Branched ethylene-based polymer compositions and processes for their production

Abstract

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

Description

[Background technology]

[0001] The level of branching in low-density polyethylene (LDPE) is primarily a function of the reactor design and polymerization conditions used to make the LDPE. Branching agents have been used to increase the level of branching in LDPE. However, the process conditions required to achieve modified LDPE with high levels of branching often result in a final product with lower crystallinity and a higher content of low molecular weight extractable fractions. Therefore, there is a need for modified LDPE that has high branching levels 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 (100 MPa or greater) free-radical polymerization. The ethylene-based polymer composition includes ethylene monomer and a mixture of hydroxyl-terminated polybutadiene molecules (PB-OH). Each PB-OH molecule includes an internal alkene group and a terminal alkene group. Each PB-OH molecule has more internal alkene groups than terminal alkene groups.

[0003] The present disclosure provides a process, in one embodiment, comprising reacting ethylene monomer with a mixture of hydroxyl-terminated polybutadiene molecules in a polymerization reactor under free radical polymerization conditions and at a pressure of 100 MPa or greater, each molecule having the structure I: [ka] In the formula, c is 0 to 90, n is 0 to 90, and t is 0 to 90. c+n+t≧4, with the proviso that c, n, and t cannot each simultaneously be 0. The process includes forming an ethylene-based polymer composition. [Brief explanation of the drawings]

[0004] [Figure 1] 1 is a graph showing average corrected melt strength (MF) versus ppm of Additive A present in formant ethylene-based polymers according to one embodiment of the present disclosure.

[0005] definition Any references to the Periodic Table of the Elements are to the table as published in 1990-1991 by CRC Press, Inc. References to groups of elements in this table are to the new notation for numbering groups.

[0006] For purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the corresponding U.S. version thereof is so incorporated by reference), particularly with respect to disclosure of definitions (to the extent that they do not contradict any definitions specifically provided in this disclosure).

[0007] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, inclusive. Ranges that include explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7) include any subranges between any two explicit values ​​(e.g., the range 1 to 7 above includes subranges such as 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.).

[0008] Unless otherwise stated, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0009] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0010] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not the same is specifically disclosed. 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" also excludes any component, step, or procedure not specifically 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.

[0011] As used herein, the term "polymer" or "polymeric material" refers to a compound prepared by polymerizing monomers, whether of the same or different types, to provide, in polymerized form, the multiple and / or repeating "units" or "mer units" that make up the polymer. Thus, the generic term "polymer" encompasses the term "homopolymer," which is typically used to refer to a polymer prepared from only one type of monomer, and the term "copolymer," which is typically 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 specific monomers, "based on" a particular monomer or monomer type, "containing" a particular monomer content, etc., it is noted that in this context, the term "monomer" is understood to refer to the polymerized residue of a particular monomer, not to the unpolymerized species. Generally, polymers herein are referred to in terms of "units" that are the polymerized form of the corresponding monomers.

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

[0013] As used herein, the terms "blend" or "polymer blend" refer to a mixture of two or more polymers. A blend may or may not be miscible (not phase separated at the molecular level). A blend may or may not be phase separated. A blend 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. A blend may be achieved by physically mixing two or more polymers at a macro level (e.g., melt blending or compounding) or a micro level (e.g., co-molding in the same reactor).

[0014] As used herein, the term "ethylene / alpha-olefin copolymer" refers to a copolymer having greater than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and at least one alpha-olefin.

[0015] As used herein, the term "ethylene-based polymer composition" refers to a composition that, in polymerized form, comprises greater than 50 weight percent, or a majority amount, of ethylene, based on the weight of the polymer, and may optionally include at least one comonomer or other molecule.

[0016] As used herein, the term "ethylene monomer" refers to a chemical unit having two carbon atoms with a double bond between them, and each carbon bonded to two hydrogen atoms, that polymerizes with other such chemical units to form an ethylene-based polymer composition.

[0017] 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 is a polymer made from ethylene and one or more C3 to C6 20An α-olefin comonomer may be included. The comonomer may 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 using either Ziegler-Natta, chromium-based, constrained geometry, or metallocene catalysts in a slurry, gas-phase, or solution reactor. Ethylene / C3-C 20 The α-olefin copolymer comprises at least 50% by weight ethylene polymerized therein, 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 ethylene in polymerized form.

[0018] As used herein, the term "hydrocarbon-based molecule" refers to a chemical entity that contains only carbon and hydrogen atoms.

[0019] As used herein, the term "linear low density polyethylene" (or "LLDPE") refers to a polymer having units derived from ethylene and at least one C3-C6 10 LLDPE refers to linear ethylene / α-olefin copolymers containing a heterogeneous distribution of short chain branches, including units derived from α-olefins or C4-C8 α-olefin comonomers. LLDPE, in contrast to conventional LDPE, is characterized by little, if any, long chain branching. LLDPE has a density of 0.910 g / cc to less than 0.940 g / cc. Non-limiting examples of LLDPE include TUFLIN™ linear low density polyethylene resin (available from The Dow Chemical Company), DOWLEX™ polyethylene resin (available from Dow Chemical Company), and MARLEX™ polyethylene (available from Chevron Phillips).

