ppm to less than 10 ppm of titanium).

[0067] In one embodiment, the composition comprises a hexene homopolymer having one, some, or all of the following properties: (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 (Abs) and / or (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 (Abs) / Mn (Abs) and / or (iii) residual amounts of germanium, or greater than 0 ppm, or between 1 ppm and less than 300 ppm, or between 10 ppm and 200 ppm, or between 12 ppm and 150 ppm, or between 14 ppm and 130 ppm, or between 14 ppm and 125 ppm; and / or (iv) Residual amounts of zirconium, or greater than 0 ppm, or from 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm of zirconium (Polymer 4).

[0068] In one embodiment, zirconium is present in the hexene homopolymer (Polymer 4) excluding titanium. In a further embodiment, the hexene homopolymer (Polymer 4) contains residual amounts of zirconium (and optionally residual amounts of germanium) and from 0 ppm to less than 10 ppm of titanium.

[0069] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples. [Example]

[0070] The catalysts used in the comparative samples (CS) are provided below in Table 1. The catalysts used in the inventive examples (IE) are provided below in Table 2.

[0071] [Table 1]

[0072] [Table 2]

[0073] A. Polymerization of 1-hexene and 1-octene For comparative sample 1 (CS1), polymerization is carried out with a Ziegler-Natta catalyst (ZN) for a period of 12 h at a temperature of 23-25 ​​°C in a 40 mL vial charged with 4 mL of 1-octene, 8 mL of solvent (Isopar E), 4 µmol of catalyst (ZN), and 5 equivalents of EtAl (as activator). The solvent is then removed under vacuum.

[0074] For comparative sample 2 (CS2), polymerization is carried out with CGC catalyst (as shown in Table 1) for a period of 12 h and at a temperature of 23-25 ​​°C in a 40 mL vial charged with 4 mL of 1-octene, 8 mL of solvent (Isopar E), 4 µmol of catalyst, and 1.2 equivalents of RIBS-2. The solvent is then removed under vacuum.

[0075] For comparative sample 3 (CS3), polymerization is carried out with the Methaselon 1 catalyst (as shown in Table 1) for a period of 12 h at a temperature of 23-25 ​​°C in a 40 mL vial charged 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. The solvent and unreacted octene isomers are then removed under vacuum.

[0076] For comparative sample 4 (CS4), polymerization is carried out with the Methaselon 2 catalyst (as shown in Table 1) for a period of 12 h at a temperature of 23-25 ​​°C in a 40 mL vial charged 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. The solvent and unreacted octene isomers are then removed under vacuum.

[0077] For Inventive Examples 1-4 (IE1-4), polymerizations were carried out with bis-biphenylphenoxy catalyst (BBP1) for a period of 12 hours and at a temperature of 23-25°C in a 40 mL vial charged with 8 mL of 1-octene and 12 mL of Isopar-E (in Isopar E), 4 µmol of catalyst, and 1.2 equivalents of RIBS-2 (RN(H)MeB(CF)), where R is hydrogenated tallow alkyl (C 14-18 The solvent is then removed under vacuum.

[0078] For Inventive Example 5 (IE5), polymerization was carried out with bis-biphenylphenoxy catalyst (BBP1) for a period of 12 hours and at a temperature of 23-25°C in a 40 mL vial charged with 8 mL of 1-hexene and 12 mL of Isopar-E, 4 µmol of catalyst, and 1.2 equivalents of RIBS-2 (RN(H)MeB(CF)), where R is hydrogenated tallow alkyl (C 14-18 The solvent and unreacted hexene isomers are then removed under vacuum.

[0079] For Inventive Examples 6-7 (IE6-7), polymerizations were carried out with bis-biphenylphenoxy catalyst (BBP2) for a period of 12 hours and at a temperature of 23-25°C in a 40 mL vial charged with 8 mL of 1-octene and 12 mL of Isopar-E (in Isopar E), 4 µmol of catalyst, and 1.2 equivalents of RIBS-2 (RN(H)MeB(CF)), where R is hydrogenated tallow alkyl (C 14-18 The solvent and unreacted octene isomers are then removed under vacuum.

[0080] The properties of the resulting octene homopolymer (and hexene homopolymer) are provided in Table 3 below.

[0081] [Table 3] 1 ppm residual catalytic metals present in homopolymer based on total homopolymer weight

[0082] Table 3 shows that, surprisingly, polymerization with a BBP catalyst (BBP1 or BBP2) resulted in high molecular weight octene or hexene homopolymers (>1,300,000 g / mol) with narrow molecular weight distributions (Mw / Mn). The resulting inventive examples IE1-IE7 contain no titanium and residual zirconium (IE1-5 also contain residual germanium).

