Ethylene / octene multiblock copolymers and processes for producing same

Abstract

The present disclosure provides a process. In one embodiment, the process comprises contacting ethylene and octene with a catalyst system comprising (i) a first polymerization catalyst having a structure of Formula (III), a second polymerization catalyst having a structure of Formula (I), and (iii) a chain shuttling agent under polymerization conditions at a temperature greater than 125°C. The process comprises forming an ethylene / octene multiblock copolymer having a normalized OOO triad content greater than 0.25. The present disclosure provides a resulting composition produced by the process. In one embodiment, the composition comprises an ethylene / octene multiblock copolymer having a normalized OOO triad content greater than 0.25.

Description

[Technical Field]

[0001] Ethylene / octene multiblock copolymers offer the durability and high heat resistance benefits of high-density polyethylene while maintaining important properties of elastomeric low-density polyolefins, such as elastic behavior, flexibility, and processability. Ethylene / octene multiblock copolymers typically contain high-density "hard" segments and low-density "soft" segments. The soft segments contain higher comonomer content, which can be soft and sticky. For commercial production of ethylene / octene multiblock copolymers, where bulk shipping is beneficial, the low-density soft blocks are a constraint that limits large-scale production and storage of pellets. While many applications could benefit from the low-density soft blocks (which incorporate more octene), existing ethylene / octene multiblock copolymer systems are limited due to poor solids handling.

[0002] The art recognizes a need for ethylene / octene multiblock copolymers with increased soft segment octene incorporation and improved solids handling performance, specifically improved (lower) unconstrained yield strength. Summary of the Invention

[0003] The present disclosure provides a process. In one embodiment, the process includes contacting ethylene and octene with a catalyst system including (i) a first polymerization catalyst having a structure of Formula (III), a second polymerization catalyst having a structure of Formula (I), and (iii) a chain shuttling agent under polymerization conditions at a temperature greater than 125° C. The process includes forming an ethylene / octene multiblock copolymer having a normalized OOO triad content greater than 0.25.

[0004] The present disclosure provides a resulting composition produced by the process. In one embodiment, the composition comprises an ethylene / octene multi-block copolymer having a normalized OOO triad content greater than 0.25. [Brief explanation of the drawings]

[0005] [Figure 1] FIG. 1 shows the extrapolation of elution temperatures for TGIC temperature calibration. The solid line is the experimental data. The dashed line is the extrapolation of the elution temperatures of the two isothermal steps. [Figure 2] 1 is a graph showing the correlation of the elution peak temperature (Tp) of ethylene-octene copolymers produced by single-site catalysts with octene weight percent. Thermal Gradient Interaction Chromatography (TGIC) is measured according to the reference (Cong et al., Macromolecules, 2011, 44(8), 3062-3072), which is incorporated herein by reference. Octene content is measured by C NMR, as disclosed in U.S. Pat. No. 7,608,668, which is incorporated herein by reference. [Figure 3] Schematic of the test apparatus for funnel flow (FF). The FF test apparatus includes a steep-slope glass funnel attached to a cylinder (4.15 inch diameter). The cylindrical section provides the necessary volume so that a substantial amount of pellets can be tested. [Figure 4] 1 is a graph showing the high temperature thermal gradient interaction chromatography (TGIC) second peak temperature (Tp2) as a function of soft segment melting temperature (SS-Tm) for inventive examples and comparative samples of ethylene / octene multiblock copolymers according to one embodiment of the present disclosure. [Figure 5] 1 is a TGIC curve showing the first peak temperature (Tp1) and second peak temperature (Tp2) for inventive Example 1 in accordance with one embodiment of the present disclosure. [Figure 6] 1 is a DSC heating curve showing the soft segment melting peak for inventive Example 1 in accordance with one embodiment of the present disclosure. [Figure 7] 1 is a graph showing soft segment melting temperature (SS-Tm) as a function of normalized OOO triad for inventive examples and comparative samples of ethylene / octene multi-block copolymers according to one embodiment of the present disclosure. [Figure 8] 1 is a graph showing glass transition temperature (Tg) as a function of normalized OOO triads for inventive examples and comparative samples of ethylene / octene multiblock copolymers in accordance with one embodiment of the present disclosure.

[0006] definition Any reference to the Periodic Table of the Elements is to that published by CRC Press, Inc., 1990-1991. References to element groups in this table are by 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 hereby incorporated by reference in their entirety (or the publication's equivalent United States patent application is likewise incorporated by reference), particularly with respect to the disclosure of definitions and general knowledge in the art (to the extent that they are in no way inconsistent with definitions specifically provided in this disclosure).

[0008] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, inclusive. Ranges containing explicit values ​​(e.g., 1 or 2, or 3-5, or 6, or 7) also include all subranges between any two explicit values ​​(e.g., the 1-7 range above includes subranges such as 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0009] Unless stated to the contrary or implicit from context, 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 term "blend" or "polymer blend" refers 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] An "ethylene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and may optionally 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-based polymer" and "polyethylene" may be used interchangeably.

[0014] An "interpolymer" is a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from three or more different monomers, such as terpolymers, tetrapolymers, etc.

[0015] An "olefin-based polymer" or "polyolefin" is a polymer that contains more than 50 weight percent polymerized olefin monomers (based on the total amount of polymerizable monomers) and may optionally include at least one comonomer. Non-limiting examples of olefin-based polymers include ethylene-based polymers or propylene-based polymers.

[0016] 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 "propylene / α-olefin polymer" refer to the aforementioned copolymers prepared from polymerizing ethylene or propylene with one or more additional polymerizable α-olefin monomers, respectively. While polymers are often referred to as "made of" one or more particular monomers, "based on" particular monomers or monomer types, "containing" 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 in terms of "units" that are the polymerized form of the corresponding monomers.

[0017] Test Method 13 C NMR 13 C nuclear magnetic resonance ( 13C nuclear magnetic resonance (NMR) samples are prepared by adding approximately 2.7 g of a 50 / 50 (w:w) mixture of tetrachloroethane-d2 / orthodichlorobenzene containing 0.025 M chromium acetylacetonate, Cr(AcAc)3 (or tetrachloroethane-d2 containing 0.025 M Cr(AcAc)3) to 0.2 g of polymer sample in a 10 mm NMR tube. Oxygen is removed from the sample by purging the tube headspace with nitrogen. The sample is then dissolved and homogenized by heating the tube and its contents to approximately 135 °C using a heating block and heat gun. Each dissolved sample is visually inspected to confirm homogeneity.

[0018] 13 C NMR data are collected using a 10 mm cryoprobe on either a Bruker 400 MHz or 600 MHz spectrometer. Data are acquired at a sample temperature of 120 °C using a 7.3 s pulse repetition delay, a 90 degree flip angle, and inverse gated decoupling. All measurements are performed in locked mode, without sample rotation. Samples are allowed to thermally equilibrate for 7 min before data acquisition. 13 C NMR chemical shifts are internally referenced to the EEE triad at 30.0 ppm.

[0019] Comonomer content was determined by literature assignment (Liu, W.; Rinaldi, PL; McIntosh, LH; and Quirk, RP; Macromolecules, 34, 2001, 4757-4767) and integration. 13The C NMR spectrum is used to solve and determine the vector equation s = fM, where M is the assignment matrix, s is the row vector representation of the spectrum, and f is the mole fraction composition vector. The elements of f are the triads of ethylene (E) and octane (O) with all permutations of E and O. The assignment matrix M is created with one row for each triad in f and a column for each integrated NMR signal. The matrix elements are integer values ​​determined by referencing the assignments (Liu, W.; Rinaldi, PL; McIntosh, LH; and Quirk, RP; Macromolecules, 34, 2001, 4757-4767). This equation is determined by the relationship between s and the integrated NMR signal of each sample. 13 Solve by changing the elements of f required to minimize the error function between the C data. This is done in Microsoft Excel by using the Solver function.

