Polymerization of a purge stream containing 1-octene

Abstract

The present disclosure provides a method. In one embodiment, the method includes providing a purge stream containing octene monomer. The method includes contacting the purge stream with a bis-biphenyl phenoxy catalyst under polymerization conditions, and forming an absolute weight average molecular weight (Mw (Abs) ) is greater than 1,300,000 g / mol and Mw (Abs) / Mn (Abs) Octene polymers ranging from 1.3 to 3.0.

Description

Background Art

[0001] In the production of ethylene / octene copolymers, ethylene, octene comonomer and polymerization catalyst are introduced into a polymerization reactor under suitable reaction conditions (in the presence of solvent and chain transfer agent) to produce an ethylene / octene copolymer polymerization product stream. The product stream is taken out from the reactor and the product stream contains ethylene / octene copolymer, as well as hydrocarbon substances of unreacted monomer (ethylene), unreacted comonomer (octene) and other related hydrocarbons (hydrogen, ethane, methane, propane, pentane, hexane, butane). Ethylene / octene copolymer is separated from solvent and unreacted monomer and unreacted comonomer by devolatilization. Granular ethylene / octene copolymer is subsequently collected after granulation and cooling. After ethylene / octene copolymer is separated from the product stream, the hydrocarbon substances are recycled back to the polymerization reactor or purged from the system.

[0002] Reuse of purged hydrocarbon material is one of the biggest challenges facing large-scale polyolefin production. For example, the conversion of octene comonomer in ethylene / octene copolymer polymerization production is usually very low, such as between 10% and 20%. This means that 80%-90% of octene can pass through the reactor without being converted into polymer.

[0003] Ideally, the octene comonomer is recycled back to the polymerization reactor. Although the recycling of volatile monomers such as ethylene is very effective, the recycling of octene is difficult, especially when other saturated hydrocarbons are present in the product stream. The boiling point of octene is very close to the boiling points of other saturated and unsaturated substances present in the product stream, making octene separation difficult. The fresh octene stream also contains other isomers of octene (1 wt % to 5 wt % octene isomers based on the total weight of octene). Octene isomers do not react with ethylene in the polymerization process. Therefore, octene isomers aggregate or otherwise "accumulate" in the continuous recycling of the recycle stream, thereby reducing the recycling efficiency as a feed stream. In this way, octene isomers can accumulate up to 70% of the total recycle stream.

[0004] Thus, the art recognizes a continuing need for a way to utilize purge stream hydrocarbon materials that avoids simply discarding the purge stream hydrocarbon materials.There is also a need to utilize the octene monomer present in the purge stream. Summary of the invention

[0005] The present disclosure provides a method. In one embodiment, the method includes providing a purge stream containing octene monomer. The method includes contacting the purge stream with a bis-biphenyl phenoxy catalyst under polymerization conditions, and forming an absolute weight average molecular weight (Mw (Abs) ) is greater than 1,300,000 g / mol and Mw (Abs) / Mn (Abs) Octene polymers ranging from 1.3 to 3.0.

[0006] The present disclosure provides a composition. In one embodiment, the composition comprises an octene homopolymer and a solvent. The octene homopolymer has an absolute weight average molecular weight (Mw (Abs) ) and Mw of 1.3 to 3.0 (Abs) / Mn (Abs) . BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The figure is a schematic representation of a polymerization system according to an embodiment of the present disclosure.

[0008] definition

[0009] Any reference to the Periodic Table of the Elements is to the Periodic Table as published by CRC Press, Inc., 1990-1991. A group of elements in this table is referred to by a new notation for numbering the groups.

[0010] For purposes of U.S. patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference), especially with respect to definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and common general knowledge in the art.

[0011] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include the lower limit and the upper limit. For ranges containing explicit values ​​(e.g., 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two explicit values ​​is included (e.g., above range 1-7 includes subranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0012] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0013] As used herein, the term "blend" or "polymer blend" is a blend of two or more polymers. The blend may or may not be miscible (not phase separated at the molecular level). The blend may or may not be phase separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art.