[0083] Comparative examples using CGC, Metallocene 1 or Metallocene 2 resulted in significantly lower molecular weights when compared to IE1-IE7. Comparative examples using a ZN catalyst resulted in broad molecular weight distributions.

[0084] In particular, the present disclosure is not limited to the embodiments and examples contained herein, but is intended to include modifications thereof. Embodiments including portions of embodiments and combinations of elements of various embodiments, as fall within the scope of the following claims. The present specification includes the following aspects. Section 1. A process comprising: Under polymerization conditions, C6 to C 14 contacting one or more monomers consisting of α-olefin monomers with a bis-biphenylphenoxy catalyst; One or more C6-C 14 It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (abs) ) and Mw of 1.3 to 3.0 (abs) / Mn (abs) forming a polymer having The process includes: Section 2. One or more C6-C 14contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the formula: [ka] During the ceremony, M is a metal selected from zirconium or hafnium, said metal being in a formal oxidation state of +2, +3 or +4; n is an integer of 0 to 3, and when n is 0, X does not exist; each X is independently a monodentate ligand which is neutral, monoanionic or dianionic, or two X together form a bidentate ligand which is neutral, monoanionic or dianionic, and X and n are selected such that the metal-ligand complex of formula (I) as a whole is neutral; Each Z is independently O, S, N (C1 to 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, 40 ) hydrocarbylene has a moiety containing a linker skeleton of 1 to 10 carbon atoms that connects the two Z groups (to which L is attached) in formula (I), or 40 ) Heterohydrocarbylene has a moiety containing a linker skeleton of 1 atom to 10 atoms that connects the two Z groups in formula (I), and the (C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R c )2, Ge(R c )2, P(R C ), or N(R C ) where each R c are independently (C1~C 30 ) hydrocarbyl or (C1-C30 ) heterohydrocarbyl, Each R 1-16 is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(R c )3, Ge(R c )3, P(R C )2, N(R c )2, OR c , S.R. 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), a halogen atom, a hydrogen atom, or a combination thereof; The process described in item 1. Section 3. One or more of C6 to C 14 contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the formula (V); [ka] One or more C6-C 14 It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (abs) ) and Mw of 1.3 to 3.0 (abs) / Mn (abs) forming a polymer having a residual amount of zirconium and a residual amount of germanium; Item 3. The process according to item 1 or 2, comprising: Section 4. One or more of C6 to C 14 contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having formula (VI); [ka] One or more C6-C 14It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (abs) ) and Mw of 1.3 to 3.0 (abs) / Mn (abs) and forming a polymer having a residual amount of zirconium; Item 3. The process according to item 1 or 2, comprising: Section 5. One or more of C6 to C 14 contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having formula (VI); [ka] One or more C6-C 14 It is composed of α-olefin monomers and has an absolute weight average molecular weight (Mw) of more than 1,300,000 g / mol. (abs) ) and Mw of 1.3 to 3.0 (abs) / Mn (abs) and forming a polymer having a residual amount of zirconium; Item 3. The process according to item 1 or 2, comprising: Section 6. contacting an octene monomer with a bis-biphenylphenoxy catalyst having formula (V) or formula (VI) under polymerization conditions; containing residual amounts of zirconium and having an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol (Abs) ) and Mw of 1.3 to 3.0 (Abs) / Mn (Abs) forming an octene homopolymer having the formula: Item 6. The process according to item 5, comprising: Section 7. contacting an octene monomer with a bis-biphenylphenoxy catalyst having formula (V) or formula (VI) under polymerization conditions; containing residual amounts of zirconium and having an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol (Abs) ) and Mw of 1.3 to 3.0 (Abs) / Mn (Abs) forming an octene homopolymer having the formula: Item 6. The process according to item 5, comprising: Section 8. 1. A composition comprising: One or more C6-C 14 a polymer comprising an α-olefin monomer, the polymer containing boron; and a residual amount of zirconium, The polymer has an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol. (Abs) ) and Mw of 1.3 to 3.0 (Abs) / Mn (Abs) A composition comprising: Section 9. Item 9. The composition of item 8, wherein the polymer contains 0 ppm of titanium. Section 10. Item 10. The composition according to item 8 or 9, wherein the polymer contains more than 0 ppm to 300 ppm of zirconium. Section 11. Item 11. The composition according to any one of items 8 to 10, wherein the polymer contains more than 0 ppm to 300 ppm of germanium. Section 12. Item 12. The composition according to any one of items 8 to 11, wherein the polymer is selected from the group consisting of an octene homopolymer and a hexene homopolymer. Section 13. Item 1. The process of item 1, wherein the contacting occurs at a temperature of 23°C to 25°C. Section 14. One or more of C6 to C 14 14. The process of claim 13, comprising contacting an α-olefin monomer with the bis-biphenylphenoxy catalyst and a boron-containing cocatalyst. Section 15. the polymer comprises a bis-biphenylphenoxy metal-ligand complex having the formula (I): [ka] During the ceremony, M is zirconium; n is an integer of 0 to 3, and when n is 0, X does not exist; each X is independently a monodentate ligand which is neutral, monoanionic or dianionic, or two X together form a bidentate ligand which is neutral, monoanionic or dianionic, and X and n are selected such that the metal-ligand complex of formula (I) is overall neutral; Each Z is independently O, S, N (C1 to 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, 40 ) hydrocarbylene has a moiety containing a linker skeleton of 1 to 10 carbon atoms that connects the two Z groups (to which L is attached) in formula (I), or 40 ) Heterohydrocarbylene has a moiety containing a linker skeleton of 1 atom to 10 atoms that connects the two Z groups in formula (I), and the (C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R C )2, Ge(R c )2, P(R C ), or N(R C ) and each R c are independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, Each R 1-16 is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(R c )3, Ge(R c )3, P(R c )2, N(R c )2, OR c , S.R. c , NO2, CN, CF3, R CS(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 )NC(O), a halogen atom, a hydrogen atom, and combinations thereof; Item 15. The composition according to any one of items 8 to 14.