[0020] For EOE / 1000C, EOO(OOE) / 1000C, and OOO / 1000C, the integrals from 8 to 46 ppm are first set to 1000, and then the methine peak integrals around 38.2 ppm are measured for EOE, around 35.9 ppm for EOO(OOE), and around 33.7 ppm for OOO. Total O / 1000C is defined as EOE / 1000C + EOO(OOE) / 1000C + OOO / 1000C. The term "1000C" is 1000 carbon atoms, and the term " / 1000C" is per 1000 carbon atoms. "Percent OOO" (or "OOO%") is calculated as OOO% = 100. * It is defined as (OOO / 1000C) / (total O / 1000C). "Normalized OOO content" (Norm OOO) is defined as (OOO%) / (NMR O mole %).

[0021] Density is measured according to ASTM D792, Method B. Results are recorded in grams per cubic centimeter (g / cc).

[0022] Differential scanning calorimetry (DSC) Differential scanning calorimetry (DSC) can be used to measure the melting, crystallization, and glass transition behavior of polymers over a wide temperature range. For example, this analysis is performed using a TA Instruments Discovery DSC equipped with a refrigerated cooling system, RCS (refrigerated cooling system), and autosampler. A nitrogen purge gas flow rate of 50 mL / min is used during testing. Each sample is melt-pressed into a thin film at approximately 190°C, and the molten sample is then air-cooled to room temperature (approximately 25°C). A 3-10 mg, 6 mm diameter specimen is extracted from the cooled polymer, weighed, placed in a lightweight aluminum pan (approximately 50 mg), and crimped shut. It is then analyzed to determine its thermal properties.

[0023] The thermal behavior of the sample is determined by ramping the sample temperature and creating a heat flow versus temperature profile. First, the sample is rapidly heated to 180°C and held isothermal for 5 minutes to remove its thermal history. The sample is then cooled to -90°C at a cooling rate of 10°C / min and held isothermal at -90°C for 5 minutes. The sample is then heated to 150°C at a heating rate of 10°C / min (this is the "second heating" ramp). The cooling and second heating curves are recorded.

[0024] The soft segment melting temperature (SS-Tm) is determined from the second heating curve of the DSC. Ethylene / octene multiblock copolymers typically have two melting peaks, one associated with the soft segment and one associated with the hard segment. SS-Tm is associated with a lower temperature peak, as shown in Figure 6. In some block copolymers, the peak associated with soft segment melting is a small hump on the baseline, making it difficult to assign a peak maximum. This difficulty can be overcome by converting a regular DSC profile to a weighted DSC profile using the following method. In DSC, heat flow depends on the amount of material melting at a particular temperature and the specific heat capacity, which is temperature-dependent. The temperature dependence of the specific heat capacity in the melting regime of linear low-density polyethylene results in an increase in the heat of fusion with decreasing comonomer content. That is, the value of the heat of fusion becomes progressively lower as crystallinity decreases with increasing comonomer content. See Wild, L. Chang, S.; Shankernarayanan, M. J. Improved method for compositional analysis of polyolefins by DSC. Polym. Prep 1990;31:270-1, which is incorporated herein by reference in its entirety. For a given point on the DSC curve (defined by heat flow in watts per gram and temperature in degrees Celsius) by taking the ratio of the expected heat of fusion to the temperature-dependent heat of fusion (ΔH(T)) for a linear copolymer, the DSC curve can be converted to a weight-dependent distribution curve. The second heating curve is baseline corrected by drawing a linear baseline between the heat flows at -30°C and 135°C. The temperature-dependent heat of fusion curve can then be calculated from the sum of the integrated heat flows between two consecutive data points, which can then be represented overall by a cumulative enthalpy curve. The expected relationship between the heat of fusion for a linear ethylene / octene copolymer at a given temperature is shown by the heat of fusion versus melting temperature curve.Using random ethylene / octene copolymers, the expected heat of fusion, ΔH, of the linear copolymer. 直鎖状コポリマー , and the melting temperature T m The following relationship can be obtained for (units °C):

[0025]

number

[0026] For each integrated data point, a fractional weight can be assigned to each point on the DSC curve by taking the ratio of the enthalpy from the cumulative enthalpy curve at a given temperature to the expected heat of fusion of a linear copolymer at that temperature. This method is applicable to ethylene / octene copolymers but can be adapted to other polymers. The soft segment Tm is assigned as the location of the maximum in the enthalpy fractional weight versus temperature curve.

[0027] The glass transition temperature, Tg, is determined from the second heating curve of a DSC where half of the sample has acquired a liquid heat capacity, as described in Bernhard Wunderlich, *The Basis of Thermal Analysis*, in *Thermal Characterization of Polymeric Materials* 92, 278-279 (Edith A. Turi ed., 2d ed. 1997). Baselines are drawn below and above the glass transition region and extrapolated through the Tg region. The temperature at which the heat capacity of the sample is midway between these baselines is the Tg.

[0028] The melting temperature Tm of a polymer is determined as the temperature corresponding to the maximum heat flow in the DSC heating curve.

[0029] Elastic recovery The 100% and 300% hysteresis are determined from cyclic loading to 100% and 300% strain using ASTM D 1708 microtensile specimens with an Instron™ instrument. Samples are loaded and unloaded at 267% / min for three cycles at 21°C. For 300% strain cyclic experiments, the retraction stress at 150% strain from the first unloading cycle is recorded. Percent recovery for all experiments is calculated from the first unloading cycle using the strain at which the load returns to baseline. Percent elastic recovery is defined as follows:

[0030]

number

[0031] funnel flow rate The funnel flow velocity, or "FF" test, quantifies pellet-to-pellet stickiness. The test is based on the basic concept that increasing inter-particle interactions (stickiness) decreases the discharge rate from a steep-slope funnel. Changes in discharge rate can be correlated with changes in the surface properties (i.e., stickiness) of the polymer pellets.

[0032] The test apparatus (see Figure 3) consisted of a steeply sloping glass funnel attached to a cylinder (4.15 inches in diameter). The cylindrical portion provided the necessary volume, allowing a significant amount of pellets to be tested and avoiding the problem of distinguishing between small values ​​of discharge time. The test was repeated five times for statistical purposes.

[0033] The discharge rates of the pellets were measured on "as received" commercial reference materials, and the inventive examples (pellets) were talc coated prior to measurement. The pellets were conditioned for the specified periods at the specified storage temperatures. The pellets were "heat treated" or "aged" for 3 weeks at 42°C. The conditioned pellets were cooled overnight at 21°C to reach a constant temperature.

[0034] As discussed above, the polymer (approximately 2500 g, in pellet form, 30±10 pellets per gram) was heat treated in an oven at 42° C. for 3 weeks. The polymer was removed from the oven and cooled at 21° C. for 12 hours. A funnel was filled with polymer pellets (2500 g), and the time it took for the pellets to completely drain from the funnel was measured, and the drainage rate was calculated using the following equation:

number

[0035] The funnel flow rate is an indicator of pellet stickiness and is reported in grams per second (g / s). A flow rate of 120 g / s was determined to be the minimum flow rate desired to achieve acceptable handling characteristics of the polymer pellets. However, higher rates are preferred for better handling of the polymer pellets. Higher pellet flow rates correspond to easier-flowing, less sticky pellets.