[0020] As used herein, the term "low density polyethylene" (or LDPE) refers to polyethylene having a density of 0.909 g / cc to less than 0.940 g / cc, or 0.917 g / cc to 0.930 g / cc, and long chain branching with a broad molecular weight distribution (MWD greater than 3.0).

[0021] As used herein, the term "terminal alkene 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 =CH2 group. Terminal double bonds are located at the end of the polymer chain and / or at the end of a branch. As used herein, the term "internal alkene group" refers to a 1,2-disubstituted carbon-carbon double bond. Internal alkene groups are located throughout the length of the polymer chain, but are not located at the end of the polymer chain or at the end of a branch along the polymer chain. Terminal alkene groups and 1,2-disubstituted internal alkene groups are measured by infrared spectroscopy ("FTIR").

[0022] Test Method Density is measured according to ASTM D792, Method B. Results are reported in grams per cubic centimeter (g / cc) of hexane extractables.

[0023] Melting Power Melt force is measured using a D-MELT apparatus (available from Goettfert GmbH, Buchen, Germany). The DMELT apparatus includes a commercially available plastometer and a digital scale incorporating a custom weighted sample. A weighted piston is used to extrude a molten polymer strand from a standard plastometer barrel at a constant temperature (190°C) 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 apparatus, the extrudate is pulled through two freely rotating rollers onto a drum driven by a stepper motor, which is ramped over a range of speeds during analysis. The force of the polymer strand pulling onto a tension roller attached to a force sensor platform is recorded by an integrated control computer within the D-MELT apparatus. From a curve-fitting function of the acquired force data, the final reported value is determined based on a constant speed ratio of polymer strand velocity to die exit velocity (the exact speed ratio is product family dependent). The results are reported as melt elasticity ("ME") in centinewtons (cN) or melt force ("MF") in millinewtons (mN), depending on the type of rheometer. Immediately after the force measurement, a melt index ("MI") measurement under ASTM conditions is performed on the same charge.

[0024] Melt Index 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. Melt index (I2) is measured in accordance with ASTM D 1238, condition 190°C / 2.16 kg, and is reported in grams eluted per 10 minutes (g / 10 min). I10 is measured in accordance with ASTM D 1238, condition 190°C / 10 kg, and is reported in grams eluted per 10 minutes (g / 10 min) by gel permeation chromatography (GPC).

[0025] The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and a four-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) two-angle laser light scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15-degree angle was used. 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. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / min.

[0026] Calibration of the GPC column set was performed using at least 20 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures with at least 10 molecular weight intervals between each standard. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

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[0027] A third- to fifth-order polynomial was used to fit each polyethylene-equivalent calibration point, with a small adjustment of A (approximately 0.375-0.440) to compensate for column resolution and band broadening effects, resulting in a homopolymer polyethylene standard with a molecular weight of 120,000.

[0028] Total plate counts for the GPC column set were performed with Eicosane (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 measured with a 200 microliter injection according to the following equations:

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[0029] Samples were prepared in a semi-automated fashion using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged septa-capped vial. Samples were dissolved at 160°C with "slow" shaking for 2 hours.

[0030] Mn (GPC) , Mw(GPC) , and Mz (GPC) The calculation of was based on GPC results using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from a narrow standard calibration curve at point (i) in Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6.

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[0031] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow marker (FM) was used to linearly correct the pump flow rate (Flow (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 (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow marker peaks, a least-squares fitting routine was used to fit the peaks in the flow 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 marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as shown in Equation 7. Processing of the flow marker peaks was performed using PolymerChar GPCOne™ software. The acceptable flow correction should be within + / - 2% of the apparent flow rate. Flow Rate (Effective) = Flow Rate (Apparent) * (RV(FM Calibrated) / RV(FM Sample)) (Equation 7)

[0032] Triple Detector GPC (TDGPC) The chromatographic system, analytical conditions, column set, column calibration and calculation and distribution of conventional molecular weight moments were performed according to the methods described in Gel Permeation Chromatography (GPC).

[0033] With regard to the determination of viscometer and light scattering detector offsets from the IR5 detector, a systematic approach for the determination of multiple detector offsets was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)) using PolymerChar GPCOne™ software to optimize triple detector log (MW and IV) results from broad homopolymer polyethylene standards (Mw / Mn>3) against narrow standard column calibration results from a narrow standard calibration curve.

[0034] Absolute molecular weight data were obtained using PolymerChar GPCOne™ software in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injection concentration used in determining the molecular weight was obtained from the mass detector area and mass detector constant derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards of known weight average molecular weight. Calculated molecular weights (using GPCOne™) were obtained using the light scattering constant and refractive index concentration coefficient, dn / dc, of 0.104 derived from one or more of the polyethylene standards described below. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight greater than about 50,000 g / mol. Viscometer calibration (determined using GPCOne™) can be achieved using the method described by the manufacturer, or alternatively, by using the published value of a suitable linear standard, such as Standard Reference Material (SRM) 1475a (available from the National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated, relating the specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. Chromatographic concentrations are assumed to be low enough to preclude addressing second viral coefficient effects (concentration effects on molecular weight).