[0014] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional components, steps or procedures, whether or not the components, steps or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed by using the term "comprising" may include any additional additives, adjuvants or compounds, whether in polymeric form or otherwise. In contrast, the term "consisting essentially of excludes any other components, steps or procedures (except those that are not essential for operability) from the scope of any subsequent statements. The term "consisting of" excludes any components, steps or procedures that are not specifically described or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination. The use of the singular includes the use of the plural, and vice versa.

[0016] "Ethylene polymers" are polymers that contain more than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene polymers" and "polyethylene" are used interchangeably.

[0017] As used herein, the term "1-octene" is a 1-octene having the molecular formula C8H 16 The unsaturated hydrocarbon α-olefin whose unsaturation is at the α position. 1-octene has the molecular structure (A) shown below.

[0018] Structure (A)

[0019]

[0020] As used herein, the term "isomers of octene" refers to isomers of the molecular formula C8H 16 And the unsaturated hydrocarbon that the unsaturation (double bond) is not in the alpha position. In other words, the term "isomer of octene" is 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.

[0021] An "octene polymer" is a polymer containing more than 50 weight percent (wt%) polymerized octene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer other than octene (such as selected from C 2-7 α-olefins and / or C 9-12Octene polymers include octene homopolymers and octene copolymers (meaning units derived from octene and one or more comonomers). The terms "octene polymers" and "polyoctene" are used interchangeably.

[0022] "Polymer" is a compound prepared by polymerizing monomers of the same or different types, which provide multiple and / or repeated "units" or "monomer units" constituting the polymer in a polymerized form. Therefore, the general term polymer covers the term homopolymer, which is usually used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is usually used to refer to polymers prepared from at least two types of monomers. It also covers all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" represent copolymers prepared by polymerizing ethylene or octene and one or more other polymerizable α-olefin monomers, respectively, as described above. It should be noted that although polymers are usually referred to as "made of" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than the unpolymerized substance. Generally, the polymers herein are referred to as "units" based on the polymerized form of the corresponding monomers.

[0023] Test Method

[0024] Gel Permeation Chromatography (GPC)

[0025] Chromatographic system is composed of PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. The column used is 4 Agilent "Mixed A" 30cm 20 micron linear mixed bed columns and 20um pre-column. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0026] The GPC column set was calibrated with 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights and arranged in 6 "cocktail" mixtures with at least ten times spacing between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. The polystyrene standards were dissolved at 80 degrees Celsius and gently stirred for 30 minutes. A third-order polytopic was used to fit the corresponding polystyrene equivalent calibration points.

[0027] Plate counts for the GPC column set were performed using decane (prepared as 0.04 g in 50 mL TCB and dissolved for 20 minutes under slow stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 μL injection according to the following equations:

[0028]

[0029] Where RV is the retention volume in milliliters, peak width is in milliliters, peak maximum is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peak maximum.

[0030]

[0031] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the maximum position of the peak, tenth height is 1 / 10 of the height of the peak maximum, and where post-peak refers to the tail of the peak with a retention volume later than the peak maximum, and where pre-peak refers to the front of the peak with a retention volume earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0032] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-covered vial previously sparged with nitrogen by the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for 2 hours under "slow" shaking.

[0033] Based on the GPC results, the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer was used, according to Equations 4-6, using the PolymerChar GPCOneTM The software was used to calculate the Mn value of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polystyrene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation.

[0034]

[0035]

[0036]

[0037] 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 (nominal)) for each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the retention volume of the decane peak in the narrow standard calibration (RV (FM calibration)). It was then assumed that any changes in the decane marker peak time were related to linear changes in the flow rate (flow rate (effective)) throughout the run. In order to facilitate the highest accuracy in measuring the RV of the flow marker peak, a least squares fitting procedure was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7. The processing of the flow marker peak was performed by the PolymerChar GPCOne TM The acceptable flow rate correction is such that the effective flow rate should be within + / - 1% of the nominal flow rate.

