Branched ethylene-based polymer composition and method for producing the same

Abstract

The present disclosure provides a composition. In one embodiment, the composition is an ethylene-based polymer composition formed by high-pressure (greater than or equal to 100 MPa) free radical polymerization. The ethylene-based polymer composition comprises a mixture of ethylene monomers and hydroxyl-terminated polybutadiene molecules (PB-OH). Each PB-OH molecule contains internal olefin groups and terminal olefin groups. Each PB-OH molecule has more internal olefin groups than terminal olefin groups.

Description

BACKGROUND OF THE INVENTION

[0001] The level of branching in low density polyethylene (LDPE) is mainly attributed to the reactor design and the polymerization conditions used to prepare LDPE. Branching agents have been used to increase the level of branching in LDPE. However, the process conditions required to obtain a modified LDPE with a high level of branching typically result in a final product with a lower degree of crystallinity and a higher content of low molecular weight extractable fractions. Therefore, there is a need for a modified LDPE that has a high level of branching and can be prepared under conditions that maintain good polymer properties. SUMMARY OF THE INVENTION

[0002] The present disclosure provides a composition. In one embodiment, the composition is an ethylene-based polymer composition formed by high pressure (greater than or equal to 100 MPa) free radical polymerization. The ethylene-based polymer composition includes a mixture of ethylene monomers and hydroxyl-terminated polybutadiene molecules (PB-OH). Each PB-OH molecule contains internal olefin groups and terminal olefin groups. Each PB-OH molecule has more internal olefin groups than terminal olefin groups.

[0003] The present disclosure provides a method. In one embodiment, the method includes reacting a mixture of ethylene monomers and hydroxyl-terminated polybutadiene molecules in a polymerization reactor under free radical polymerization conditions and at a pressure greater than or equal to 100 MPa. Each molecule has Structure I

[0004] Structure I

[0005]

[0006] where c is from 0 to 90, n is from 0 to 90, t is from 0 to 90, and

[0007] c + n + t ≥ 4, provided that c, n, and t cannot all be 0 simultaneously. The method includes forming an ethylene-based polymer composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 is a graph showing the average corrected melt force (MF) versus ppm of additive A present in an ethylene-based resonance peak polymer according to one embodiment of the present disclosure.

[0009] DEFINITIONS

[0010] Any reference to the Periodic Table of the Elements is to the Periodic Table published by CRC Press, Inc. in 1990 - 1991. A group of elements in the table is referred to by the new notation used to number the groups.

[0011] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication is hereby incorporated by reference in its entirety (or its equivalent U.S. version is incorporated by reference), particularly with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure).

[0012] The numerical ranges disclosed herein include all values from the upper and lower limits thereof, and all such values include the upper and lower limits. For ranges containing explicit values (e.g., 1 or 2, or 3 to 5, or 6, or 7), any sub-ranges between any two of the explicit values are included (e.g., the above range of 1 to 7 includes sub-ranges of 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0013] Unless stated to the contrary, implicit from the context or customary in the art, all parts and percentages are by weight and all test methods are the current methods as of the date of filing of this disclosure.

[0014] The term "composition" refers to a mixture of the materials that make up 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 specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed by use of 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 from the scope of any subsequent recitation any other components, steps, or procedures (except those that are not essential to the operability thereof). The term "consisting of" excludes any component, step, or procedure not specifically recited or listed. Unless otherwise stated, the term "or" 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.

[0016] As used herein, the term "polymer" or "polymeric material" refers to a compound prepared by polymerizing monomers, whether of the same type or different types, which provides multiple and / or repeating "units" or "monomer units" that make up the polymer in polymeric form. Thus, the general term "polymer" hereby 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 monomers. It also encompasses all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" denote copolymers prepared as described above by polymerizing ethylene or propylene and one or more additional polymerizable α-olefin monomers, respectively. It should be noted that although polymers are commonly referred to as being "made of", "based on", "containing" a specified monomer content, etc., one or more specified monomers, in this context, the term "monomer" should be understood to refer to the polymeric residue of the specified monomer rather than the unpolymerized material. Generally speaking, the polymers referred to herein are based on the "units" in polymeric form of the corresponding monomers.

[0017] Unless stated to the contrary, implied by the context, or conventional in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this application.

[0018] As used herein, the term "blend" or "polymer blend" refers to a mixture of two or more polymers. The blend can be miscible or can be immiscible (not phase-separating at the molecular level). The blend can be or can not be phase-separated. The blend can contain or can 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. The blend can be effected by physically mixing two or more polymers at the macroscopic level (e.g., melt blending the resins or compounding) or at the microscopic level (e.g., forming simultaneously within the same reactor).

[0019] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer having greater than 50 mole % of polymerized ethylene monomer (based on the total amount of polymerizable monomers) and at least one α-olefin.

[0020] As used herein, the term "ethylene-based polymer composition" refers to a composition that comprises more than 50 wt% or a majority amount of ethylene in polymeric form, based on the weight of the polymer, and optionally, can contain at least one comonomer or other molecule.

[0021] As used herein, the term "ethylene monomer" refers to a chemical unit having two carbon atoms with a double bond therebetween, and each carbon is bonded to two hydrogen atoms, wherein the chemical unit is polymerized with other such chemical units to form an ethylene-based polymer composition.

[0022] As used herein, the term "high density polyethylene" (or "HDPE") refers to an ethylene-based polymer having a density of at least 0.94 g / cc, or at least 0.94 g / cc to 0.98 g / cc. HDPE has a melt index of 0.1 g / 10 min to 25 g / 10 min. HDPE may include ethylene and one or more C 3 –C 20 α-olefin comonomers. The comonomers can be linear or branched. Non-limiting examples of suitable comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. HDPE can be prepared in a slurry reactor, a gas phase reactor, or a solution reactor using Ziegler-Natta, chromium-based, constrained geometry, or metallocene catalysts. Ethylene / C 3 –C 20 α-olefin copolymers include those in which at least 50% by weight of the polymerized ethylene, or at least 70% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight of the ethylene is in polymerized form.

[0023] As used herein, the term "hydrocarbon molecule" refers to a chemical component having only carbon and hydrogen atoms.