[0035] Absolute weight average molecular weight (MW (Abs) ) is obtained (using GPCOne™) by dividing the light scattering (LS) area integrated chromatogram (factored by the light scattering constant) by the mass recovered from the mass constant and the mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated (using GPCOne™) at the chromatographic end where the signal to noise is low. The other respective moments, Mn(Abs) and Mz (Abs) is calculated according to the following equations 8 and 9.

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[0036] gpcBR branching index by triple detector GPC (3D-GPC) The gpcBR branching index is determined by first calibrating the light scattering, viscosity, and concentration detectors, as previously described. Baselines are then subtracted from the light scattering, viscometer, and concentration chromatograms. Integration windows are then set to ensure full integration of the low molecular weight retention volume range of the light scattering and viscometer chromatograms, which indicates the presence of detectable polymer from the infrared (IR5) chromatogram. Linear polyethylene standards are then used to establish the Mark-Houwink constants for polyethylene and polystyrene. Once the constants are obtained, 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). M PE =(K PS / K PE ) 1 / α PE +1 M PS αPS+1 / αPE+1 (Formula 10) [η] PE =K PS M PS α+1 / M PE (Equation 11). 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 "slice-by-slice" 3D-GPC calculations traditionally used to determine g' values ​​and calculate branching frequencies in favor of the entire polymer detector area. From 3D-GPC data, the bulk absolute weight-average molecular weight (MW, Abs) of a sample can be obtained by a light scattering (LS) detector using the peak area method. This method avoids the "slice-by-slice" ratio of the light scattering detector signal to the concentration detector signal, as required for traditional g' determination.

[0037] In 3D-GPC, the intrinsic viscosity of the sample was also obtained separately using equation (8). The area calculation in equations (5) and (8) provides greater precision because the overall sample area is less susceptible to detector noise at the baseline and integration limits and variations caused by the 3D-GPC settings. More importantly, the peak area calculation is insensitive to detector volume offsets. Similarly, the sample intrinsic viscosity (IV) with high precision can be obtained by the area method shown in equation (12).

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[0038] 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 for the sample polymer is used to determine the intrinsic viscosity (IV or [η]) of the sample. First, the molecular weight and intrinsic viscosity for a linear polyethylene standard, such as SRM1475a or equivalent, are determined using conventional calibrations for both molecular weight and intrinsic viscosity as a function of elution volume ("cc").

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[0039] All statistical values ​​with a "cc" subscript are determined using the respective elution volume, the corresponding conventional calibration as described above, and the concentration (Ci). Values ​​without a subscript are measurements based on the mass detector, LALLS, and viscometer area. K PE The values ​​of α and Log K are iteratively adjusted until the linear reference sample has a gpcBR measurement of zero. For example, the final values ​​of α and Log K for determining the gpcBR in this particular case are 0.725 and -3.391, respectively, for polyethylene and 0.722 and -3.993, respectively, for polystyrene. These polyethylene coefficients were then entered into Equation 13.

[0040] Once the K and α values ​​have been determined using the procedure described above, the procedure is repeated using a branched sample that is analyzed using the final Mark-Houwink constants obtained from the linear reference when the best-fit "cc" calibration value is applied.

[0041] 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 viscometers will be close to conventional calibration standards. For branched polymers, especially those with high levels of long-chain branching, the gpcBR will be higher than zero. This is 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 effect, the gpcBR value represents the fractional change in IV due to the molecular size shrinkage effect as a result of polymer branching. gpcBR values ​​of 0.5 and 2.0 represent a molecular size shrinkage effect on IV at levels of 50% and 200%, respectively, relative to an equivalent weight of linear polymer molecules.

[0042] In these particular examples, the advantage of using gpcBR compared to traditional "g' index" and branching frequency calculations is due to the higher accuracy of gpcBR. All of the parameters used in determining the gpcBR index are obtained with high 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 accuracy of the gpcBR index determination.

[0043] Fourier Transform Infrared Analysis ("FTIR") Determination of the amount of terminal and internal alkenes per 1000 carbons (or 1000C) was by Fourier transform infrared analysis ("FTIR"). Sample films (approximately 250-300 microns thick) used for FTIR analysis were compression molded by pressing approximately 0.5 g pellets of sample in a Carver hydraulic press with heated platens set at 190 °C. The amount of terminal and internal alkenes per 1000 carbons was measured according to a procedure similar to that outlined in ASTM method D6248. FTIR measures internal alkene linkages in 1,2- and trans-configuration, internal alkene linkages in cis-configuration, or tri- or tetra-substituted internal alkene linkages when not measured by FTIR. DETAILED DESCRIPTION OF THE INVENTION

[0044] The present disclosure provides an ethylene-based polymer composition formed by high-pressure (100 MPa or greater) free-radical polymerization of ethylene monomer and a mixture of hydroxyl-terminated polybutadiene molecules (PB-OH). Each PB-OH molecule contains an internal alkene group and a terminal alkene group, with each PB-OH molecule having more internal alkene groups than terminal alkene groups.