[0036] Talc pellet coating Place the pellets to be coated into a Ziploc bag sized to fill approximately halfway with pellets to ensure proper mixing. Use the following equation to calculate the amount of coating agent (talc) needed to coat the pellets to the desired ppm level: Weight of coating material (gm) = Weight of pellets (gm) x Desired coating level (ppm) / 1,000,000

[0037] Weigh out the amount of coating material using a 4-decimal balance and divide it into 4 equal portions. Take the first portion (1 / 4 of the coating material) and sprinkle it on top of the pellets in the Ziploc bag. Fill the bag with air and mix the pellets thoroughly for 30 seconds by rocking the pellets back and forth vigorously. Repeat for each of the three remaining portions.

[0038] High temperature thermal gradient interaction chromatography (TGIC).

[0039] High-temperature thermal gradient interaction chromatography (HT-TGIC or TGIC) measurements were performed using a commercially available crystallization elution fractionation instrument (CEF) (Polymer Char, Spain) (Cong, et al., Macromolecules, 2011, 44(8), 3062-3072). The CEF instrument was equipped with either an IR-4 or IR-5 detector. Graphite was used as the stationary phase in the HT-TGIC column (Freddy, A. Van Damme et al., U.S. Pat. No. 8,476,076; Winniford et al., U.S. Pat. No. 8,318,896). A single graphite column (250 × 4.6 mm) was used for the separation. The graphite was packed into the column using dry packing followed by slurry packing techniques, as disclosed in EP 2714226 (B1). The contents of the aforementioned European patent are incorporated herein by reference. The experimental parameters were as follows: top oven / transfer line / needle temperature 150°C, dissolution temperature 150°C, dissolution agitation setting 2, pump stabilization time 15 seconds, pump flow rate for column wash 0.500 mL / m, pump flow rate for column packing 0.300 mL / min, stabilization temperature 150°C, stabilization time (pre, before packing the column) 2.0 minutes, stabilization time (post, after packing the column) 1.0 minute, SF (soluble fraction) time 5.0 minutes, cooling rate from 150°C to 30°C 3.00°C / min, flow rate during the cooling process 0.04 mL / min, heating rate from 30°C to 160°C 2.00°C / min, isothermal time 160°C for 10 minutes, elution flow rate 0.500 mL / min, and injection loop size 200 microliters.

[0040] The flow rate during the cooling process is adjusted according to the length of the graphite column to ensure that all polymer fraction remains on the column at the end of the cooling cycle.

[0041] Samples were prepared at a concentration of 4.0 mg / ml in ODCB (defined below) using a PolymerChar autosampler at 150 °C for 120 min. Silica gel 40 (particle size 0.2–0.5 mm, catalog no. 10181-3, EMD) was dried in a vacuum oven at 160 °C for approximately 2 h before use. 2,6-Di-tert-butyl-4-methylphenol (1.6 g, BHT, catalog no. B1378-500G, Sigma-Aldrich) and silica gel 40 (5.0 g) were added to 2 L of ortho-dichlorobenzene (ODCB, 99% anhydrous grade, Sigma-Aldrich). For a CEF system equipped with an autosampler with N2 purge capability, silica gel 40 was packed into three 300 x 7.5 mm GPC-sized stainless steel columns, and the silica gel 40 columns were attached to the inlet of the CEF system pump to dry the ODCB. Additionally, no BHT was added to the mobile phase. Hereinafter, this "ODCB containing BHT and silica gel" or ODCB dried with silica gel 40 will be referred to as "ODCB." TGIC data were processed with the "GPC One" software platform from PolymerChar (Spain). Temperature calibration was performed using a mixture of approximately 4-6 mg of eicosane with 14.0 mg of isotactic homopolymer polypropylene (iPP) (polydispersity of 3.6-4.0, molecular weight M reported as polyethylene equivalents of 150,000-190,000, and polydispersity (Mw / Mn) of 3.6-4.0; the DSC melting temperature of iPP was measured to be 158-159 °C (DSC method described herein below). 14.0 mg of homopolymer polyethylene HDPE (zero comonomer content, weight average molecular weight (Mw) reported as polyethylene equivalents of 115,000-125,000, and polydispersity 2.5-2.8) in a 10 mL vial filled with 7.0 mL of ODCB. The dissolution time was 2 h at 160 °C.

[0042] The calibration process uses a solution of eicosane and HDPE. For elution temperatures ranging from 30°C to 150°C, the process consists of the following steps: 1. Extrapolate the elution temperature for each isothermal step during elution according to the heating rate (shown in Figure 1). 2. Calculate the delay. Shift the temperature (x-axis) corresponding to the IR measurement channel chromatogram (y-axis) so that the maximum value of the eicosane peak (y-axis) coincides with the elution temperature of 30.0°C. The delay is calculated by dividing the temperature difference (30°C - the actual elution temperature of the eicosane peak maximum) by the heating rate of the method and then multiplying by the elution flow rate. 3. Adjust each recorded elution temperature using the same delay adjustment. 4. The heating rate is increased or decreased linearly so that the eicosane elution peak maximum temperature is maintained at 30.0°C while the observed HDPE reference material has an elution peak maximum temperature of 150.0°C.

[0043] At least 20 random ethylene octene copolymers have been prepared with single-site catalysts with Mw (ethylene equivalent average molecular weight) ranging from 36,000 to 150,000 and polydispersities ranging from 2.0 to 2.2. The measured elution peak temperature (Tp) of each ethylene octene copolymer and the octene content (wt%) of the copolymer follow the correlation demonstrated in Figure 2.

[0044] The data processing for the HT-TGIC polymer samples is described below.

[0045] Solvent blanks (pure solvent injections) were run under the same experimental conditions as the polymer samples. Data processing for the polymer samples included subtraction of the solvent blank for each detector channel, calculated from the calibration heating rate, temperature extrapolation as described in the calibration process, temperature correction by the delay measured in the calibration process, and adjustment of the elution temperature axis to the range of 30 °C to 160 °C.

[0046] The chromatograms (measurement channels of the IR-4 or IR-5 detector) were integrated using PolymerChar "GPC One" software. When the peaks fell into a flat baseline (approximately zero in the blank-subtracted chromatogram) at the high elution temperature and into the minimum or flat region of the detector signal on the high-temperature side of the soluble fraction (SF), a linear baseline was drawn from the visible difference. For some ethylene / octene multiblock copolymers of the present disclosure, the TGIC chromatogram contains three peaks, as illustrated in Figure 5. p1 is the elution temperature corresponding to the peak maximum of the highest temperature elution peak. T p2 is the elution temperature corresponding to the peak maximum of the second highest temperature elution peak.

[0047] The DSC method is used to measure the melting temperature of homopolymer polypropylene designated HT-TGIC.

[0048] The melting point is determined using a differential scanning calorimeter (DSC). The temperature at the maximum heat flow rate relative to the linear baseline was used as the melting point. The linear baseline was established from the onset of melting (above the glass transition temperature) and to the end of melting. The temperature was increased from room temperature to 200°C at 10°C / min, held at 200°C for 5 minutes, decreased to 0°C at 10°C / min, held at 0°C for 5 minutes, and then increased from 0°C to 200°C at 10°C / min, and data was obtained from this second heating cycle.

[0049] Triple Detector GPC (TD-GPC) The chromatographic system for triple detector gel permeation chromatography (TD-GPC) consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns used were four Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns and a 20 μm precolumn. The chromatographic 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 μL, and the flow rate was 1.0 mL / min.