[0038] Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (Equation 7)

[0039] Triple Detector GPC (TDGPC)

[0040] The chromatography system, running conditions, column setup, column calibration and calculation of conventional molecular weight moments and distributions were performed according to the methods described in Gel Permeation Chromatography (GPC).

[0041] To determine the offset of the viscometer and light scattering detectors relative to the IR5 detector, a systematic method for determining multi-detector offset was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)) using the PolymerChar GPCOne TM The software optimizes the triple detector log (MW and IV) results from broad homopolymer polyethylene standards (Mw / Mn>3) with the narrow standards column calibration results from the narrow standards calibration curve.

[0042] Using PolymerChar GPCOne TM The software obtains absolute molecular weight data 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 to determine the molecular weight is obtained based on the mass detector area and the mass detector constant, which is derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards of known weight average molecular weight. The calculated molecular weight (using GPCOne TM ) is obtained using the light scattering constants from one or more of the polyethylene standards mentioned below and a refractive index concentration coefficient dn / dc of 0.104. Typically, the mass detector response (IR5) and the light scattering constant (using GPCOne TM The viscosity should be determined by a linear polyethylene standard with a molecular weight of approximately 120,000 g / mole. Viscometer calibration (using GPCOne TM Determination) can be achieved using methods described by the manufacturer, or alternatively, by using published values ​​for appropriate linear standards. Calculation of viscometer constants (using GPCOne TM The specific viscosity area (DV) and injected mass of the calibration standards are related to their intrinsic viscosity. The chromatographic concentrations are assumed to be low enough to eliminate the effects of the 2nd viral coefficient (the effect of concentration on molecular weight).

[0043] Absolute weight average molecular weight (Mw (Abs)) is (using GPCOne TM ) is obtained from the area of ​​the light scattering (LS) integrated chromatogram (calculated from the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area. Molecular weight and intrinsic viscosity responses are at the end of the chromatogram where the signal-to-noise ratio becomes low (using GPCOne TM ) linear extrapolation. Other corresponding moments Mn (Abs) and Mz (Abs) The calculations based on equations 8 to 9 are as follows:

[0044]

[0045]

[0046] Residual amount of catalyst metal. The "residual amount" of catalyst metal (Ti, Hf, Zr and Ge) is 0 ppm or more to less than 300 ppm and is determined by a mass balance based on the amount of catalyst added and the amount of polymer formed during the reaction. The results are reported in parts per million (ppm).

[0047] Viscosity. The viscosity was measured at a shear rate of 0.01-100 l / sec using the viscosity steady state method using an Anton Paar MCR102 equipped with a CC27 cylinder measuring system and a C-ETD300 heating system. About 20 ml of sample was added to a measuring cup and then heated to 100 ° C. The measuring system was then lowered into the sample until it reached 0.0 mm. This was done over a period of time so that the force did not reach more than 15 Newtons (N). Once the measuring system reached 0.0 mm, the sample was kept at 100 ° C together with the measuring system for 10 minutes to allow the temperature to equilibrate. The results are reported in milliPascal seconds (m-Pas). DETAILED DESCRIPTION

[0048] The present disclosure provides a method. In one embodiment, the method includes providing a purge stream comprising octene monomer. The method includes contacting the purge stream with a bis-biphenyl phenoxy catalyst under polymerization conditions. The method includes forming an absolute weight average molecular weight (Mw (Abs) ) is greater than 1,300,000 g / mol and Mw (Abs) / Mn (Abs) Octene polymers ranging from 1.3 to 3.0.

[0049] The present method includes providing a purge stream. The purge stream comprises octene monomer, or otherwise contains octene monomer. As used herein, a "purge stream" is one of several fractions separated or otherwise recovered from the effluent leaving the polymerization reactor after the polymerization reaction occurs. The liquid effluent leaving the polymerization reactor contains solid (granular) polymer products, which are removed. The recycle stream is also removed from the effluent, which is further processed and returned to the polymerization reactor. The purge stream is (i) the stream remaining after the polymer product has been recovered from the effluent and (ii) after the recycle stream has been separated from the effluent. The purge stream contains unreacted olefin monomers and other hydrocarbons used during the polymerization reaction (hereinafter referred to as "hydrocarbon substances"). It should be understood that the purge stream does not contain or is substantially free of solid polymer products.