[0045] Hydroxyl-terminated polybutadiene molecules An ethylene-based polymer composition is a polymerization reaction product of ethylene and a mixture of hydroxyl-terminated polybutadiene molecules (PB-OH). As used herein, the term "hydroxyl-terminated polybutadiene molecule" (interchangeably referred to as "PB-OH") refers to a chemical moiety that is a polymer chain composed exclusively of carbon and hydrogen atoms and two hydroxyl groups (-OH), where the polymer chain is branched and has internal alkene groups (i.e., carbon-carbon double bonds) and terminal alkene groups, where the polymer chain has more internal alkene groups than terminal alkene groups. As used herein, the term "mixture of hydroxyl-terminated polybutadiene molecules" refers to two or more hydroxyl-terminated polybutadiene molecules, where at least two of the molecules differ in structure, properties, and / or composition.

[0046] In one embodiment, each of the PB—OH molecules in the mixture has the structure I: [ka] In the formula, c is 0 to 90, n is 0 to 90, and t is 0 to 90. c+n+t≧4, provided that c, n, and t cannot each be 0 simultaneously.

[0047] In one embodiment, Structure I comprises c, which is 0, or 1 to 10; n, which is 0, or 1 to 10; t, which is 0, or 1 to 20; and c+n+t≧4, with the proviso that c, n, and t cannot each simultaneously be 0.

[0048] In one embodiment, the mixture of PB—OH based molecules consists of two or more hydrocarbon based molecules having structure I: [ka] In the formula, n is the number of terminal alkene groups, c is the number of cis internal alkene groups, and t is the number of trans internal alkene groups, the average c content is 0 or 1 to 10, the average n content is 0 or 1 to 10, the average t content is 0 or 1 to 20, and the average c+n+t content is greater than 4, with the proviso that c, n, and t cannot each be 0 at the same time.

[0049] The "average n content" is calculated by dividing the number average molecular weight (Mn) of the hydrocarbon-based molecules by the weight average molecular weight (Mw) and then multiplying by the fraction of terminal alkene groups. The "average c content" is calculated by dividing the number average molecular weight (Mn) of the hydrocarbon-based molecules by the weight average molecular weight (Mw) and then multiplying by the fraction of internal cis alkene groups. The "average t content" is calculated by dividing the number average molecular weight (Mn) of the hydrocarbon-based molecules by the weight average molecular weight (Mw) and then multiplying by the fraction of internal trans alkene groups.

[0050] In one embodiment, the mixture of PB—OH molecules has respective average c, n, and t values ​​(denoted as “c / n / t”) as follows: 0-10 / 0-10 / 0-20, or 2-8 / 2-8 / 6-18.

[0051] In one embodiment, the mixture of PB—OH molecules according to structure I has a molecular weight distribution of 1.2 to 20. In another embodiment, the mixture of PB—OH molecules according to 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 further embodiments, the mixture of PB—OH molecules according to structure I has a molecular weight distribution of 1.2 to 20, or 1.3 to 10, or 1.5 to 5.

[0052] In one embodiment, each of the PB—OH molecules has the structure II: [ka] wherein c is 0 to 90, n is 0 to 90, t is 0 to 90, x is 0 to 90, y is 0 to 90, and c+n+t≧4, with the proviso that c, n, and t cannot simultaneously be 0. In another embodiment, c is 0 or 1 to 10, n is 0 or 1 to 10, t is 0 or 1 to 20, x is 0, or 1, or 5, or 10 to 20, or 30, or 60, and y is 0, or 1, or 5, or 10, or 20 to 30, or 60, and c+n+t≧4, with the proviso that c, n, and t cannot simultaneously be 0. In a further embodiment, c is 2 to 8, n is 2 to 8, and t is 6 to 18, and c+n+t≧4.

[0053] The hydrocarbon-based molecules of Structure I and / or Structure II are hereinafter referred to interchangeably as "branching agents."

[0054] Notation in Structure I and Structure II [ka] represents a cis- or trans-alkyl group relative to the double bond.

[0055] In one embodiment, a mixture of hydrocarbon-based molecules having Structure I and / or Structure II with different molecular weights is used.

[0056] It is understood that the ethylene-based polymer composition can comprise (i) only Structure I, (ii) only Structure II, or (iii) a combination of Structure I and Structure II. It is understood that the term "ethylene-based polymer composition," as used herein, refers to a polymer that is the reaction product of ethylene with Structure I and / or Structure II.

[0057] In one embodiment, the ethylene-based polymer composition comprises, in polymerized form, 95%, or 96%, or 97%, or 98% to 99%, or 99.5%, or 99.7%, or 99.9% ethylene and an inverse amount of a mixture of PB—OH molecules, or from 5.0%, or 4.0%, or 3.0%, or 2.0% to 1.0%, or 0.5%, or 0.3%, or 0.1% PB—OH molecules, where the weight percentages are based on the total weight of the ethylene-based polymer composition. In further embodiments, the ethylene-based polymer composition comprises from 95.0% to 99.9% by weight, or from 96% to 99.8% by weight, or from 98% to 99.8% by weight, of ethylene in polymerized form, and the mixture of PB—OH molecules is present in an amount from 5.0% to 0.1% by weight, or from 4.0% to 0.2% by weight, or from 2.0% to 0.2% by weight.