[0050] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000. The standards were prepared as six "cocktail" mixtures with at least a 10-fold separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights ≥ 1,000,000 and 0.05 grams in 50 milliliters for molecular weights < 1,000,000. The polystyrene standards were dissolved at 80°C with gentle agitation for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×(M ポリスチレン ) B (Equation 1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0051] A fifth-order polynomial was used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band-broadening effects for a linear homopolymer polyethylene standard obtained at 120,000 MW.

[0052] Total plate counts for the GPC column set were performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate counts (Equation 2) and symmetry (Equation 3) were determined for a 200 microliter injection according to the following equations:

[0053]

number

[0054] Samples were prepared in a semi-automated fashion using PolymerChar "Instrument Control" Software. Samples were targeted at 2 mg / mL weight, and the solvent (containing 200 ppm BHT) was added via the PolymerChar high-temperature autosampler to a septa-capped vial that had been pre-sparged with nitrogen. Samples were dissolved at 160°C with "slow" shaking for 2 hours.

[0055] Mn (GPC) , Mw (GPC) , and Mz (GPC)was calculated based on GPC results using PolymerChar GPCOne™ software and the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6 using the baseline-subtracted IR chromatogram at each equally spaced data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) from Equation 1.

[0056]

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[0057] 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 aligning the RV of each 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 time of the decane marker peak is thus assumed to be related to a linear shift in flow rate (flow rate (effective)). To facilitate the highest accuracy in the RV measurement of the flow rate marker peaks, a least-squares fitting routine was used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to determine 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) was calculated as shown in Equation 7. Processing of the flow rate marker peaks was performed using PolymerChar GPCOne™ software. For acceptable flow correction, the effective flow should be within + / - 1% of the apparent flow. Flow rate (effective) = Flow rate (apparent) * (RV(FM calibrated) / RV(FM sample)) (Equation 7)

[0058] Melt index (MI) (I2) in g / 10 min is measured according to ASTM D1238 (190°C / 2.16 kg).

[0059] Unconstrained yield strength (blocking test) Specific blocking tests were performed on Inventive Examples (IE) 1, 2, and 4, and comparative samples (CS) CS B (INFUSE 9507), CS D (INFUSE 9107), and CS G (INFUSE 9817), to evaluate their anti-massing behavior. Blocking tests are performed according to the following procedure to measure the strength of consolidated pellet masses at known stress levels and temperatures for a predetermined duration. A 2-inch diameter cylinder composed of two halves held together by a hose clamp is used. A thin Teflon sheet is inserted into the cell to line the cylinder walls, thereby minimizing wall friction. A 60-150 gram quantity of pellet sample is poured into the cylinder. The side wall of the cylinder is gently tapped during loading to allow the solids to settle. A 2-inch circular TEFLON® sheet is placed on the weight load. The test load, temperature, and test duration are set to simulate relatively harsh shipping or storage conditions. A weight load is placed on the sheet, and the cylinder is placed at predetermined intervals in a 37°C oven. A 4.5 lb load is used to obtain a 195 lbf / ft 2 After the test interval, the load is removed and the cylinder is allowed to cool at ambient conditions for at least 12 hours. The specimen is then removed from the cylinder. Unconfined yield strength (UYS) is measured using an INSTRON® tensile machine in compression mode, and the results are reported in pounds per square foot (lb / ft 2 ) will be reported.

[0060] If the pellets in the consolidated sample were completely free-flowing, they would not retain their cylindrical shape but would simply gather into a pile. If the consolidated pellet mass retained its cylindrical shape, an Instron machine was used to measure the maximum force required to crush the cylinder. The consolidated pellets were crushed using an Instron frame to measure the maximum force required to break the "cylinder form" of the consolidated pellets. The consolidated pellets were positioned vertically in the Instron (the longer dimension was vertical). A constant strain rate of 2 mm / min (room temperature) was used for this test. To ensure data consistency, each composition (coated pellets) was measured twice, and the average was reported.

[0061] The unconfined yield strength (UYS) was calculated as follows: UYS(lb / ft 2 ) = Peak force / Cylindrical cross-sectional area.

[0062] UYS is a measure of blocking strength (the higher the unconfined yield strength, the higher the blocking strength). A value of zero corresponds to a free-flowing pellet.

[0063] XRF X-ray fluorescence (XRF) was performed using a Spectro-Asoma (Marble Falls, TX) Phoenix energy-dispersive XRF spectrometer. The spectrometer was equipped with a Mo anode X-ray tube, a 30 kV power supply, a Mo (2 mil thick) tube filter, a Neon sealed gas proportional detector with a 1 mil thick Be window, and operating software version 220. The spectrometer was used to obtain Zn Kα characteristic X-ray intensities and X-ray tube backscatter intensities for samples and standards. The operating conditions used in the Phoenix method validation are listed in Table A below. Ethylene / octene multiblock copolymer pellets were poured into an XRF sample cup (catalog number 1730) obtained from Chemplex Industries, Inc., fitted with a polypropylene film (catalog number 436). The cup was filled with pellets but not overfilled so that the pellets were above the top of the cup. The film was secured in the cup with the provided ring, and the pellets were gently tapped down onto a flat surface covered with a clean, lint-free paper towel. Data were analyzed using a calibration developed based on ICP and XRF from Analytical Sciences. Reported Zn concentration values ​​(parts per million, ppm) were within ±10%.

[0064] [Table 1] DETAILED DESCRIPTION OF THE INVENTION

[0065] The present disclosure provides a process. In one embodiment, the process comprises contacting ethylene and octene with a catalyst system under polymerization conditions at a temperature greater than 125° C. The catalyst system comprises (i) a first polymerization catalyst, (ii) a second polymerization catalyst, and (iii) a chain shuttling agent. The first polymerization catalyst has the structure of formula (III):

[0066] [ka] During the ceremony, M is titanium, zirconium or hafnium; Each Y 1 and Y 2 is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) are independently selected from the group consisting of trihydrocarbylsilylhydrocarbyl, halogen, alkoxide, or amine, or two Y groups together are a divalent hydrocarbylene, hydrocarbadiyl, or trihydrocarbylsilyl group; Each Ar 1 and Ar 2 are independently (C6~C 40 ) Aryl, substituted (C6-C 40 ) Aryl, (C3-C 40 ) heteroaryl and substituted (C3-C 40 ) heteroaryl; T 1 independently for each occurrence, T 1 is a saturated C2-C4 alkyl that forms a bridge between the two oxygen atoms to which Each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are independently hydrogen, halogen, (C1-C 40 ) Hydrocarbyl, substituted (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, substituted (C1-C 40 ) heterohydrocarbyl, (C6-C 40 ) Aryl, substituted (C6-C 40 ) Aryl, (C3-C 40 ) heteroaryl and substituted (C3-C 40) heteroaryl, and nitro (NO2).