[0050] In one embodiment, the purge stream is the effluent from a polymerization reactor in which ethylene and octene are copolymerized. The purge stream comprises hydrocarbon material consisting of unreacted octene monomer and other hydrocarbons.

[0051] In one embodiment, the sweep stream comprises

[0052] (i) 20 to 50 wt% or 30 to 40 wt% of 1-octene monomer,

[0053] (ii) 10 to 50 wt % or 20 to 40 wt % of a hydrocarbon solvent, and

[0054] (iii) 10 wt % to 70 wt %, or 20 wt % to 60 wt %, or 30 wt % to 50 wt % of octene isomers other than 1-octene, the weight percentages being based on the total weight of the purge stream.

[0055] In one embodiment, the method includes removing any ethylene that may be present in the purge stream. The purge stream is sparged with nitrogen so that no ethylene is present in the purge stream. The purge stream contains no or substantially no ethylene monomer, i.e., 0 wt. %, or greater than 0 wt. % to less than 0.01 wt. % ethylene based on the total weight of the purge stream. The purge stream comprises

[0056] (i) 20 to 50 wt% or 30 to 40 wt% of 1-octene monomer,

[0057] (ii) 10 to 50 wt % or 20 to 40 wt % of a hydrocarbon solvent,

[0058] (iii) 10 to 70 wt%, or 20 to 60 wt%, or 30 to 50 wt% of octene isomers other than 1-octene,

[0059] (iv) is free or substantially free of ethylene monomer, and the weight percentages are based on the total weight of the purge stream. It is understood that components (i)-(iv) total up to 100 weight percent of the purge stream.

[0060] The method comprises contacting the sweep stream with a bis-biphenylphenoxy catalyst under polymerization conditions. As used herein, "polymerization conditions" are temperature, pressure, reactant concentrations, solvent selection, chain transfer agent (CTA), reactant mixing / addition parameters, and other conditions within a polymerization reactor that promote the reaction between the reactants and the formation of the resulting product (i.e., octene polymer or polyoctene). The polymerization can be carried out in a batch process or a continuous process in a tubular reactor, a stirred autoclave reactor, a continuous stirred tank reactor, a gas phase polymerization reactor, a slurry phase polymerization reactor, a loop reactor, an isothermal reactor, a fluidized bed gas phase reactor, and combinations thereof.

[0061] Under polymerization conditions, the purge stream is contacted with a bis-biphenylphenoxy catalyst (or "BBP" interchangeably). The bis-biphenylphenoxy catalyst is a metal-ligand complex having the structure shown in Formula (I) below:

[0062] Formula (I)

[0063]

[0064] in

[0065] M is a metal selected from zirconium or hafnium, the metal being in a formal oxidation state of +2, +3 or +4;

[0066] n is an integer from 0 to 3, and wherein when n is 0, X is absent; and

[0067] Each X is independently a neutral, monoanionic or dianionic monodentate ligand; or two X taken together form a neutral, monoanionic or dianionic bidentate ligand; and X and n are selected in such a way that the metal-ligand complex of formula (I) is neutral overall; and

[0068] Each Z is independently O, S, N (C1-C 40 ) alkyl or P(C1-C 40 ) a hydrocarbon group; and

[0069] O is O (oxygen atom);

[0070] L is (C1-C 40 )alkylene or (C1-C 40 ) heteroalkylene, wherein the (C1-C 40 )alkylene has a moiety comprising a 1-carbon atom to a 10-carbon atom main chain connecting two Z groups in formula (I) (L is bonded to the two Z groups), or the (C1-C40 ) heteroalkylene has a moiety comprising a 1-atom to 10-atom connecting backbone connecting two Z groups in formula (I), wherein the (C1-C 40 ) wherein each of the 1 to 10 atoms of the 1-atom to 10-atom connected main chain of the heteroalkylene group is independently a carbon atom or a heteroatom, wherein 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 ), where each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl; and

[0071] Each R 1-16 Selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, 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), halogen atoms, hydrogen atoms and combinations thereof.