[0024] As used herein, the term "linear low density polyethylene" (or "LLDPE") refers to a linear ethylene / α-olefin copolymer containing a heterogeneous short chain branching distribution, which comprises units derived from ethylene and units derived from at least one C 3 –C 10 α-olefin or C 4 -C 8 α-olefin comonomer. LLDPE is characterized by very few long chain branches (if any) compared to conventional LDPE. LLDPE has a density of 0.910 g / cc to less than 0.940 g / cc. Non-limiting examples of LLDPE include TUFLIN TM linear low density polyethylene resin (available from The Dow Chemical Company), DOWLEX TM polyethylene resin (available from The Dow Chemical Company), and MARLEX TM polyethylene (available from Chevron Phillips).

[0025] As used herein, the term "low density polyethylene" (or LDPE) refers to polyethylene having a density of from 0.909 g / cc to less than 0.940 g / cc, or from 0.917 g / cc to 0.930 g / cc and having long chain branching with a broad molecular weight distribution (MWD greater than 3.0).

[0026] As used herein, the term "terminal olefin group" refers to a double bond between two carbon atoms in a polymer chain, where one of the carbons in the double bond is a =CH 2 group. The terminal double bond is located at the end of the polymer chain and / or at the end of a side chain. As used herein, the term "internal olefin group" refers to a 1,2-disubstituted carbon-carbon double bond. The internal olefin groups are located throughout the length of the polymer chain but not at the end of the polymer chain or along the end of a side chain of the polymer chain. Terminal olefin groups and 1,2-trans disubstituted internal olefin groups are measured by Fourier transform infrared spectroscopy ("FTIR").

[0027] Test Methods

[0028] Density is measured according to ASTM D792 Method B. Results are reported in grams per cubic centimeter (g / cc). Hexane Extractables

[0029] Melt Force

[0030] A D-MELT device (available from Goettfert GmbH Buchen, Germany) is used to determine the melt force. The D-MELT device consists of a commercial plastometer and a digital balance containing a custom weighted sample. At a constant temperature (190 °C), the molten polymer strand is extruded from the standard plastometer barrel using a weighted piston through a standard ASTM D1238 MFR die (orifice height [8.000 ± 0.025 mm] and diameter [2.0955 ± 0.005 mm]). In the D-MELT device, the extrudate is pulled onto a drum driven by a stepper motor by two freely rotating rollers, the stepper motor ramping within a certain speed range during the analysis. The integrated control computer in the D-MELT device records the force required to pull the polymer strand upwards on a tension roller mounted on a force sensor platform. Based on the curve fitting function of the obtained force data, the final reported value is determined based on a constant speed ratio of the polymer strand speed to the die exit speed (the exact speed ratio depends on the product group). Depending on the rheometer type, the measurement results are reported as melt elasticity ("ME") in centinewtons (cN) or melt force ("MF") in millinewtons (mN). Immediately after the force measurement, the melt index ("MI") is measured under ASTM conditions using the same charge.

[0031] Melt Index

[0032] As used herein, the term "melt index" or "MI" refers to a measure of how easily a thermoplastic polymer flows when in a molten state. The melt index or I is measured according to ASTM D 1238, Condition 190°C / 2.16 kg 2 , and is reported in grams eluted per 10 minutes (g / 10 min). I10 is measured according to ASTM D 1238, Condition 190°C / 10 kg, and is reported in grams eluted per 10 minutes (g / 10 min).

[0033] Gel Permeation Chromatography (GPC)

[0034] The chromatographic system consists of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and a 4-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) 2-angle laser light scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15-degree angle is used for measurement. The autosampler oven chamber is set to 160°C, and the column chamber is set to 150°C. The columns used are 4 Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns. The chromatographic solvent used is 1,2,4-trichlorobenzene and contains 200 ppm of butylated hydroxytoluene (BHT). The solvent source is purged with nitrogen. The injection volume used is 200 microliters, and the flow rate is 1.0 mL / min.

[0035] The GPC column set is calibrated with at least 20 narrow molecular weight distribution polystyrene standards having molecular weights in the range of 580 to 8,400,000 and arranged in 6 "mixture" mixtures with at least a ten-fold separation between individual molecular weights. The standards are purchased from Agilent Technologies. The polystyrene standards are prepared in an amount of 0.025 grams in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 and in an amount of 0.05 grams in 50 mL of solvent for molecular weights less than 1,000,000. The polystyrene standards are gently agitated for 30 minutes at 80°C to dissolve. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 1 (as described by Williams and Ward, Journal of Polymer Science (J. Polym. Sci.), Polymer Letters (Polym. Let., 6, 621 (1968)):

[0036] M 聚乙烯 = A × (M 聚苯乙烯 ) B(Equation 1)

[0037] Where M is the molecular weight, A has a value of 0.4315 and B equals 1.0.

[0038] A polynomial between the 3rd and 5th order is used to fit the corresponding polyethylene equivalent calibration points. A small adjustment is made to A (from about 0.375 to 0.440) to correct for column resolution and band broadening effects such that the homopolymer polyethylene standard has a molecular weight of 120,000.

[0039] The total plate count of the GPC column set is performed with eicosane (prepared at 0.04 g in 50 ml of TCB and dissolved with gentle stirring for 20 minutes). The plate count (Equation 2) and symmetry (Equation 3) are measured with an injection of 200 μl according to the following equations:

[0040]

[0041] Where RV is the retention volume in ml, the peak width is in ml, the peak maximum is the maximum height of the peak, and 1 / 2 height is 1 / 2 of the peak maximum height.

[0042]

[0043] Where RV is the retention volume in ml and the peak width is in ml, the peak maximum is the maximum position of the peak, the one-tenth height is 1 / 10 of the peak maximum height, and where the back peak refers to the peak tail at a retention volume later than the peak maximum, and where the front peak refers to the peak front at a retention volume earlier than the peak maximum. The plate count of the chromatographic system should be greater than 24,000 and the symmetry should be between 0.98 and 1.22.