[0067] The second polymerization catalyst (ii) has the structure of formula (I):

[0068] [ka] During the ceremony, M is titanium, zirconium, or hafnium; each Z 1 and Z 2 is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) are independently selected from the group consisting of trihydrocarbylsilylhydrocarbyl, halogen, alkoxide, or amine, or two Z groups together are a divalent hydrocarbylene, hydrocarbadiyl, or trihydrocarbylsilyl group; Each Q 1 and Q 10 are independently (C6~C 40 ) Aryl, substituted (C6-C 40 ) Aryl, (C3-C 40 ) heteroaryl and substituted (C3-C 40 ) heteroaryl; Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 , and Q 9 are independently hydrogen, (C1 to C 40 ) Hydrocarbyl, substituted (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, substituted (C1-C 40 ) selected from the group consisting of heterohydrocarbyl, halogen, and nitro (NO2); Each Q 5 and Q 6 are independently (C1~C 40 ) Alkyl, substituted (C1-C 40 ) alkyl, and [(Si)1-(C+Si) 40]-substituted organosilyl; each N is independently nitrogen; Optionally, Q 1~5 two or more of the groups can combine together to form a ring structure, such ring structure having 5 to 16 atoms in the ring, excluding any hydrogen atoms; Optionally, Q 6~10 Two or more of the groups can combine together to form a ring structure, such ring structure having 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0069] The catalyst system also includes a chain shuttling agent (iii). The process includes forming an ethylene / octene multi-block copolymer having a normalized OOO triad content greater than 0.25.

[0070] The process involves contacting ethylene and octene with a catalyst system under polymerization conditions at a temperature above 125°C. As used herein, the term "polymerization conditions" refers to the process parameters under which ethylene and octene are copolymerized in the presence of a catalyst system. Polymerization conditions include, for example, polymerization reactor conditions (reactor type), reactor pressure, reactor temperature, reagent and polymer concentrations, solvents, carriers, residence times and distributions, molecular weight distributions, and polymer structure. As used herein, the term polymerization conditions includes polymerization temperatures above 125°C.

[0071] In one embodiment, the polymerization conditions include a temperature of from 130°C to 170°C, or from 130°C to 160°C, or from 140°C to 150°C.

[0072] The process involves contacting ethylene and octene with a catalyst system under polymerization conditions at a temperature above 125° C. The catalyst system includes (i) a first polymerization catalyst of formula (III) (supra), (ii) a second polymerization catalyst of formula (I) (supra), and (iii) a chain shuttling agent.

[0073] The catalyst system includes a chain shuttling agent. As used herein, "chain shuttling agent" refers to a compound capable of inducing polymeric transfer between various active catalytic sites under polymerization conditions. That is, transfer of polymer fragments occurs both to and from active catalytic sites in a readily reversible manner. In contrast to shuttling agents or chain shuttling agents, agents that simply act as "chain transfer agents," such as some main group alkyl compounds, can exchange, for example, alkyl groups on the chain transfer agent with growing polymer chains on the catalyst, which generally results in termination of polymer chain growth. In this case, the main group center may act as a reservoir for dead polymer chains rather than participating in reversible transfer to and from catalytic sites in the manner that chain shuttling agents do. Desirably, the intermediate formed between the chain shuttling agent and the polymeric chain is not sufficiently stable to exchange between this intermediate and any other growing polymeric chains, and therefore chain termination is relatively rare.

[0074] The process involves forming an ethylene / octene multiblock copolymer having a normalized OOO triad content greater than 0.25. The term "ethylene / octene multiblock copolymer" refers to a copolymer of ethylene and octene comonomers in polymerized form, characterized by multiple blocks or segments of two polymerized monomer units (i.e., ethylene and octene) with different chemical or physical properties, and the blocks are linked (or covalently linked) in a linear fashion, i.e., the polymer contains chemically distinct units linked end-to-end with respect to the polymerized ethylenic functional groups. Ethylene / octene multiblock copolymers include block copolymers having two blocks (diblock) and three or more blocks (multiblock). Ethylene / octene multiblock copolymers do not contain or otherwise exclude styrene (i.e., styrene-free), and / or do not contain or otherwise exclude vinyl aromatic monomers and / or conjugated dienes. When referring to the amount of "ethylene" or "octene" or "comonomer" in a copolymer, it is understood that it refers to the polymerized units thereof. The ethylene / octene multiblock copolymer can be represented by the following formula: (AB)n, where n is at least 1 and preferably greater than 1, e.g., 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more; "A" represents a hard block or segment, and "B" represents a soft block or segment. A and B are linked or covalently bonded in a substantially linear or linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, the A and B blocks are randomly distributed along the polymer chain. In other words, the block copolymer typically does not have a structure such as: AAA-AA-BBB-BB. In one embodiment, the ethylene / octene multiblock copolymer does not have a third type of block containing a different comonomer. In another embodiment, each of the A and B blocks has monomers or comonomers distributed substantially randomly within the block.In other words, neither block A nor block B includes two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment having a substantially different composition than the remainder of the block.

[0075] Ethylene constitutes the majority mole fraction of the total ethylene / octene multiblock copolymer. Ethylene constitutes at least 50 mol% (mol%) of the total ethylene / octene multiblock copolymer. In one embodiment, the ethylene / octene multiblock copolymer contains 50 mol%, or 60 mol%, or 65 mol% to 80 mol%, or 85 mol%, or 90 mol%, or 95 mol% ethylene and a relative amount of octene, or 5 mol%, or 10 mol%, or 15 mol%, or 20 mol% to 35 mol%, or 40 mol%, or less than 50 mol% octene, based on the total moles of the ethylene / octene multiblock copolymer. In further embodiments, the ethylene / octene multiblock copolymer contains 5 mol% to 30 mol% octene (and 95 mol% to 70 mol% ethylene), or 10 mol% to 25 mol% octene (and 90 mol% to 75 mol% ethylene).

[0076] Ethylene / octene multiblock copolymers contain varying amounts of "hard" and "soft" segments. The "hard" segments are blocks of polymerized units in which ethylene is present in an amount greater than 90%, or greater than 95%, or greater than 95%, or greater than 98%, up to 100% by weight based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10%, or less than 5%, or less than 5%, or less than 2% by weight based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments contain all or substantially all units derived from ethylene. The "soft" segments are blocks of polymerized units in which the comonomer content (octene content) is greater than 5%, or greater than 8%, or greater than 10%, or greater than 15% by weight based on the weight of the polymer. In one embodiment, the comonomer content of the soft segment is greater than 20 weight percent, or greater than 25 weight percent, or greater than 30 weight percent, or greater than 35 weight percent, or greater than 40 weight percent, or greater than 45 weight percent, or greater than 50 weight percent, or greater than 60 weight percent, and can be up to 100 weight percent.

[0077] The soft segments in the ethylene / octene multiblock copolymer may be present at 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 99 wt% of the total weight of the ethylene / octene multiblock copolymer. Conversely, the hard segments may be present in a similar range. The weight percentages of the soft segments and the hard segments can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in U.S. Pat. No. 7,608,668, the disclosure of which is incorporated herein by reference in its entirety. In particular, the weight percent of the hard and soft segments and the melting temperature of the soft segment, SS-Tm, can be determined as described in U.S. Pat. No. 7,608,668, columns 57-63, which are incorporated herein by reference.

[0078] Ethylene / octene multiblock copolymers contain two or more chemically distinct regions or segments (referred to as "blocks") linearly linked (or covalently linked), i.e., they contain chemically distinct units that are linked end-to-end with respect to polymerized ethylenic functional groups, rather than in a pendant or grafted manner. The blocks differ in the amount or type of incorporated comonomer, density, amount of crystallinity, crystallite size attributable to polymers of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long-chain branching or hyperbranching), homogeneity, or any other chemical or physical property. Compared to prior art block interpolymers, including those produced by continuous monomer addition, flow catalyst, or anionic polymerization techniques, the ethylene / octene multi-block copolymers of the present invention are, in one embodiment, characterized by a unique distribution of both polymer polydispersity (PDI or Mw / Mn or MWD), polydisperse block length distribution, and / or polydisperse block number distribution due to the effect of shuttle agents in combination with the multiple catalysts used in their preparation.