[0072] The bis-biphenylphenoxy catalyst having the structure of formula (I) can be rendered catalytically active by contacting the metal-ligand complex with an activating co-catalyst, or by combining the metal-ligand complex with an activating co-catalyst.

[0073] Non-limiting examples of suitable activating cocatalysts for use herein include alkylaluminums; polymeric or oligomeric aluminoxanes (also referred to as alumoxanes); 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" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0074] Non-limiting examples of suitable Lewis acid activators (cocatalysts) include those containing 1 to 3 (C1-C 20 In one embodiment, the Group 13 metal compound is tri((C1-C 20 ) alkyl) substituted aluminum, tri((C1-C 20 )alkyl)-boron compounds, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 ) aryl) boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tetra((C1-C 20 ) alkyl) borate or tetra((C1-C 20 )alkyl)boric acid tri((C1-C 20 As used herein, the term "ammonium" means a (C1-C 20 )alkyl)N(H)3 + or N(H)4 + of nitrogen cations, each of which (C1-C 20 ) The hydrocarbon groups, when present in two or more, may be the same or different.

[0075] Non-limiting examples of combinations of neutral Lewis acid activators (cocatalysts) include those comprising tri((C1C4)alkyl)aluminum and tri((C6C 18 In some embodiments, the present invention relates to a mixture of a combination of a (( ...

[0076] The bis-biphenyl phenoxy catalyst having the structure of formula (I) can be activated by combining with one or more cocatalysts (e.g., a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof) to form an active catalyst composition. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl) methyltetrakis(pentafluorophenyl)borate (1<->)amine (i.e., [HNMe(C 18 H 37 )2][B(C6F5)4]) and a combination of the two.

[0077] One or more of the aforementioned activating co-catalysts are used in combination with each other. 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 aluminoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more activating co-catalysts in the activating co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When aluminoxane is used alone as an activating co-catalyst, preferably, the number of moles of aluminoxane employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). In some other embodiments, when tris(pentafluorophenyl)borane is used alone as an activating co-catalyst, the ratio of the number of moles of tris(pentafluorophenyl)borane employed to the total number of moles of the 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 activating co-catalyst is typically employed in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of formula (I).

[0078] In one embodiment, the bis-biphenylphenoxy catalyst having the structure of formula (I) includes a metal M that is zirconium.

[0079] The method comprises contacting a purge stream with a bis-biphenyl phenoxy catalyst of formula (I) under polymerization conditions and forming an absolute weight average molecular weight (Mw (Abs) ) is greater than 1,300,000 g / mol and Mw (Abs) / Mn (Abs) Octene polymers ranging from 1.3 to 3.0.

[0080] The method includes avoiding or otherwise excluding the titanium-containing catalyst and / or titanium-containing promoter from the contacting step.

[0081] In one embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the following structural formula (V):

[0082] Formula (V)

[0083]

[0084] wherein Ge is germanium, Me is a methyl group, tBu is a tert-butyl group, and iPr is an isopropyl group. The method comprises contacting the sweep stream with a bis-biphenyl phenoxy catalyst of formula (V) under polymerization conditions, and forming an octene polymer having

[0085] (i) Mw 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) ;

[0086] (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) ;as well as

[0087] (iii) residual amounts of zirconium and residual amounts of germanium.

[0088] The method includes avoiding or otherwise excluding the titanium-containing catalyst and / or titanium-containing promoter from the contacting step.

[0089] In one embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the following structural formula (VI):

[0090] Formula (VI)

[0091]

[0092] wherein Me is a methyl group and tBu is a tert-butyl group. The method comprises contacting the sweep stream with a bis-biphenyl phenoxy catalyst of formula (VI) under polymerization conditions and forming an octene polymer having

[0093] (i) Mw 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) ;

[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 (Abs) / Mn (Abs) ;as well as

[0095] (iii) Residual amounts of zirconium.