Claims

1. A process comprising: Under polymerization conditions, C ６ ~C １４ contacting one or more monomers consisting of α-olefin monomers with a bis-biphenylphenoxy catalyst; One or more C ６ ~C １４ It is made up of α-olefin monomers and has an absolute weight average molecular weight (Mw （ａｂｓ） ) and Mw of 1.3 to 3.0 （ａｂｓ） / Mn （ａｂｓ） forming a polymer having The process includes:

2. One or more C ６ ~C １４ contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the formula: 【Chemistry 1】 During the ceremony, M is a metal selected from zirconium or hafnium, said metal being in 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 which is neutral, monoanionic or dianionic, or two X together form a bidentate ligand which is neutral, monoanionic or dianionic, and X and n are selected such that the metal-ligand complex of formula (I) as a whole is neutral; Each Z is independently O, S, N(C １ ~C ４０ ) hydrocarbyl, or P(C １ ~C ４０ ) hydrocarbyl, O is O (oxygen atom), L is (C １ ~C ４０ ) hydrocarbylene or (C １ ~C ４０ ) heterohydrocarbylene, １ ~C ４０ ) hydrocarbylene has a moiety that includes a linker skeleton of 1 carbon atom to 10 carbon atoms that connects the two Z groups in formula (I) (to which L is attached), or １ ~C ４０ ) heterohydrocarbylene has a moiety containing a linker skeleton of 1 atom to 10 atoms connecting the two Z groups in formula (I), １ ~C ４０ ) Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the 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 each R ｃ are independently １ ~C ３０ ) hydrocarbyl or (C １ ~C ３０ ) heterohydrocarbyl, Each R １－１６ is (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, Si(R ｃ ) ３ , Ge(R ｃ ) ３ , P(R Ｃ ) ２ , N(R ｃ ) ２ , OR ｃ , S.R. ｃ , NO ２ , C.N., C.F. ３ , R Ｃ S(O), R Ｃ S (O) ２ , (R Ｃ ) ２ C=N, R Ｃ C(O)O,R ｃ OC(O), R ｃ C(O)N(R), (R ｃ ) ２ NC(O), a halogen atom, a hydrogen atom, or a combination thereof; 10. The process of claim 1.