[0044] Samples are prepared semi-automatically using PolymerChar "Instrument Control" software, where the target weight of the sample is set at 2 mg / ml, and the solvent (containing 200 ppm BHT) is added to a septum-capped vial pre-bubbled with nitrogen through a PolymerChar high-temperature autosampler. The samples are dissolved at 160 °C for 2 hours with "low-speed" shaking.

[0045] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4 - 6, using PolymerChar GPCOne TM software, the Mn is determined from the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the calibration curve of the narrow standard at point (i) according to Equation 1(GPC) and Mw (GPC) and Mz (GPC) calculation.

[0046]

[0047]

[0048]

[0049] To monitor the deviation over time, a flow rate marker (decane) is introduced into each sample via a micro pump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) is used to linearly correct the pump flow rate (flow rate (nominal)) of each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(calibrated with FM)) of the alkane peak within the narrow standard calibration. Then, any change in the decane marker peak time is assumed to be related to a linear change in the flow rate (flow rate (effective)) throughout the run. To facilitate the highest accuracy in the measured RV of the flow marker peak, a least-squares fitting procedure is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. Then the first derivative of the quadratic equation is used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to narrow standard calibration) is calculated according to Equation 7. The processing of the flow marker peak is completed by PolymerChar GPCOne TM software. An acceptable flow rate correction results in the effective flow rate being within + / - 2% of the nominal flow rate.

[0050] Flow rate (effective) = Flow rate (nominal) * (RV(FM calibrated) / RV(FM sample)) (Equation 7)

[0051] Triple detector GPC (TDGPC)

[0052] The chromatographic system, run conditions, column settings, column calibration, and calculation of conventional molecular weight moments and distributions are performed according to the methods described in gel permeation chromatography (GPC).

[0053] To determine the offsets of the viscometer and light scattering detector relative to the IR5 detector, the systematic method for determining multi-detector offsets is carried out in a manner consistent with the way published by Balke, Mourey, etc. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), thus using PolymerChar GPCOne TM software to optimize the triple-detector log (MW and IV) results from a broad homopolymer polyethylene standard (Mw / Mn > 3) and the narrow standard column calibration results from the narrow standard calibration curve.

[0054] Absolute molecular weight data is obtained using PolymerChar GPCOne in a manner consistent with the way published by Zimm (Zimm, B.H., Journal of Chemical Physics, 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, New York, Oxford (1987)). TM The total injection concentration for determining molecular weight is obtained based on the mass detector area and the mass detector constant, where the mass detector constant is from one of the appropriate linear polyethylene homopolymers or polyethylene standards with known weight-average molecular weight. The calculated molecular weight (using GPCOne TM ) is obtained using the light scattering constant from one or more of the polyethylene standards mentioned below and the refractive index concentration coefficient dn / dc of 0.104. Generally, the mass detector response (IR5) and the light scattering constant (using GPCOne TM determination) should be determined by linear standards with molecular weights exceeding approximately 50,000 g / mol. Viscometer calibration (using GPCOne TM determination) can be done using the method described by the manufacturer or, alternatively, by using the published values of suitable linear standards (such as Standard Reference Material (SRM) 1475a) available from the National Institute of Standards and Technology (NIST). The viscometer constant (using GPCOne TM obtained) is calculated, which will be used to relate the specific viscosity area (DV) of the calibration standard and the injected mass to its intrinsic viscosity. It is assumed that the chromatographic concentration is low enough to eliminate the solution second virial coefficient effect (the effect of concentration on molecular weight).

[0055] Absolute weight-average molecular weight (MW (Abs) ) is obtained by dividing the area from light scattering (LS) integral chromatography (calculated from the light scattering constant) by the mass recovered from the mass constant and the area of the mass detector (IR5). The molecular weight and the inherent viscosity response are linearly extrapolated at the chromatographic end where the signal-to-noise ratio becomes low (using GPCOne TM ). The other corresponding moments Mn TM and Mz (Abs) are calculated according to Equations 8 to 9 as follows: (Abs)

[0056]

[0057]

[0058] The gpcBR branching index by triple detector GPC (3D-GPC)

[0059] The gpcBR branching index is determined by first calibrating the light scattering, viscosity, and concentration detectors as described above. Then, the baselines are subtracted from the light scattering, viscometer, and concentration chromatograms. Then, the integration window is set to ensure the integration of all low molecular weight retention volume ranges in the light scattering and viscometer chromatograms, and the chromatograms indicate the presence of detectable polymers from the infrared (IR5) chromatogram. Then, the polyethylene and polystyrene Mark-Houwink constants are established using linear polyethylene standards. After obtaining the constants, the two values are used to construct two linear reference conventional calibrations of polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution volume, as shown in Equations (10) and (11):

[0060] M PE = (K PS / K PE 1 / α ) +1 PE PS · M αPS+1 / αPE+1 PS (Equation 10)

[0061] [η] PE = K PS · M PS α+1 / M PE (Equation 11).

[0062] The gpcBR branching index is a robust method for characterizing long-chain branching, as described in Yau, Wallace W., "Examples of Using 3D-GPC—TREF for Polyolefin Characterization", Macromol. Symp., 2007, 257, 29-45. This index avoids the traditional "slice-by-slice" 3D-GPC calculations and branching frequency calculations used to determine g′ values, which is beneficial for the entire polymer detector region. From the 3D-GPC data, the absolute weight-average molecular weight (Mw, Abs) of the sample bulk can be obtained using the peak area method through a light scattering (LS) detector. The method avoids the "slice-by-slice" ratio of the light scattering detector signal to the concentration detector signal required in traditional g' determination.

[0063] For 3D-GPC, the sample intrinsic viscosity is also obtained independently using Equation (8). The area calculations in Equations (5) and (8) provide higher precision because, as the total sample area, it is less sensitive to variations caused by detector noise and 3D-GPC settings on the baseline and integration limits. More importantly, the peak area calculation is not affected by detector volume offsets. Similarly, a high-precision sample intrinsic viscosity (IV) is obtained by the area method shown in Equation (12):

[0064]

[0065] where η spi represents the specific viscosity obtained from the viscometer detector.

[0066] To determine the gpcBR branching index, the light scattering elution area of the sample polymer is used to determine the molecular weight of the sample. The viscosity detector elution area of the sample polymer is used to determine the intrinsic viscosity (IV or [η]) of the sample.