[0096] The method includes avoiding or otherwise excluding the titanium-containing catalyst and / or titanium-containing promoter from the contacting step.

[0097] The present disclosure provides a composition. In one embodiment, a composition is provided, which comprises (i) an absolute weight average molecular weight (Mw (Abs) ) is greater than 1,300,000 g / mol and Mw (Abs) / Mn (Abs) The composition further comprises (ii) a solvent.

[0098] Dissolve the octene homopolymer in a solvent. The solvent is a linear, branched or cyclic C4-C 14 or C6-C 12 Aliphatic Hydrocarbons. Non-limiting examples of suitable aliphatic hydrocarbon solvents include butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and combinations thereof.

[0099] In one embodiment, the composition comprises an octene homopolymer dissolved in a solvent, the octene homopolymer polymerized using a catalyst of formula (I), or formula (V) or formula (VI), the octene homopolymer having one, some or all of the following characteristics:

[0100] (i) Mw 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

[0101] (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

[0102] (iii) 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; and / or

[0103] (iv) residual amounts 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

[0104] (v) 0 ppm, or more than 0 ppm and less than 10 ppm of titanium.

[0105] In one embodiment, the composition comprises (i) 10 wt% to 50 wt% of an octene homopolymer, (ii) 0 wt% to 70 wt% of an octene isomer, and (iii) 90 wt% to 10 wt% of a solvent, wherein components (i), (ii) and (iii) total 100 wt% of the composition.

[0106] In an embodiment, the composition comprises

[0107] (i) 10 wt%, or 20 wt%, or 30 wt% to 40 wt%, or 50 wt% of octene homopolymer;

[0108] (ii) 0%, or 10%, or 25% to 50%, or 75% by weight of octene isomers;

[0109] (iii) from 90 wt%, or 80 wt%, or 70 wt% to 60 wt%, or 50 wt% of a solvent; wherein (i), (ii) and (iii) total 100 wt% of the composition.

[0110] In an embodiment, the composition comprises

[0111] (i) 25 wt% or 30 wt% to 35 wt% of octene homopolymer;

[0112] (ii) 30 wt%, or 35 wt% to 40 wt%, or 45 wt%, or 50 wt% octene isomers;

[0113] (iii) from 10 wt%, or 15 wt% to 20 wt%, or 25 wt% of a solvent; wherein (i), (ii) and (iii) total 100 wt% of the composition.

[0114] In one embodiment, the composition comprises from 80 wt%, or 85 wt% to 90 wt%, or 95 wt% of the octene homopolymer and from 20 wt%, or 15 wt% to 10 wt%, or 5 wt% of the solvent, the octene homopolymer and the solvent totaling 100 wt% of the composition.

[0115] In an embodiment, the composition comprises

[0116] (i) 35 to 45 wt. % of an octene homopolymer;

[0117] (ii) 65% to 55% by weight, wherein (i) and (ii) total 100% by weight of the composition, and

[0118] The viscosity of the composition is 2.9014*10 +05 m-Pas to 3.573*10 +07 m-Pas.

[0119] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0120] Example

[0121] The catalysts used in the comparative samples (CS) and the inventive examples (IE) are provided in Table 1 below.

[0122] Table 1

[0123]

[0124] A. Polymerization using a sweep stream

[0125] FIG. 1 is a schematic diagram of an ethylene and octene polymerization process. Ethylene monomer, octene comonomer, solvent and catalyst are fed into a reactor. The resulting ethylene / octene copolymer is recovered and the recycle stream is introduced into the reactor, and a purge stream is separated from the ethylene and octene polymerization process. The purge stream contains 20 wt% to 50 wt% 1-octene, 10 wt% to 70 wt% octene isomers and 10 wt% to 50 wt% ISOPAR-E based on the total weight of the purge stream. ISOPAR-E is C 8-12 Aliphatic solvent, available from Exxon Chemical Co.