[0079] In one embodiment, the ethylene / octene multi-block copolymers are produced in a continuous process and have a polydispersity index (Mw / Mn) of 1.7 to 3.5, or 1.8 to 3, or 1.8 to 2.5, or 1.8 to 2.2. When produced in a batch or semi-batch process, the ethylene / octene multi-block copolymers have a Mw / Mn of 1.0 to 3.5, or 1.3 to 3, or 1.4 to 2.5, or 1.4 to 2.

[0080] Additionally, the ethylene / octene multiblock copolymers have PDI (or Mw / Mn) values ​​that conform to a Schultz-Flory distribution rather than a Poisson distribution. The ethylene / octene multiblock copolymers of the present invention have both a polydisperse block distribution and a polydisperse distribution of block sizes. This results in polymer products with improved, identifiable physical properties. The theoretical benefits of a polydisperse block distribution have been previously modeled and discussed in Potemkin, Physical Review E (1998) 57(6), pp. 6902-6912, and Dobrynin, J. Chem. Phvs. (1997) 107(21), pp. 9234-9238.

[0081] In one embodiment, the ethylene / octene multi-block copolymer has a most probable distribution of block lengths.

[0082] The process forms ethylene / octene multiblock copolymers having a normalized OOO triad content greater than 0.25.

[0083] In one embodiment, the process includes forming an ethylene / octene multi-block copolymer having a normalized OOO content of from 0.30 to 0.75, or from 0.30 to 0.70, or from 0.35 to 0.70.

[0084] In one embodiment, the process comprises contacting ethylene and octene with a catalyst system under polymerization conditions at a temperature between 130° C. and 170° C. The catalyst system comprises (i) hafnium, [[2′,2′′′-[1,4-butanediylbis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-5-(1,1-dimethylnonyl)-5′-fluoro[1,1′-biphenyl]-2-olato-κO]](2-)]dimethyl-, having the structure Catalyst 1

[0085] [ka] a first catalyst having (ii) hafnium, dimethylbis[N-(2-methylpropyl)-6-(2,4,6-trimethylphenyl)-2-pyridineaminato-κN1,κN2], and the structure of catalyst 2

[0086] [ka] a second catalyst having (iii) a chain shuttling agent, which is diethyl zinc. The process includes forming an ethylene / octene multi-block copolymer having hard segments and soft segments. The soft segments have a soft segment melting temperature (SS-Tm) of -30°C to 35°C, or -30°C to 30°C, and the ethylene / octene multi-block copolymer has a first TGIC peak temperature (T p1 ) and the second TGIC peak temperature (T p2 ), wherein T p2 satisfies equation (A). T p2 ≦0.0068×(SS-Tm) 2 +0.07×(SS-Tm)+73.2 Equation A

[0087] The present disclosure provides a composition formed from the aforementioned polymerization process. In one embodiment, the composition comprises an ethylene / octene multi-block copolymer having a normalized OOO triad content greater than 0.25.

[0088] In one embodiment, the composition comprises forming an ethylene / octene multi-block copolymer having a normalized OOO content of from 0.30 to 0.75, or from 0.30 to 0.70, or from 0.35 to 0.70.

[0089] In one embodiment, the ethylene / octene multi-block copolymer of the composition comprises 10 mol% to 30 mol% octene and a relative amount of ethylene, or 90 mol% to 70 mol% ethylene, based on the total moles of the ethylene / octene multi-block copolymer.

[0090] In one embodiment, the ethylene / octene multi-block copolymer of the composition has hard segments and soft segments, and the soft segments have a soft segment melting temperature (SS-Tm) of -30°C to 35°C, or -30°C to 30°C. The ethylene / octene multi-block copolymer has a first TGIC peak temperature (T p1 ) and the second TGIC peak temperature (T p2 ), wherein T p2 satisfies equation (A). T p2 ≦0.0068×(SS-Tm) 2 +0.07×(SS-Tm)+73.2 Equation (A)

[0091] In one embodiment, the ethylene / octene multiblock copolymer of the composition satisfies equation (A) and has a T p1 , and T of 54℃ to 96℃ or 68℃ to 90℃ p2 It has.

[0092] In one embodiment, the ethylene / octene multi-block copolymer has a glass transition temperature (Tg) of from -70°C to -55°C, or from -67°C to -57°C.

[0093] In one embodiment, the ethylene / octene multi-block copolymer of the composition has a density from 0.855 g / cc to 0.890 g / cc.

[0094] In one embodiment, the ethylene / octene multi-block copolymer of the composition has a Tm from 115°C to 125°C, or from 118°C to 123°C.

[0095] In one embodiment, the ethylene / octene copolymer of the composition has a melt index (I2) from 0.1 g / 10 min to 35.0 g / 10 min, or from 0.5 g / 10 min to 32 g / 10 min, or from 1.0 to 17 g / 10 min.

[0096] In one embodiment, the ethylene / octene multi-block copolymer of the composition has a melting point of 300% / min at 21°C. 1 At a deformation rate of 100°C, the material has an elastic recovery (Re) of 50%, or 60% to 70%, or 80%, or 90%.

[0097] In one embodiment, the ethylene / octene multi-block copolymers of the composition have a polydisperse distribution of blocks and a polydisperse distribution of block sizes.

[0098] In one embodiment, the ethylene / octene multi-block copolymer of the composition has a viscosity of 0 lb / ft at 21° C. after 2 months. 2 to 200 lb / ft 2 In a further embodiment, the ethylene / octene multiblock copolymer of the composition has an unconstrained yield strength (UYS) of less than 0 lb / ft after 2 months at 21°C. 2 ~200lb / ft 2 Less than or 0 lb / ft after 2 months 2 ~100lb / ft 2 Less than or 0 lb / ft after 2 months 2 ~50lb / ft 2 Less than or 0 lb / ft after 2 months 2 ~10lb / ft 2 Less than or 0 lb / ft after 2 months 2 ~5lb / ft 2 Less than or greater than 0 to 5 lb / ft after 2 months 2 It has an unconfined yield strength (UYS) of less than

[0099] In one embodiment, the ethylene / octene multi-block copolymer of the composition has a viscosity of 0 lb / ft at 0° C. after 2 months. 2 ~73lb / ft 2 In a further embodiment, the ethylene / octene multiblock copolymer of the composition has an unconstrained yield strength (UYS) of less than 0 lb / ft at 0° C. after 2 months. 2 ~54lb / ft 2 Unrestrained yield strength (UYS) of less than 0 lb / ft at 0°C or after 2 months 2 It has an unconfined yield strength (UYS) of

[0100] In one embodiment, the ethylene / octene multi-block copolymer of the composition has a funnel flow rate of greater than 150 g / sec to 200 g / sec after 6 weeks.

[0101] In one embodiment, the ethylene / octene multi-block copolymer of the composition consists solely of ethylene and octene comonomers and has one, some, or all of the following properties: (i) a normalized OOO triad value between 0.35 and 0.70, and / or (ii) 10 mol% to 30 mol% octene and 90 mol% to 70 mol% ethylene, and / or (iii) SS-Tm of -30°C to 35°C or -30°C to 30°C, T p2 ≦0.0068×(SS-Tm) 2 an SS-Tm that is +0.07×(SS-Tm)+73.2, and / or (iv) T of 125℃ to 150℃ p1 and T of 54°C to 96°C or 68°C to 90°C p2 and / or (v) a Tg of -70°C to -55°C, and / or (vi) a density between 0.855 g / cc and 0.890 g / cc, and / or (vii) a Tm of 115°C to 125°C, and / or (viii) a melt index (I2) of 0.1 g / 10 min to 20.0 g / 10 min, and / or (ix) an elastic recovery (Re) of 50% to 90%, and / or (x) Mw / Mn between 1.7 and 3.5, and / or (xi) a polydisperse distribution of blocks and a polydisperse distribution of block sizes, and / or (xii) After 2 months, at 21°C, 0 lb / ft 2 ~5lb / ft 2 Unconfined yield strength (UYS) of less than (xiii) Funnel flow rates exceeding 150-200 g / sec.