[0067] First, the molecular weight and intrinsic viscosity of a linear polyethylene standard sample (e.g., SRM1475a) or equivalent are determined using conventional calibration ("cc") for both the molecular weight and intrinsic viscosity that vary with the elution volume.

[0068]

[0069] Equation (14) is used to determine the gpcBR branching index:

[0070]

[0071] where [η] is the measured intrinsic viscosity, [η] ccis the intrinsic viscosity from conventional calibration, Mw is the measured weight-average molecular weight, and Mw ,cc is the weight-average molecular weight of conventional calibration. The weight-average molecular weight by light scattering (LS) is usually referred to as the "absolute weight-average molecular weight" or "Mw,Abs". Mw,cc using the conventional GPC molecular weight calibration curve ("conventional calibration") is usually referred to as the "polymer chain backbone molecular weight", "conventional weight-average molecular weight", and "Mw, GPC ".

[0072] All statistical values with the subscript "cc" are determined using their respective elution volumes, the corresponding conventional calibration and concentration (Ci) as described above. The non-subscript values are based on the measured values of the mass detector, LALLS, and viscometer area. Iteratively adjust the K PE value until the gpcBR measured value of the linear reference sample is zero. For example, in this specific case, the final values of α and Log K for determining gpcBR are 0.725 and -3.391 for polyethylene, and 0.722 and -3.993 for polystyrene, respectively. Then these polyethylene coefficients are input into Equation 13.

[0073] Once the K and α values are determined using the previously discussed procedure, repeat the procedure using the branched sample. Due to applying the optimal "cc" calibration value, the final Mark-Houwink constants obtained from the linear reference are used to analyze the branched sample.

[0074] The interpretation of gpcBR is straightforward. For linear polymers, the gpcBR calculated from Equation (14) will be close to zero because the values measured by LS and viscometry will be close to the conventional calibration standard. For branched polymers, gpcBR will be higher than zero, especially for high levels of long-chain branching, because the measured polymer molecular weight will be higher than the calculated Mw,cc, and the calculated IVcc will be higher than the measured polymer IV. In fact, the gpcBR value represents the fractional IV change due to the molecular size contraction effect as a result of polymer branching. A gpcBR value of 0.5 or 2.0 means that the molecular size contraction effect of IV is 50% and 200% respectively relative to the equivalent linear polymer molecule.

[0075] For these specific examples, compared with the traditional "g' index" and branching frequency calculations, the advantage of using gpcBR is due to the higher precision of gpcBR. All parameters used in the gpcBR index determination are obtained with good precision and are not adversely affected by the low 3D-GPC detector response at high molecular weights from the concentration detector. Errors in detector volume alignment also do not affect the precision of gpcBR index determination.

[0076] Fourier transform infrared analysis ("FTIR")

[0077] The amounts of terminal and internal olefins per 1000 carbons (or “1000C”) are determined by Fourier transform infrared analysis (“FTIR”). Sample films (about 250 to 300 microns thick) for FTIR analysis are compression molded by pressing about 0.5 g of sample pellets in a Carver hydraulic press with a heated platen set to 190 °C. The amounts of terminal and internal olefins per 1000 carbons are measured according to a procedure similar to that outlined in ASTM method D6248. FTIR measures internal olefin bonds in the 1,2-substituted and trans configurations, and internal olefin bonds in the cis configuration or tri- or tetra-substituted (where not measured by FTIR). Detailed Description

[0078] The present disclosure provides ethylene-based polymer compositions. The ethylene-based polymer compositions are formed by high-pressure (greater than or equal to 100 MPa) free radical polymerization, and the polymer compositions comprise a mixture of ethylene monomer and hydroxy-terminated polybutadiene molecules (PB-OH). Each PB-OH molecule comprises internal olefin groups and terminal olefin groups, and each PB-OH molecule has more internal olefin groups than terminal olefin groups.

[0079] Hydroxy-terminated polybutadiene molecules

[0080] The ethylene-based polymer composition is a polymerization reaction product of a mixture of ethylene and hydroxy-terminated polybutadiene molecules (PB-OH). As used herein, the term “hydroxy-terminated polybutadiene molecule” (which may be referred to interchangeably as “PB-OH”) refers to a chemical composition of a polymer chain consisting of only carbon atoms, hydrogen atoms, and two hydroxy groups (-OH), the polymer chain being branched and having internal olefin groups (i.e., carbon-carbon double bonds) and terminal olefin groups, and the polymer chain having more internal olefin groups than terminal olefin groups. As used herein, the term “mixture of hydroxy-terminated polybutadiene molecules” refers to two or more hydroxy-terminated polybutadiene molecules, where at least two molecules are different in structure, properties, and / or composition.

[0081] In one embodiment, each of the PB-OH molecules in the mixture has Structure I:

[0082] Structure I

[0083]

[0084] where c is from 0 to 90, n is from 0 to 90, t is from 0 to 90, and

[0085] c + n + t ≥ 4, provided that c, n, and t cannot all be 0.

[0086] In one embodiment, Structure I includes c of 0 or 1 to 10, n of 0 or 1 to 10, t is 0 or 1 to 20, and c + n + t >= 4, provided that c, n, and t cannot be 0 simultaneously.

[0087] In one embodiment, the mixture of PB-OH-based molecules consists of two or more hydrocarbon molecules having Structure I:

[0088] Structure I

[0089]

[0090] where n is the number of terminal olefin groups, c is the number of cis-internal olefin groups, t is the number of trans-internal olefin groups, the average c content is 0 or 1 to 10, the average n content is 0 or 1 to 10, and the average t content is 0 or 1 to 20, and the average c + n + t content is greater than 4, but c, n, and t cannot be 0 simultaneously.

[0091] The "average n content" is calculated by dividing the number-average molecular weight (Mn) by the weight-average molecular weight (Mw) of the hydrocarbon molecule, and then multiplying by the fraction of terminal olefin groups. The "average c content" is calculated by dividing the number-average molecular weight (Mn) by the weight-average molecular weight (Mw) of the hydrocarbon molecule, and then multiplying by the fraction of internal cis-olefin groups. The "average t content" is calculated by dividing the number-average molecular weight (Mn) by the weight-average molecular weight (Mw) of the hydrocarbon molecule, and then multiplying by the fraction of internal trans-olefin groups.