[0058] The ethylene-based polymer composition has a density from 0.909 g / cc to 0.940 g / cc. In one embodiment, the ethylene-based polymer composition has a density from 0.909 g / cc, or from 0.915 g / cc, or from 0.920 g / cc to 0.930 g / cc, or from 0.935 g / cc, or from 0.940 g / cc. In another embodiment, the ethylene-based polymer composition has a density 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.

[0059] The ethylene-based polymer composition has a terminal alkene content of from 0.05 / 1000 carbons, or 0.08 / 1000 carbons, or 0.1 / 1000 carbons, and the ethylene-based composition also has a trans internal alkene content of from 0.08 / 1000 carbons, or 0.10 / 1000 carbons, to 1.2 / 1000 carbons, or 1.5 / 1000 carbons.

[0060] In one embodiment, the ethylene-based polymer composition has a terminal to internal alkene ratio of from 0.1 to 2.0, hi another embodiment, the ethylene-based polymer composition has a terminal to internal alkene ratio of from 0.2 to 1.0, or from 0.2 to 0.8.

[0061] In one embodiment, the ethylene based polymer composition has a total alkene content (the sum of terminal double bonds and 1,2-disubstituted trans double bonds) as measured by FTIR of greater than 0.4 / 1000 C, or from 0.5 to 2.0 / 1000 C, or from 0.5 to 1.5 / 1000 C. In one embodiment, the ethylene based polymer composition has one, some, or all of the following properties: (i) an MI of 0.1, or 0.5, or 1.0 to 5, or 10 g / 10 min; and / or (ii) MF between 64 and 85 mN, and / or (iii) a terminal alkene content of 0.15 / 1000 carbons, or 0.20 / 1000 carbons, or 0.24 / 1000 carbons; and / or (iv) a trans-internal alkene content of 0.1 / 1000 carbons, or 0.2 / 1000 carbons to 1.2 / 1000 carbons, or 1.5 / 1000 carbons; and / or (v) Terminal to trans-internal alkene ratio of 0.5 to 1.0 or 0.6 to 0.9 (vi) Density of 0.910 g / cc to 0.935 g / cc. (vii) Terminal to trans -internal alkene ratio normalized to 0.3–1.0 or 0.4–0.7

[0062] In one embodiment, the ethylene-based polymer composition comprises a blend component. The blend component is a polymer that does not contain a mixture of hydrocarbon-based molecules (i.e., does not contain a branching agent having Structure I or Structure II). Non-limiting examples of suitable blend components include ethylene-based polymers, ethylene / alpha-olefin copolymers, ethylene / C3-C8 alpha-olefin copolymers, ethylene / C4-C8 alpha-olefin copolymers, and copolymers of ethylene and one or more of the following comonomers: acrylates, (meth)acrylic acid, (meth)acrylic esters, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, monoesters of maleic acid, diesters of maleic acid, vinyltrialkoxysilanes, vinyltrialkylsilanes, and any combination thereof.

[0063] In one embodiment, the blend component is an ethylene-based polymer that does not contain admixtures of hydrocarbon-based molecules.

[0064] In one embodiment, the blend component is high density polyethylene (HDPE).

[0065] In one embodiment, the blend component is linear low density polyethylene (LLDPE).

[0066] In another embodiment, the blend component is an ethylene / alpha-olefin copolymer. In a further embodiment, the alpha-olefin of the blend component is a C3 to C8 alpha-olefin, or a C4 to C8 alpha-olefin.

[0067] The present disclosure also provides an article comprising at least one component formed from the ethylene-based polymer composition or a combination of two or more embodiments, as described herein.

[0068] In one embodiment, the article is a film coating.

[0069] In one embodiment, the article is a coating.

[0070] In one embodiment, the article is a film.

[0071] The ethylene-based polymer composition comprises a combination of two or more embodiments as described herein.

[0072] An article comprises a combination of two or more embodiments as described herein.

[0073] process The present disclosure also provides a process for producing the inventive ethylene-based polymer composition. The process includes polymerizing ethylene monomer in the presence of a mixture of PB-OH molecules (Structure I and / or Structure II) in a reactor configuration that provides high-pressure (greater than 100 MPa) polymerization conditions. The reactor configuration is one or more tubular reactors and / or one or more autoclave reactors.

[0074] High-pressure, free-radical initiated polymerization processes are used to produce highly branched ethylene-based polymer compositions. Two different types of high-pressure, free-radical initiated polymerization processes are known. In the first process type, a stirred autoclave reactor with one or more reaction zones is used. Autoclave reactors typically have several injection points for initiator or monomer feed, or both. In the second process type, a jacketed tube is used as the reactor, which has one or more reaction zones. Suitable, but not limited to, reactor lengths can be 100 meters to 3,000 meters (m), or 1,000 meters to 2,000 meters. In both types of reactors, the beginning of a reaction zone is typically defined by a side injection of either initiator, ethylene, chain transfer agent (or telomer), comonomer(s), or combinations thereof. High-pressure processes can be carried out in autoclave or tubular reactors with one or more reaction zones, or in a combination of autoclave and tubular reactors, each containing one or more reaction zones. In one embodiment, the initiator is injected prior to the reaction zone where free radical polymerization is to be induced.