[0102] The ethylene / octene multiblock copolymers of the present invention described herein are useful in many applications. The improved pellet handling and reduced tendency of the pellets to adhere to themselves (stickiness) make the ethylene / octene multiblock copolymers disclosed herein beneficial for film applications, such as cast film for elastic films. Improved tack can lead to lower overall density, increased soft segment comonomer content, and / or higher melt flow products, which can provide better elastic hysteresis and shrink behavior in films, such as cast films.

[0103] The ethylene / octene multiblock copolymers of the present invention described herein are also useful in foam applications, such as midsole foam applications for footwear. Sole foams made from the ethylene / octene multiblock copolymers of the present invention provide athletic shoes with improved flexibility and improved rebound from the soft segment component of the ethylene / octene multiblock copolymers of the present invention.

[0104] By way of example and not limitation, several embodiments of the present disclosure are detailed in the following examples. [Example]

[0105] Table 1 below provides the catalysts, cocatalysts, and chain shuttling agents used to prepare Comparative Sample (CS) A and Inventive Examples (IE) 1-7.

[0106] [Table 2]

[0107] Polymerization of CS A and IE1-7 All raw materials (ethylene and octene) and process solvents (high-purity narrow-boiling range isoparaffinic solvent, Isopar-E) are purified with molecular sieves before being introduced into the reaction environment. Hydrogen is supplied under pressure as a high-purity grade and is not further purified. The reactor monomer feed stream is pressurized to a pressure above the reaction pressure by a mechanical compressor. Solvent and comonomer feeds are pressurized above the reaction pressure via pumps. Individual catalyst components are manually batch diluted with purified solvent and pressurized above the reaction pressure. All reaction feed streams are metered using mass flow meters and independently controlled by a computer-automated control system.

[0108] The continuous solution polymerization reactor consists of a liquid-filled, non-adiabatic, isothermal circulating loop reactor that mimics a continuously stirred tank reactor (CSTR) with heat removal. Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. The total fresh feed streams to the reactor (solvent, monomer, and hydrogen) are temperature controlled by passing the feed streams through heat exchangers. The total fresh feed to the polymerization reactor is injected into the reactor at two locations, with approximately equal reactor volume between each injection location. The fresh feed is controlled with each injector receiving half of the total fresh feed mass flow rate. The catalyst components are injected into the polymerization reactor through specially designed injection stingers. The first polymerization catalyst component feed (Catalyst A and Catalyst 1 in Table 1) is computer-controlled to maintain reactor monomer conversion at a specific target value. The molar ratio of the second polymerization catalyst feed (Catalyst B and Catalyst 2 in Table 1) to the total catalyst feed is adjusted to maintain the desired split between the polymer soft and hard segments. The cocatalyst components (Cocatalyst 3 and Cocatalyst 4 in Table 1) are fed based on a calculated specific molar ratio to the catalyst components. Immediately after the injection point of each reactor feed, the feed stream is mixed with the contents of a circulation polymerization reactor with static mixing elements. The reactor contents are continuously circulated through a heat exchanger, which serves to remove the majority of the heat of reaction, with the coolant side temperature serving to maintain an isothermal reaction environment at a specified temperature. Circulation around the reactor loop is effected by a pump.

[0109] The reactor effluent enters a zone where the effluent is deactivated by addition and reaction with a suitable reagent (water). At this same reactor exit point, other additives are added for polymer stabilization. Following catalyst deactivation and additive addition, the reactor effluent enters a devolatilization system where the polymer is removed from the non-polymer stream. The isolated polymer melt is pelletized and collected. The non-polymer stream passes through various equipment that separates most of the ethylene removed from the system. Most of the solvent and unreacted comonomer pass through a purification system before being recycled to the reactor. A small amount of solvent and comonomer is purged from the process.

[0110] The polymerization conditions for the comparative sample (CS) CS A and the inventive examples (IE) IE1-7 are provided in Table 2 below.

[0111] [Table 3]

[0112] The polymerization conditions described above and those shown in Table 2 produce ethylene / octene multi-block copolymers CS A and IE1-7. The ethylene / octene multi-block copolymers CS A and IE1-7 are then compared to a conventional ethylene / octene multi-block copolymer sold under the trade name INFUSE. The conventional ethylene / octene multi-block copolymer is provided in Table 3 below.

[0113] [Table 4]

[0114] The characteristics of CS A and IE1 to IE7 in Table 2 and the characteristics of CS B to G in Table 3 are shown in Table 4 below.

[0115] [Table 5] FF funnel flow rates measured at 3 and 6 weeks (results reported in grams per second, g / sec) UYS - Unconfined yield strength measured at 1 month and 2 months at temperatures of 0°C and 21°C (results reported in lb / ft2) *In the UYS test, the talc content is IE1: 3000 ppm, IE2 / IE3: 5000 ppm each, and the talc content of INFUSE 9107 / 9507 / 9817 is 3000 / 5000 / 5000 ppm respectively.

[0116] The ethylene / octene multiblock copolymers IE1, IE2, IE3, IE4, IE5, IE6, and IE7 have higher total octene content than the ethylene / octene multiblock copolymers CS A, CS B, CS C, CS D, CS E, CS F, and CS G, which have the same design targets for density, MI, and SS Tm. Typically, polyethylene copolymers of the same density will have the same comonomer content. The ethylene / octene multiblock copolymers IE1-7, produced using the Catalyst 1 / Catalyst 2 system and polymerization conditions at temperatures above 125°C (or temperatures between 130°C and 150°C), contain different comonomer distributions along the polymer backbone, evident in the EOE, EOO, and OOO sequences, when comparing IE1-7 with Comparative Samples A-G. IE1 and CS D are similar in density, MI, and SS Tm. However, Inventive Example 1 exhibits a greater than six-fold increase in normalized OOO triad content (0.40 normalized OOO triads) when compared to Comparative Sample D (0.06 normalized OOO triads).

[0117] IE2 and CS B are similar in density and MI, however, Inventive Example 2 shows a greater than 5-fold increase in normalized OOO triad content (0.35 normalized OOO triads) when compared to Comparative Sample B (0.07 normalized OOO triads).

[0118] IE3 and CS C are similar in density, MI, and SS Tm. However, inventive Example 3 shows a greater than two-fold increase in normalized OOO triad content (0.36 normalized OOO triads) when compared to comparative sample C (0.14 normalized OOO triads).

[0119] IE4 and CS G are similar in density, MI, and SS Tm. However, inventive Example 4 shows a greater than six-fold increase in normalized OOO triad content (0.46 normalized OOO triads) when compared to comparative sample G (0.07 normalized OOO triads).

[0120] IE5 and CS E are similar in density, MI, and SS Tm. However, inventive Example 5 shows a greater than three-fold increase in normalized OOO triad content (0.59 normalized OOO triads) when compared to comparative sample E (0.16 normalized OOO triads).

[0121] IE6 and CS A are similar in density, MI, and SS Tm. However, inventive Example 6 shows an almost five-fold increase in normalized OOO triad content (0.44 normalized OOO triads) when compared to comparative sample A (0.09 normalized OOO triads).