[0092] In one embodiment, the mixture of PB-OH molecules has the following corresponding average c, n, and t values (expressed as "c / n / t"): 0-10 / 0-10 / 0-20 or 2-8 / 2-8 / 6-18.

[0093] In one embodiment, the mixture of PB-OH molecules based on Structure I has a molecular weight distribution of 1.2 to 20. In another embodiment, the mixture of PB-OH molecules based on Structure I has a molecular weight distribution of 1.2, or 1.3, or 1.4 to 2, or 5 to 10 or 20. In another embodiment, the mixture of PB-OH molecules based on Structure I has a molecular weight distribution of 1.2 to 20, or 1.3 to 10, or 1.5 to 5.

[0094] In an embodiment, each of the PB-OH molecules has Structure II:

[0095] Structure II

[0096]

[0097] Where c ranges from 0 to 90, n ranges from 0 to 90, t ranges from 0 to 90, x ranges from 0 to 90, y ranges from 0 to 90, and c + n + t >= 4, provided that c, n, and t cannot be 0 simultaneously. In another embodiment, c is 0 or from 1 to 10, n is 0 or from 1 to 10, t is 0 or from 1 to 20, x is 0, or 1 or 5, or from 10 to 20, or 30 or 60, and y is 0, or 1, or 5, or 10, or from 20 to 30, or 60, and c + n + t >= 4, but the condition is that c, n, and t cannot be 0 simultaneously. In another embodiment, c is from 2 to 8, n is from 2 to 8, t is from 6 to 18, and c + n + t >= 4.

[0098] The hydrocarbon molecules of Structure I and / or Structure II may hereinafter be interchangeably referred to as "branching agents".

[0099] The symbols in Structure I and Structure II represent a cis-alkyl group or a trans-alkyl group relative to the double bond.

[0100] In an embodiment, a mixture of hydrocarbon molecules having Structure I and / or Structure II with different molecular weights is used.

[0101] It should be understood that the ethylene-based polymer composition may include (i) only Structure I, (ii) only Structure II, or (iii) a combination of Structure I and Structure II. It should be understood that as used herein, the term "ethylene-based polymer composition" refers to a polymer that is a reaction product of ethylene having Structure I and / or Structure II.

[0102] In an embodiment, the ethylene-based polymer composition comprises a mixture of 95 wt%, or 96 wt%, or 97 wt%, or 98 wt% to 99 wt%, or 99.5 wt%, or 99.7 wt%, or 99.9 wt% of ethylene in polymeric form and a co-mount of PB-OH molecules, or a mixture of 5.0 wt%, or 4.0 wt%, or 3.0 wt%, or 2.0 wt% to 1.0 wt%, or 0.5 wt%, or 0.3 wt%, or 0.1 wt% of PB-OH molecules. The weight percentages are based on the total weight of the ethylene-based polymer composition. In another embodiment, the ethylene-based polymer composition includes 95.0 wt% to 99.9 wt%, or 96 wt% to 99.8 wt%, or 98 wt% to 99.8 wt% of ethylene in polymeric form, and the mixture of PB-OH molecules is present in an amount of 5.0 wt% to 0.1 wt%, or 4.0 wt% to 0.2 wt%, or 2.0 wt% to 0.2 wt%.

[0103] The ethylene-based polymer composition has a density of from 0.909 g / cc to 0.940 g / cc. In an embodiment, the ethylene-based polymer composition has a density of 0.909 g / cc, or 0.915 g / cc, or from 0.920 g / cc to 0.930 g / cc, or 0.935 g / cc, or 0.940 g / cc. In another embodiment, the ethylene-based polymer composition has a density of from 0.910 g / cc to 0.940 g / cc, or from 0.915 g / cc to 0.935 g / cc, or from 0.917 g / cc to 0.930 g / cc, or from 0.917 g / cc to 0.926 g / cc.

[0104] The ethylene-based polymer composition has a terminal olefin content of 0.05 / 1000 carbons, or 0.08 / 1000 carbons, or 0.1 / 1000 carbons; the ethylene-based composition also has a trans internal olefin content of 0.08 / 1000 carbons, or from 0.10 / 1000 carbons to 1.2 / 1000 carbons, or 1.5 / 1000 carbons.

[0105] In one embodiment, the ethylene-based polymer composition has a terminal olefin to internal olefin ratio of from 0.1 to 2.0. In another embodiment, the ethylene-based polymer composition has a terminal olefin to internal olefin ratio of from 0.2 to 1.0 or from 0.2 to 0.8.

[0106] In one embodiment, the ethylene-based polymer composition has a total olefin content (sum of terminal double bonds and 1,2-disubstituted trans double bonds) measured by FTIR of greater than 0.4 / 1000C, or from 0.5 to 2.0 / 1000C, or from 0.5 to 1.5 / 1000C. In an embodiment, the ethylene-based polymer composition has one, some, or all of the following properties:

[0107] (i) The MI is 0.1, or 0.5, or from 1.0 to 5, or 10 g / 10 min; and / or

[0108] (ii) The MF is from 64 to 85 mN; and / or

[0109] (iii) The terminal olefin content is 0.15 / 1000 carbons, or 0.20 / 1000 carbons, or 0.24 / 1000 carbons; and / or

[0110] (iv) The trans internal olefin content is 0.1 / 1000 carbons, or 0.2 / 1000 carbons to 1.2 / 1000 carbons, or 1.5 / 1000 carbons; and / or

[0111] (v) The terminal olefin to trans internal olefin ratio is from 0.5 to 1.0 or from 0.6 to 0.9

[0112] (vi) having a density of from 0.910 g / cc to 0.935 g / cc;

[0113] (vii) the ratio of terminal olefins to trans internal olefins normalized to from 0.3 to 1.0 or from 0.4 to 0.7

[0114] In an embodiment, the ethylene-based polymer composition includes a blend component. The blend component is a polymer that is a mixture that does not include hydrocarbon molecules (i.e., does not include a branching agent having Structure I or Structure II). Non-limiting examples of suitable blend components include ethylene-based polymers, ethylene / α-olefin copolymers, ethylene / C 3 -C 8 α-olefin copolymers, ethylene / C 4 -C 8 α-olefin copolymers, and copolymers of ethylene with one or more of the following comonomers: acrylate, (meth)acrylic acid, (meth)acrylate, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, monoester of maleic acid, diester of maleic acid, vinyltrialkoxysilane, vinyltrialkylsilane, and any combination thereof.