3. The one or more C ６ ~C １４ contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having the formula (V); 【Chemistry 2】 One or more C ６ ~C １４ It is made up of α-olefin monomers and has an absolute weight average molecular weight (Mw （ａｂｓ） ) and Mw of 1.3 to 3.0 （ａｂｓ） / Mn （ａｂｓ） forming a polymer having a residual amount of zirconium and a residual amount of germanium; 3. The process of claim 1 or 2, comprising:

4. The one or more C ６ ~C １４ contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having formula (VI); 【Transformation 3】 One or more C ６ ~C １４ It is made up of α-olefin monomers and has an absolute weight average molecular weight (Mw （ａｂｓ） ) and Mw of 1.3 to 3.0 （ａｂｓ） / Mn （ａｂｓ） and forming a polymer having a residual amount of zirconium; 3. The process of claim 1 or 2, comprising:

5. Under polymerization conditions, one or more C ６ ~C ８ contacting an α-olefin monomer with a bis-biphenylphenoxy catalyst having formula (V) or formula (VI); One or more C ６ ~C ８ forming a polymer comprised of α-olefin monomers, said polymer containing a residual amount of zirconium and having an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol; （Ａｂｓ） ) and Mw of 1.3 to 3.0 （Ａｂｓ） / Mn （Ａｂｓ） forming a 5. The process of claim 3 or 4, comprising:

6. contacting an octene monomer with a bis-biphenylphenoxy catalyst having formula (V) or formula (VI) under polymerization conditions; containing residual amounts of zirconium and having an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol （Ａｂｓ） ) and Mw of 1.3 to 3.0 （Ａｂｓ） / Mn （Ａｂｓ） forming an octene homopolymer having the formula:

6. The process of claim 5, comprising:

7. contacting octene monomer with a bis-biphenylphenoxy catalyst having formula (V) above under polymerization conditions; containing residual amounts of germanium and having an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol （Ａｂｓ） ) and Mw of 1.3 to 3.0 （Ａｂｓ） / Mn （Ａｂｓ） forming an octene homopolymer having the formula:

7. The process of claim 6, comprising:

8. 10. The process of claim 1, wherein the contacting occurs at a temperature of from 23°C to 25°C.

9. The one or more C ６ ~C １４ 9. The process of claim 8, comprising contacting an α-olefin monomer with said bis-biphenylphenoxy catalyst and a boron-containing cocatalyst.

10. 1. A composition comprising: One or more C ６ ~C １４ a polymer of α-olefin monomers, the polymer comprising boron, a residual amount of zirconium, and a bis-biphenylphenoxy metal-ligand complex; The polymer has an absolute weight average molecular weight (Mw) of greater than 1,300,000 g / mol. （Ａｂｓ） ) and Mw of 1.3 to 3.0 （Ａｂｓ） / Mn （Ａｂｓ） and The composition wherein said bis-biphenylphenoxy metal-ligand complex is a bis-biphenylphenoxy metal-ligand complex having the formula (I): 【Chemistry 4】 During the ceremony, 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 which is neutral, monoanionic or dianionic, or two X together form a bidentate ligand which is neutral, monoanionic or dianionic, and X and n are selected such that said metal-ligand complex of formula (I) is, overall, neutral; each Z is independently O, S, N(C 1 -C 40 )hydrocarbyl, or P(C 1 -C 40 )hydrocarbyl; O is O (oxygen atom), L is a (C 1 -C 40 )hydrocarbylene or a (C 1 -C 40 )heterohydrocarbylene, wherein the (C 1 -C 40 )hydrocarbylene has a moiety comprising a linker backbone of 1 to 10 carbon atoms connecting the two Z groups in formula (I) (to which L is attached), or the (C 1 -C 40 )heterohydrocarbylene has a moiety comprising a linker backbone of 1 to 10 atoms connecting the two Z groups in formula (I), wherein each of the 1 to 10 atoms of the linker backbone of 1 to 10 atoms of the (C 1 -C 40 )heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently selected from the group consisting of O, S, S(O), S(O) 2 , Si(R c ) 2 , Ge(R c ) 2 , P(R c ), or N(R c ), where each R c is independently a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl; Each R 1-16 is selected from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, Si(R c ) 3 , Ge(R c ) 3 , P(R c ) 2 , N(R c ) 2 , OR c , SR c , NO 2 , CN, CF 3 , R C S(O), R C S(O) 2 , (R C ) 2 C═N, R C C(O)O, R c OC(O), R c C(O)N(R), (R C ) 2 NC(O), halogen atoms, hydrogen atoms, and combinations thereof.

11. 11. The composition of claim 10, wherein the polymer contains 0 ppm titanium.

12. 12. The composition of claim 10 or 11, wherein the polymer comprises from greater than 0 ppm to 300 ppm zirconium.

13. 13. The composition of any one of claims 10 to 12, wherein the polymer comprises from greater than 0 ppm to 300 ppm germanium.

14. The composition of any one of claims 10 to 13, wherein the polymer is selected from the group consisting of octene homopolymers and hexene homopolymers.

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