[0122] IE7 and CS F are similar in density, MI, and SS Tm. However, inventive Example 7 shows a three-fold increase in normalized OOO triad content (0.68 normalized OOO triads) when compared to comparative sample F (0.20 normalized OOO triats).

[0123] The high total octene content and the increased likelihood of adjacent insertion of octene monomers were expected to result in reduced solids handling performance for the inventive examples compared to the comparative samples. That is, the inventive examples were expected to be stickier compared to the comparative samples. However, Applicants have unexpectedly discovered that IE1, IE2, and IE4 ethylene / octene multiblock copolymers have improved solids handling properties when compared to conventional ethylene / octene multiblock copolymers with similar density, MI, and SS Tm. Table 4 shows that IE1 has lower UYS and higher FF compared to CS D, IE2 has lower UYS and higher FF compared to CS B, and IE4 has lower UYS compared to CS G.

[0124] The present disclosure is not limited to the embodiments and examples contained herein, but is expressly intended to include portions of the embodiments and modified forms of those embodiments, including combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims. Examples of the invention of this application include the following. [1] A process, contacting ethylene and octene with a catalyst system under polymerization conditions at a temperature above 125°C, said catalyst system comprising: (i) a first polymerization catalyst having the structure of Catalyst 1; [ka] (ii) a second polymerization catalyst having the structure of Catalyst 2; and [ka] (iii) a first promoter that is a borate-based promoter; and (iv) a second promoter that is an aluminum-based promoter; and (v) contacting with a chain shuttling agent; maintaining an aluminum to hafnium molar ratio between 7.1 and 15.6 during said contacting; forming an ethylene / octene multi-block copolymer having a normalized OOO triad content greater than 0.25. [2] contacting the ethylene and octene under polymerization conditions at a temperature of 130°C to 170°C; and forming an ethylene / octene multi-block copolymer having hard segments and soft segments, wherein the soft segments have a soft segment melting temperature (SS-Tm) of -30°C to 30°C, and the ethylene / octene multi-block copolymer has a first TGIC peak temperature (T p1 ) and the second TGIC peak temperature (T p2 ) and T p2 But equation (A) T p2 ≦0.0068×(SS-Tm) 2 The process according to [1] above, wherein the reaction rate satisfies +0.07×(SS-Tm)+73.2. [3] A composition comprising: an ethylene / octene multiblock copolymer comprising hafnium and aluminum in a molar ratio of aluminum to hafnium of 7.1 to 15.6; The composition, wherein the ethylene / octene multiblock copolymer has a normalized OOO triad content greater than 0.25. [4] The composition according to [3] above, wherein the ethylene / octene multiblock copolymer contains 10 mol% to 30 mol% of octene. [5] The ethylene / octene multi-block copolymer comprises hard segments and soft segments, the soft segments have a soft segment melting temperature (SS-Tm) of -30°C to 30°C, and the ethylene / octene multi-block copolymer has a first TGIC peak temperature (T p1 ) and the second TGIC peak temperature (T p2 ) and T p2 But equation (A) T p2 ≦0.0068×(SS-Tm) 2 The composition according to [4] above, which satisfies +0.07×(SS-Tm)+73.2. [6] The ethylene / octene multiblock copolymer has a T p1 and T of 68℃~90℃ p2 The composition according to [5] above, [7] The composition according to [6] above, wherein the ethylene / octene multiblock copolymer has a glass transition temperature (Tg) of -70°C to -55°C. [8] The composition according to [7] above, wherein the ethylene / octene multiblock copolymer has a density of 0.855 to 0.890 grams per cubic centimeter (g / cc). [9] The ethylene / octene multiblock copolymer has a modulus of 0 lb / ft at 21°C after 2 months. 2 ~200lb / ft 2 The composition according to [8] above, having an unconfined yield strength (UYS) of less than 1000 kJ / g.

[10] The composition according to [8] or [9] above, wherein the ethylene / octene multiblock copolymer has a funnel flow rate of greater than 150 g / sec to 200 g / sec after 6 weeks.

[11] The ethylene / octene multiblock copolymer has a viscosity of 0 lb / ft at 0°C after 2 months. 2 ~73lb / ft 2 The composition according to any one of the above [8] to

[10] , having an unconstrained yield strength (UYS) of less than 1000 kJ / g.

Claims

1. A process comprising: contacting ethylene and octene with a catalyst system under polymerization conditions at a temperature of from 130°C to 170°C, said catalyst system comprising: (i) a first polymerization catalyst having the structure of Catalyst 1; 【Chemical 1】 (ii) a second polymerization catalyst having the structure of Catalyst 2; and 【Chemistry 2】 (iii) Tetrakis-(pentafluorophenyl)borate methyldi(C １４～１８ a first cocatalyst which is a mixture of (alkyl)ammonium salts; (iv) a second cocatalyst which is modified methylaluminoxane (MMAO); and (v) a chain shuttling agent which is diethyl zinc; maintaining an aluminum to hafnium molar ratio between 7.1 and 15.6 during said contacting; forming an ethylene / octene multi-block copolymer having a normalized OOO triad content of 0.30 to 0.75; The process includes:

2. forming an ethylene / octene multi-block copolymer having hard segments and soft segments, wherein the soft segments have a soft segment melting temperature (SS-Tm) of -30°C to 30°C, and the ethylene / octene multi-block copolymer has a first TGIC peak temperature (T ｐ１ ) and the second TGIC peak temperature (T ｐ２ ) T ｐ２ But equation (A) T ｐ２ ≦0.0068×(SS-Tm) ２ The process of claim 1, wherein the reaction temperature satisfies +0.07×(SS−Tm)+73.

2.

3. 1. A composition comprising: an ethylene / octene multi-block copolymer comprising hafnium and aluminum in a molar ratio of aluminum to hafnium of 7.1 to 15.6; A composition wherein the ethylene / octene multi-block copolymer has a normalized OOO triad content of 0.30 to 0.75 and comprises 10 mol% to 30 mol% octene.

4. The ethylene / octene multi-block copolymer comprises hard segments and soft segments, the soft segments having a soft segment melting temperature (SS-Tm) of -30°C to 30°C, and the ethylene / octene multi-block copolymer has a first TGIC peak temperature (T ｐ１ ) and the second TGIC peak temperature (T ｐ２ ) T ｐ２ But equation (A) T ｐ２ ≦0.0068×(SS-Tm) ２ The composition according to claim 3, which satisfies +0.07 × (SS − Tm) + 73.

2.

5. The ethylene / octene multi-block copolymer has a T ｐ１ and T of 68°C to 90°C ｐ２ The composition of claim 4 having:

6. 6. The composition of claim 5, wherein the ethylene / octene multi-block copolymer has a glass transition temperature (Tg) of from -70°C to -55°C.

7. 7. The composition of claim 6, wherein the ethylene / octene multi-block copolymer has a density of 0.855 to 0.890 grams per cubic centimeter (g / cc).

8. The ethylene / octene multiblock copolymer exhibited a viscosity of 0 lb / ft at 21° C. after 2 months. ２ ~200 lb / ft ２ 8. The composition of claim 7, having an unconfined yield strength (UYS) of less than

9. 9. The composition of claim 7 or 8, wherein the ethylene / octene multi-block copolymer has a funnel flow rate of greater than 150 g / sec to 200 g / sec after 6 weeks.

10. The ethylene / octene multi-block copolymer exhibited a viscosity of 0 lb / ft at 0° C. after 2 months. ２ ~73 lb / ft ２ The composition of any one of claims 7 to 9, having an unconfined yield strength (UYS) of less than

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