[0075] In one embodiment, the process involves polymerizing 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 free radical initiator in a tubular reactor under high-pressure (greater than 100 MPa) polymerization conditions. The tubular reactor is a multi-zone tubular reactor with alternative locations for supplying fresh ethylene to control the ratio of ethylene to CTA and, therefore, the polymer properties. Fresh ethylene monomer is added simultaneously at multiple locations to achieve a desired ethylene monomer to chain transfer ratio. The addition of fresh CTA addition points is selected to control the polymer properties. Fresh CTA is added simultaneously at multiple locations to achieve a desired CTA to ethylene monomer ratio. Similarly, the addition points and the amount of fresh PB-OH molecules (Structure I and / or Structure II) are controlled to control gel formation while maximizing the desired properties of improved melt strength and performance in the target application. Fresh PB-OH molecules (Structure I and / or Structure II) are added simultaneously at multiple locations to achieve a desired PB-OH molecule to ethylene monomer ratio. The use of a mixture of PB-OH molecules to broaden the molecular weight distribution and increase the melt strength of the polymer imposes additional requirements on the distribution of the CTA and the mixture of PB-OH molecules along the reactor system to achieve the desired changes in product properties while minimizing potential adverse effects such as gel formation, reactor fouling, process instability, etc. Non-limiting examples of suitable tubular polymerization reactors include the tubular reactors and polymerization conditions disclosed in WO2013 / 059042 (A1) and WO2013 / 078018 (A2), the entire contents of each reference being incorporated herein by reference.

[0076] Non-limiting examples of ethylene monomers used in producing the ethylene-based polymer compositions include purified ethylene obtained by removing polar components from a loop recycle stream or by using a reaction system configuration such that only fresh ethylene is used to make the inventive ethylene-based polymer compositions. Further examples of ethylene monomers include ethylene monomer from a recycle loop, where the process includes a recycle loop to improve conversion efficiency.

[0077] One or more chain transfer agents (CTAs) are added to the tubular reactor to control 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 isopropanol, and mixtures thereof. The amount of CTA used in the process 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.

[0078] In one embodiment, the CTA is propionaldehyde.

[0079] In one embodiment, the CTA is propylene.

[0080] One or more free radical initiators are fed into the tubular reactor to produce the ethylene-based polymer composition. Non-limiting examples of suitable free radical initiators include organic peroxides, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals, t-butyl peroxypivalate, di-t-butyl peroxide, t-butyl peroxyacetate, and t-butyl peroxy-2-hexanoate, and combinations thereof. In one embodiment, the free radical initiator comprises at least one peroxide group incorporated into a ring structure. Non-limiting examples of free radical initiators with peroxide groups incorporated into the ring structure include TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane) and TRIGONOX 311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane) (both available from Akzo Nobel), and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane) available from United Initiators. Organic peroxy initiators are used in amounts of 0.001% to 0.2% by weight, based on the weight of the polymerizable monomers.

[0081] In one embodiment, the free radical initiator is a combination of tert-butyl peroxy-2-ethylhexanoate and di-tert-butyl peroxide.

[0082] In one embodiment, the polymerization is carried out in a tubular reactor having multiple reactor zones (3 to 6 reactor zones). The maximum temperature in each reactor zone is 150°C to 360°C, 170°C to 350°C, or 200°C to 340°C. The pressure in each reactor zone is 100 MPa to 380 MPa, 110 MPa to 340 MPa, or 110 MPa to 300 MPa. PB-OH molecules (Structure I and / or Structure II) are fed directly to the reaction zone via a compression stage or directly to the feed to the reaction zone.

[0083] In one embodiment, the PB-OH molecules (Structure I and / or Structure II) are added at the entrance to the reaction zone prior to or simultaneously with the addition of the free radical initiator. In another embodiment, the hydrocarbon-based molecules (Structure I and / or Structure II) are added prior to the addition of the initiator to allow for good dispersion.

[0084] In one embodiment, PB—OH molecules (structure I and / or structure II) are provided only to reaction zone 1.

[0085] In one embodiment, the ethylene fed to the first reaction zone is from 10 percent to 100 percent of the total ethylene fed to the polymerization. In further embodiments, the ethylene fed to the first reaction zone is from 20 percent to 80 percent, further from 25 percent to 75 percent, further from 30 percent to 70 percent, and further from 40 percent to 60 percent of the total ethylene fed to the polymerization.

[0086] In one embodiment, the tubular reactor has three reactor zones. The process includes maintaining a first reactor peak temperature of 290°C to 310°C and a pressure of 230 MPa to 200 MPa, a second reactor peak temperature of 290°C to 310°C and a pressure of 225 MPa to 195 MPa, and a third reactor peak temperature of 290°C to 310°C and a pressure of 220 MPa to 190 MPa. The process includes feeding CTA (propionaldehyde) and peroxy radical initiators (tert-butyl peroxy-2-ethylhexanoate and di-tert-butyl peroxide) into each of the three reactor zones to control the peak temperature within the reactor and the MI of the final product. Ethylene monomer, PB-OH molecules (Structure I and / or Structure II), are fed only to the first reactor zone at a ratio of 0.0016 to 0.0048 kg of hydrocarbon molecules to kg (kilogram) of ethylene. The process involves polymerizing 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 free radical initiator.