[0115] In an embodiment, the blend component is an ethylene-based polymer that is a mixture that does not include hydrocarbon molecules.

[0116] In an embodiment, the blend component is high density polyethylene (HDPE).

[0117] In an embodiment, the blend component is linear low density polyethylene (LLDPE).

[0118] In another embodiment, the blend component is an ethylene / α-olefin copolymer. In a further embodiment, the α-olefin of the blend component is C 3 -C 8 α-olefin, or C 4 -C 8 α-olefin.

[0119] The present disclosure also provides an article comprising at least one component formed from the ethylene-based polymer composition described herein or a combination of two or more embodiments.

[0120] In an embodiment, the article is a coating for a film.

[0121] In an embodiment, the article is a coating.

[0122] In an embodiment, the article is a film.

[0123] The ethylene-based polymer composition includes a combination of two or more embodiments as described herein.

[0124] The article includes a combination of two or more embodiments as described herein.

[0125] Method

[0126] The present disclosure also provides a process for producing the ethylene-based polymer composition. The method includes polymerizing ethylene monomer in a reactor configuration providing high pressure (greater than 100 MPa) polymerization conditions in the presence of a mixture of PB-OH molecules (Structure I and / or Structure II). The reactor configuration is one or more tubular reactors and / or one or more autoclave reactors.

[0127] To produce a highly branched ethylene-based polymer composition, a high-pressure free-radical initiated polymerization process is used. Two different types of high-pressure free-radical initiated polymerization processes are known. In the first type of process, a stirred autoclave reactor having one or more reaction zones is used. The autoclave reactor typically has several injection points for initiator or monomer feed or both. In the second type of process, a jacketed tube is used as the reactor having one or more reaction zones. Suitable but non-limiting reactor lengths can be from 100 meters to 3000 meters (m), or from 1000 meters to 2000 meters. The start of the reaction zone of either type of reactor is typically defined by side injection of the initiator, ethylene, chain transfer agent (or telogen), comonomer, and any combination thereof. The high-pressure process can be carried out in an autoclave reactor or a tubular reactor having one or more reaction zones, or in a combination of an autoclave reactor and a tubular reactor each containing one or more reaction zones. In an embodiment, the initiator is injected prior to the reaction zone where free-radical polymerization is initiated.

[0128] In one embodiment, the method includes polymerizing ethylene monomer in a tubular reactor under high pressure (greater than 100 MPa) polymerization conditions in the presence of a mixture of PB-OH molecules (Structure I and / or Structure II), a chain transfer agent (CTA), and a free radical initiator. The tubular reactor is a multi-zone tubular reactor having alternating locations for feeding fresh ethylene to control the ratio of ethylene to CTA and thereby control polymer properties. Fresh ethylene monomer is added simultaneously at multiple locations to achieve the desired ethylene monomer to chain transfer ratio. The addition points of fresh CTA are carefully selected to control polymer properties. Fresh CTA is added simultaneously at multiple locations to achieve the desired CTA to ethylene monomer ratio. Similarly, the addition points and amounts of fresh PB-OH molecules (Structure I and / or Structure II) are controlled to control gel formation while maximizing the desired properties of increased melt strength and performance in the target application. Fresh PB-OH molecules (Structure I and / or Structure II) are added simultaneously to multiple locations to achieve the desired PB-OH molecule to ethylene monomer ratio. Using a mixture of PB-OH molecules to broaden the molecular weight distribution and increase the melt strength of the polymer will place further requirements on the distribution of the mixture of CTA and PB-OH molecules along the reactor system in order to achieve the desired changes in product properties while minimizing potential negative impacts such as gel formation, reactor fouling, and process instability. Non-limiting examples of suitable tubular polymerization reactors include the tubular reactors and polymerization conditions disclosed in WO2013059042 (A1) and WO2013078018 (A2), the entire contents of each reference being incorporated herein by reference.

[0129] Non-limiting examples of ethylene monomers for producing ethylene-based polymer compositions include purified ethylene, which is obtained by removing polar components from the loop recycle stream or by using a reaction system configuration such that only fresh ethylene is used to prepare the ethylene-based polymer compositions of the present invention. Other examples of ethylene monomers include ethylene monomers from a recycle loop, wherein the method includes a recycle loop that improves conversion efficiency.

[0130] One or more chain transfer agents (CTAs) are added to the tubular reactor to control the molecular weight. Non-limiting examples of suitable CTAs include propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMobil Chemical Co.), and isopropyl alcohol, and combinations thereof. The amount of CTA used in the method is from 0.01 weight percent to 10 weight percent, or from 0.01 weight percent to 5 weight percent, or from 0.1 weight percent to 1.0 weight percent, or from 0.1 weight percent to 0.5 weight percent, or from 0.01 weight percent to 0.1 weight percent of the total reaction mixture.

[0131] In one embodiment, the CTA is propionaldehyde.

[0132] In one embodiment, the CTA is propylene.

[0133] One or more free radical initiators are fed into a tubular reactor to produce an ethylene-based polymer composition. Non-limiting examples of suitable free radical initiators include organic peroxides, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, diperoxycarbonates, peroxy esters, peroxyketals, tert-butyl peroxy pivalate, di-tert-butyl peroxide, tert-butyl peroxyacetate, and tert-butyl peroxy-2-ethylhexanoate, and combinations thereof. In one embodiment, the free radical initiator includes at least one peroxide group incorporated in a ring structure. Non-limiting examples of free radical initiators having a peroxide group incorporated in a ring structure include TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane) and TRIGONOX 311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane), available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxanonane), available from United Initiators. These organic peroxide initiators are used in an amount of 0.001 wt% to 0.2 wt% based on the weight of the polymerizable monomers.