[0126] The purge flows used to prepare the comparative sample (CS) and the inventive example (IE) were provided as follows:

[0127] Purge Stream A: 45 wt% 1-octene, 45 wt% octene isomers, and 10% ISOPAR-E, based on the total weight of Purge Stream A; and

[0128] • Purge Stream B: 37 wt% 1-octene, 46 wt% octene isomers, and 17% ISOPAR-E, based on the total weight of Purge Stream B.

[0129] The purge stream was collected and purged with nitrogen and stored over molecular sieves in a nitrogen-filled glove box.

[0130] For comparative sample (CS), polymerization was carried out at a temperature of 23° C. to 25° C. for a period of 12 hours with Ziegler-Natta catalyst (ZN) in a 40 mL vial containing 12 mL purge flow, 4 μmol catalyst (ZN) and 5 equivalents (eq.) of Et3Al (as activator). Then, the solvent and unreacted octene isomers were removed under vacuum. CS5 was polymerized in the same manner, except that the solution temperature was maintained at −35° C. for a period of 48 hours during the polymerization.

[0131] For Examples (IE1-14) of the present invention, a bis-biphenyl phenoxy catalyst (BBP1 or BBP2) was used in a reaction mixture containing 12 mL of purge flow, 4 μmol of catalyst and 1.2 equivalents of ((R2N(H)MeB(C6F5)4, where R is a hydrogenated tallow alkyl (C 14–18 The polymerization was carried out in a 40 mL vial containing 2-(4-(2-octene-1-yl)-4-nitro-2-ol (CAS No. 200644-82-2) as an activator) at a temperature of 23-25° C. for a period of twelve hours. The solvent and unreacted octene isomers were then removed under vacuum.

[0132] The polymerization results are reported in Table 2 below.

[0133] The properties of the resulting octene homopolymer are provided in Table 2 below.

[0134] Table 2

[0135]

[0136]

[0137] 1 ppm of residual catalyst metal present in octene homopolymer based on total weight of octene homopolymer.

[0138] 2 The polymerization was carried out at -35°C.

[0139] Table 2 shows that polymerization of 1-octene from a purge stream (CS 1-4) with a ZN catalyst at room temperature produced polyoctenes with molecular weights ranging from 1,500,000 g / mol to 1,900,000 g / mol and a broad molecular weight distribution (Mw / Mn) ranging from 6.94 to 8.97. When the polymerization temperature was reduced to -35°C (CS5), the molecular weight was significantly higher.

[0140] For the polymerization of 1-octene from a purge stream at room temperature, the molecular weight of the polyoctenes was significantly higher, with molecular weights greater than 1,300,000 g / mol, specifically in the range of 1,400,000 g / mol to 8,600,000 g / mol, using inventive catalysts BBP1 and BBP2 (IE 1-14). Only inventive examples IE1-IE14 yielded high molecular weight polyoctenes (greater than 1,300,000 g / mol) with a narrow molecular weight distribution (1.3-3.0 and specifically 1.42-2.09). The resulting high molecular weight polyoctenes were free of titanium, or titanium-free; the high molecular weight polyoctenes obtained in inventive examples IE1-IE14 contained residual zirconium, and the high molecular weight polyoctenes obtained in inventive examples IE1-IE12 contained residual zirconium and residual germanium.

[0141] It is particularly intended that the present disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments including parts of the embodiments and combinations of elements of different embodiments as appear within the scope of the following claims.

Claims

1. A method, comprising: Providing a purge stream, wherein the purge stream consists of: 20 to 50% by weight of 1-octene, 10% to 50% by weight of a solvent, 10 to 70 wt. % of octene isomers, and removing any ethylene present in the purge stream and providing a purge stream comprising 0 wt % ethylene; The purge stream is contacted under polymerization conditions with a bis-biphenyl phenoxy catalyst having the formula (V) Or having formula (VI) as well as The absolute weight average molecular weight (Mw) was determined by triple detector gel permeation chromatography (TDGPC). (Abs) ) greater than 1,300,000 g / mol and Mw measured by TDGPC (Abs) / Mn (Abs) Octene polymers ranging from 1.3 to 3.0.

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