[0087] In one embodiment, the process comprises polymerizing ethylene monomer 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 free radical initiator under the aforementioned polymerization conditions. Non-limiting examples of the additional monomers include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene, acrylates, (meth)acrylic acid, (meth)acrylic acid esters, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, monoesters of maleic acid, diesters of maleic acid, vinyltrialkoxysilanes, vinyltrialkylsilanes, and any combination thereof.

[0088] additives In one 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 suppressants, viscosity control agents, and anti-blocking agents. The polymer composition may, for example, include less than 10 percent by total weight of the one or more additives, based on the weight of the ethylene-based polymer composition.

[0089] In one embodiment, the ethylene-based polymer composition is treated with one or more stabilizers, for example, antioxidants such as IRGANOX 1010, IRGANOX 1076, and IRGAFOS 168. Generally, the ethylene-based polymer composition is treated with one or more stabilizers prior to extrusion or other melt processing.

[0090] Purpose The ethylene-based polymer compositions of the present disclosure can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including, but not limited to, monolayer and multilayer films; agricultural films, molded articles such as blow-molded, injection-molded, or rotationally molded articles; coatings; fibers; and woven or nonwoven fabrics, cables, pipes, greenhouse films, silo bag films, collated shrink films, food packaging films, or foams.

[0091] The ethylene-based polymer composition can be used in a variety of films, including, but not limited to, transparent shrink film, agricultural film, collated shrink film, cast stretch film, silage film, stretch hood, sealant, and diaper backsheet. Other suitable applications include, but are not limited to, wire and cable, gaskets and profiles, adhesives, footwear components, and automotive interior parts. The ethylene-based polymer composition can be used as part of a blend with LLDPE for agricultural films (large blown films).

[0092] Applicants have unexpectedly discovered that a mixture of PB—OH molecules used in the reactor, PB—OH having more internal alkene groups than terminal alkene groups, results in an ethylene-based polymer composition with an increased number of branch points, resulting in greater melt power. [Example]

[0093] Polybutadiene (Additive A: Poly bd® R20LM, Structure I) was supplied by Cray Valley USA. The properties of this material are shown in Table 1 below. [Table 1]

[0094] Polymerization: Autoclave reactor Invention Example I (IE I): Additive A was charged to a 316 stainless steel supply vessel and diluted with Isopar™ E to produce a final concentration of 1.7 wt %. The vessel was purged with nitrogen for 3 hours prior to use and kept under a 70 psig nitrogen pad during operation.

[0095] Various feed levels of this solution were introduced into the reactor to produce polymer samples.

[0096] Initiator: In a second 316 stainless steel feed vessel, the peroxide initiators tert-butyl peroxyacetate (TPA, a 20 wt % solution in ISOPAR™ H) and di-tert-butyl peroxide (DTBP, a 20 wt % solution in ISOPAR™ H) were combined with ISOPAR E to produce 1500 ppm by weight TPA and 415 ppm by weight DTBP (4:1 molar TPA / mole DTBP ratio). The vessel was padded and unpadded five times with 70 psig nitrogen prior to use and kept under the nitrogen pad during operation.

[0097] Ethylene was injected at 5500 gm / h at 193 MPa into a stirred (1600 rpm) 300 mL high-pressure CSTR reactor, with an external heating jacket controlling the internal reactor temperature at 220 °C. Propylene (CTA) was added to the ethylene stream at 6.2 MPa pressure at a controlled rate to produce a final product MI of approximately 4 g / 10 min, and the mixture was then compressed to 193 MPa and injected. A solution of the appropriate additive solution was pumped directly into the reactor at 193 MPa via a high-pressure pump. A peroxide initiator solution was added directly to the reactor through the sidewall at 193 MPa pressure at a rate that controlled the ethylene conversion to near 12%.

[0098] The polymerization procedures for each experiment are detailed in Table 2 below. [Table 2]

[0099] 2. Melt Strength Experiment Additional samples were prepared under the autoclave polymerization conditions disclosed above. Specifically, the feed rate of Additive A was varied while the melt index (MI) was held constant (at or near 4 g / 10 min). Applicant discovered that increasing the amount of Additive A while holding the melt index constant increased the melt strength (MS) of the polymer. The results of the melt strength experiments are shown in Table 3 below (MF(corrected) = log(MI) / log(4) * MF(measured)). [Table 3]

[0100] Figure 1 is a graph showing the average corrected melt strength (MF) versus ppm of Additive A present in formant ethylene-based polymers. Figure 1 shows the melt strength normalized to 4 MI by the formula: MF(corrected) = log(MI) / log(4)*MF(measured).

[0101] FIG. 1 shows that when the MI is held constant (at or near 4 MI), the melt strength of the ethylene-based polymer increases as the amount of additive A (Poly bd) present in the ethylene-based polymer increases.