[0134] In one embodiment, the free radical initiator is a combination of tert-butyl peroxy-2-ethylhexanoate and di-tert-butyl peroxide.

[0135] In one embodiment, the polymerization is carried out in a tubular reactor having a plurality of reactor zones (3 to 6 reactor zones). The maximum temperature of each reactor zone is 150 °C to 360 °C, or 170 °C to 350 °C, or 200 °C to 340 °C. The pressure in each tubular reactor zone is typically 100 MPa to 380 MPa, 110 MPa to 340 MPa, or 110 MPa to 300 MPa. The PB-OH molecules (Structure I and / or Structure II) are fed directly into the reaction zone or into the feed zone of the reaction zone through a compression stage.

[0136] In one embodiment, the PB-OH molecules (Structure I and / or Structure II) are added at the inlet of the reaction zone before or simultaneously with the addition of the free radical initiator. In another embodiment, the hydrocarbon molecules (Structure I and / or Structure II) are added before the addition of the initiator to achieve good dispersion.

[0137] In one embodiment, the PB-OH molecules (Structure I and / or Structure II) are fed only to Reaction Zone 1.

[0138] In an embodiment, the ethylene fed to the first reaction zone is 10% to 100% of the total ethylene fed to the polymerization. In a further embodiment, the ethylene fed to the first reaction zone is 20% to 80% of the total ethylene fed to the polymerization, further 25% to 75%, further 30% to 70%, and further 40% to 60%.

[0139] In one embodiment, the tubular reactor has three reactor zones. The method includes maintaining the first reactor peak temperature at 290 °C to 310 °C and the pressure at 230 MPa to 200 MPa, maintaining the second reactor peak temperature at 290 °C to 310 °C and the pressure at 225 MPa to 195 MPa, and maintaining the peak temperature of the third reactor at 290 °C to 310 °C and the pressure at 220 MPa to 190 MPa. The method includes feeding CTA (propionaldehyde) and a peroxy radical initiator (tert-butyl peroxy-2-ethylhexanoate and di-tert-butyl peroxide) to each of the three reactor zones to control the peak temperature in the reactor and the MI of the final product. The ethylene monomer, PB-OH molecules (Structure I and / or Structure II) are fed to the first reactor zone only at a ratio of 0.0016 to 0.0048 kg of hydrocarbon-based molecules per kg of ethylene. The method includes polymerizing the ethylene monomer in the presence of a mixture of PB-OH molecules (Structure I and / or Structure II), a chain transfer agent (CTA), and a radical initiator.

[0140] In one embodiment, the method includes polymerizing the ethylene monomer under the above polymerization conditions in the presence of a mixture of PB-OH molecules (Structure I and / or Structure II), one or more additional monomers, a chain transfer agent (CTA), and a radical initiator. Non-limiting examples of additional monomers include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene, acrylate, (meth)acrylic acid, (meth)acrylate, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, monoesters of maleic acid, diesters of maleic acid, vinyltrialkoxysilane, vinyltrialkylsilane, and any combination thereof.

[0141] Additive

[0142] In an embodiment, the composition includes one or more additives. Non-limiting examples of additives include stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, flame retardants, processing aids, smoke inhibitors, viscosity control agents, and antiblocking agents. Based on the weight of the ethylene-based polymer composition, the polymer composition can, for example, contain less than 10% by combined weight of one or more additives.

[0143] In an embodiment, the ethylene-based polymer composition is treated with one or more stabilizers, such as antioxidants, e.g., IRGANOX 1010, IRGANOX 1076, and IRGAFOS 168. Typically, the ethylene-based polymer composition is treated with one or more stabilizers prior to extrusion or other melt processes.

[0144] Applications

[0145] The ethylene-based polymer compositions of the present disclosure can be used in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including but not limited to single-layer and multi-layer films; agricultural films, molded articles such as blow molded, injection molded, or rotomolded articles; coatings; fibers; and woven or non-woven fabrics, cables, pipes, greenhouse films, silo bag films, shrink wrap films, food packaging films, foams.

[0146] The ethylene-based polymer compositions can be used in a variety of films, including but not limited to clear shrink films, agricultural films, shrink wrap films, cast stretch films, silage films, stretch hoods, sealants, and diaper backsheets. Other suitable applications include but are not limited to wires and cables, gaskets and profiles, adhesives; footwear components, and automotive interior parts. The ethylene-based polymer compositions of the present invention can be used as part of a blend with LLDPE for agricultural films - large blown films.

[0147] The applicant unexpectedly found that a mixture of PB-OH molecules used in the reactor, when the internal olefin groups of PB-OH are more than the terminal olefin groups, results in an ethylene-based polymer composition having an increased number of branching points, which leads to greater melt strength.

[0148] Examples

[0149] Polybutadiene (Additive A: Poly R20LM, Structure I) was provided by Cray Valley USA. The properties of this material are listed in Table 1 below.

[0150] Table 1

[0151]

[0152] 1 Provided by Cray Valley

[0153] 2 Calculated by dividing Mn by the Mw of the butadiene monomer (hydrocarbon molecule) and multiplying by the fractional amounts of the terminal olefin groups of n and the internal olefin groups of m. Example: Mn = 1,300 g / mol, average n = (1,300 - 32 g / mol) / (54.09 g / mol butadiene monomer) = ~23.44 repeat units * 0.2 (terminal olefins / total olefins) = an average of ~4.69 terminal vinyl groups per chain

[0154] Polymerization: autoclave reactor

[0155] Inventive Example I (IE I): Additive A was charged into a 316 stainless steel supply vessel and diluted with Isopar TM E to produce a final concentration of 1.7 wt%. The vessel was purged with nitrogen for three hours prior to use and maintained under a 70 psig nitrogen blanket during operation.

[0156] Various feed levels of this solution were introduced into the reactor to produce polymer samples.