[0102] 3.FTIR Measurement The amount of terminal double bonds (or vinyl) and the amount of trans-internal double bonds per 1000 C were measured by FTIR (Table 4), where normalized vinyl / trans = (vinyl of the inventive example - vinyl of the baseline) / (trans of the inventive example - trans of the baseline). [Table 4]

[0103] It is expressly intended that the present disclosure is not limited to the embodiments and examples contained herein, but includes modifications of these embodiments, including portions of the embodiments and combinations of elements from different embodiments that fall within the scope of the following claims. The inventions described in the original claims of this application are set forth below. [1] An ethylene-based polymer composition formed by high-pressure (100 MPa or greater) free-radical polymerization, 1. An ethylene-based polymer composition comprising: ethylene monomer; and a mixture of hydroxyl-terminated polybutadiene molecules (PB—OH), each PB—OH molecule comprising an internal alkene group and a terminal alkene group, each PB—OH molecule having more internal alkene groups than terminal alkene groups. [2] The hydrocarbon molecule has the structure I,

change

change

[10] The ethylene-based polymer composition according to any one of [1] to [9], further comprising a blend component, wherein the blend component does not contain a mixture of hydroxyl-terminated polybutadiene molecules.

[11] An article comprising the composition according to any one of [1] to

[10] .

[12] The article of

[11] , wherein the article is selected from the group consisting of a film, a coating, a coating for a cable, a coating for a wire, and a coated sheet.

[13] A process, reacting ethylene monomer with a mixture of hydroxyl-terminated polybutadiene molecules in a polymerization reactor under free radical polymerization conditions and at a pressure of at least 100 MPa, each molecule having the structure I:

change

[14] The process of

[13] , wherein the polymerization is carried out in a reactor configuration comprising at least one tubular reactor.

[15] The process of

[13] , wherein the polymerization is carried out in a reactor configuration comprising at least one autoclave reactor.

Claims

1. 1. An ethylene-based polymer composition comprising, in polymerized form, 95% to 99.98% by weight ethylene and 0.02% to 5.0% by weight of a mixture of hydroxyl-terminated polybutadiene molecules (PB-OH), based on the total weight of the ethylene-based polymer composition; each PB-OH molecule comprises an internal alkene group and a terminal alkene group, and each PB-OH molecule has more internal alkene groups than terminal alkene groups; Ethylene-based polymer compositions.

2. the hydroxyl-terminated polybutadiene molecule has structure I: 【Chemical Formula 1】 [Wherein c is 0 to 90, n is 0 to 90, and t is 0 to 90, c+n+t≧4, with the proviso that c, n, and t cannot simultaneously be 0. The ethylene-based polymer composition of claim 1.

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

4. the hydroxyl-terminated polybutadiene molecule has structure II: 【Chemistry 2】 [Wherein c is 0 to 90, n is 0 to 90, t is 0 to 90, x is 0 to 90, and y is 0 to 90; c+n+t≧4, with the proviso that c, n, and t cannot simultaneously be 0. The ethylene-based polymer composition of claim 1.

5. 5. The ethylene-based polymer composition of claim 4, wherein the mixture of hydroxyl-terminated polybutadiene molecules according to Structure II has a molecular weight distribution from 1.2 to 10.

6. The ethylene-based polymer composition of any one of claims 1 to 5, wherein the ethylene-based polymer composition has a terminal alkene content from 0.15 / 1000 carbons to 0.9 / 1000 carbons.

7. The ethylene-based polymer composition of any one of claims 1 to 5, wherein the ethylene-based polymer composition has an internal trans-alkene content of from 0.1 / 1000 carbon to 1 / 1000 carbon.

8. The ethylene-based polymer composition of any one of claims 1 to 7, wherein the ethylene-based polymer composition has a density from 0.909 g / cc to 0.940 g / cc.

9. The ethylene-based polymer composition of any one of claims 1 to 8, further comprising a blend component, wherein the blend component does not comprise the mixture of hydroxyl-terminated polybutadiene molecules.

10. An article comprising the composition of any one of claims 1 to 9.

11. 11. The article of claim 10, wherein the article is selected from the group consisting of a film, a coating, a coating for a cable, a coating for a wire, and a coated sheet.

12. 1. A process for producing an ethylene-based polymer composition, comprising: reacting ethylene monomer with a mixture of hydroxyl-terminated polybutadiene molecules in a polymerization reactor under free radical polymerization conditions and at a pressure of at least 100 MPa, wherein each hydroxyl-terminated polybutadiene molecule has the structure I: 【Chemistry 3】 In the formula, c is 0 to 90, n is 0 to 90, and t is 0 to 90; c+n+t≧4, with the proviso that c, n, and t cannot simultaneously be 0; forming an ethylene-based polymer composition comprising, in polymerized form, 95 wt % to 99.98 wt % ethylene and 0.02 wt % to 5.0 wt % of a mixture of hydroxyl-terminated polybutadiene molecules (PB-OH), based on the total weight of the ethylene-based polymer composition; Including, Each PB-OH molecule contains an internal alkene group and a terminal alkene group, and each PB-OH molecule has more internal alkene groups than terminal alkene groups. process.

13. 13. The process of claim 12, wherein the polymerization is carried out in a reactor configuration comprising at least one tubular reactor.

14. 13. The process of claim 12, wherein the polymerization is carried out in a reactor configuration comprising at least one autoclave reactor.

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