[0157] Initiators: The peroxide initiator tert-butyl peroxyacetate (TPA, a 20 wt% solution in ISOPAR TM H), and the peroxide initiator di-tert-butyl peroxide (DTBP, a 20 wt% solution in ISOPAR TM H) were combined with ISOPAR E in a second 316 stainless steel supply vessel to produce 1500 mass ppm of TPA and 415 mass ppm of DTBP (a 4:1 molar TPA / mole DTBP ratio). The vessel was filled and emptied five times with nitrogen at 70 psig prior to use and maintained under a nitrogen blanket during operation.

[0158] Ethylene was injected into a stirred (1600 rpm) 300 mL high-pressure CSTR reactor at 5500 gm / hr at a pressure of 193 MPa, where an external heating jacket was set to control the internal reactor temperature at 220 °C. Propylene (CTA) was added to the ethylene stream at a pressure of 6.2 MPa, and the rate was controlled to produce a final product with an MI of ~4 g / 10 min, then the mixture was compressed to 193 MPa and injected into the reactor. A solution of the appropriate additive solution was pumped directly into the reactor via a high-pressure pump at a pressure of 193 MPa. The peroxide initiator solution was added directly to the reactor through the sidewall at a pressure of 193 MPa at a rate to control the ethylene conversion to be close to 12%.

[0159] Details of the polymerization procedures for each experiment are shown in Table 2 below.

[0160] Table 2: Autoclave Polymerization Conditions (at an ethylene feed of 5,500 g / h and at 220 °C)

[0161]

[0162] 2. Melt Strength Experiments

[0163] Additional samples were prepared under the autoclave polymerization conditions disclosed above. Specifically, the feed rate of additive A was varied while maintaining the melt index (MI) constant (at or near 4 g / 10 min). The Applicant has found that increasing the amount of additive A while maintaining the melt index constant increases the melt strength (MS) of the polymer. The results of the melt strength experiments are shown in Table 3 below (MF (corrected value) = log(MI) / log(4) * MF (measured value)).

[0164] Table 3: Results of Melt Strength Experiments

[0165]

[0166] Figure 1 is a graph showing the average corrected melt force (MF) versus the ppm of additive A present in the ethylene-based resonance peak polymer. Figure 1 Shows the melt force normalized to 4 MI by the following equation:

[0167] MF (corrected value) = log(MI) / log(4) * MF (measured value).

[0168] Figure 1 Shows that, with the MI maintained constant (equal to or near 4 MI), the melt force of the ethylene-based polymer increases as the amount of additive A (Poly bd) present in the ethylene-based polymer increases.

[0169] 3. FTIR Measurements

[0170] The amount of terminal double bonds (or vinyl groups) and the amount of trans internal double bonds per 1000 °C were measured by FTIR (Table 4), where vinyl / trans normalization = (vinyl in the inventive example - vinyl in the baseline) / (trans in the inventive example - trans in the baseline)

[0171] Table 4: FTIR Results

[0172]

[0173] 1 Vinyl = terminal olefin double bond; 2 Only the internal olefin bonds in the trans configuration were measured.

[0174] Particularly desired is that the present disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments, including combinations of parts of the embodiments and elements of different embodiments that occur within the scope of the following claims.

Claims

1. An ethylene-based polymer composition formed by high-pressure free radical polymerization at a pressure of 100 MPa or higher, said polymer composition comprising: A mixture of ethylene in polymerized form and hydroxy-terminated polybutadiene molecules PB-OH, each PB-OH molecule comprising internal olefin groups and terminal olefin groups, with more internal olefin groups than terminal olefin groups in each PB-OH molecule; Wherein said hydroxy-terminated polybutadiene molecules have Structure I or Structure II: Structure I Wherein the average c is from 1 to 14.06, the average n is from 1 to 10, the average t is from 1 to 20, and c + n + t >= 4, provided that c, n, and t cannot all be 0; Structure II Wherein the average c is from 1 to 14.06, the average n is from 1 to 10, the average t is from 1 to 20, x is from 0 to 90, y is from 0 to 90: and c + n + t >= 4, provided that c, n, and t cannot all be 0.

2. The ethylene-based polymer composition according to claim 1, wherein the mixture of hydroxy-terminated polybutadiene molecules based on Structure I has a molecular weight distribution of 1.2 to 10.

3. The ethylene-based polymer composition according to claim 1, wherein the mixture of hydroxy-terminated polybutadiene molecules based on Structure II has a molecular weight distribution of 1.2 to 10.

4. The ethylene-based polymer composition according to any one of claims 1-3, wherein the ethylene-based polymer composition has a terminal olefin content of 0.15 / 1000 carbons to 0.9 / 1000 carbons.

5. The ethylene-based polymer composition according to any one of claims 1-3, wherein the ethylene-based polymer composition has an internal trans-olefin content of 0.1 / 1000 carbons to 1 / 1000 carbons.

6. The ethylene-based polymer composition according to any one of claims 1-3, wherein the ethylene-based polymer composition has a density of 0.909 g / cc to 0.940 g / cc.

7. The ethylene-based polymer composition according to any one of claims 1-3, which further comprises a blend component, wherein the blend component does not include the mixture of hydroxy-terminated polybutadiene molecules.

8. An article comprising the composition according to any one of claims 1-7.

9. The article according to claim 8, wherein the article is selected from the group consisting of: films, coatings, and coated sheets.

10. The article according to claim 9, wherein the article is selected from the group consisting of: coatings for cables and coatings for wires.

11. A method, the method comprising: Reacting 95 wt% to 99.98 wt% of ethylene monomer and 0.02 wt% to 5.0 wt% of a mixture of hydroxy-terminated polybutadiene molecules in a polymerization reactor under free radical polymerization conditions and at a pressure of 100 MPa or higher, based on the total weight of the ethylene-based polymer composition, each molecule having Structure I: Structure I where c is from 1 to 14.06, n is from 1 to 10, t is from 1 to 20, and c + n + t ≥ 4, provided that c, n, and t are not simultaneously 0; and an ethylene-based polymer composition is formed.

12. The method according to claim 11, wherein the polymerization occurs in a reactor configuration comprising at least one tubular reactor.

13. The method according to claim 11, wherein the polymerization occurs in a reactor configuration comprising at least one autoclave reactor.

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