Thermally cross-linked, ethylene-based, rigid articles

Abstract

Embodiments are directed to a thermally cross-linked, ethylene-based, rigid article comprising an ethylene-based polymer formed by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules. Each of the one or more hydrocarbon-based molecules comprises three or more terminal alkene groups. The thermally cross-linked ethylene-based, rigid article, thermally cross-linked in the presence of oxygen, has a greater melt elongation relative to an ethylene-based, rigid article not subjected thermal crosslinking in the presence of oxygen.

Description

[0001] 86130-WO-PCT / DOW 86130 WO

[0002] 1

[0003] THERMALLY CROSS-LINKED, ETHYLENE-BASED, RIGID ARTICLES

[0004] CROSS-REFERENCE TO RELATED APPLICATIONS

[0005] [1] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 725,660 filed November 27, 2024, the contents of which are incorporated in their entirety herein.

[0006] TECHNICAL FIELD

[0007] [2] Embodiments of the present disclosure generally relate to rigid articles and specifically relate to thermally cross-linked, ethylene-based, rigid articles.

[0008] BACKGROUND

[0009] [3] High-pressure reactors have been used in industry for making low density polyethylene (LDPE) products for many years. The level of branching in LDPE at given melt index correlates to melt elongation, with higher branching correlating to a higher melt elongation. The level of branching in LDPE is affected by the reactor design and the polymerization conditions used to make the LDPE. But, the process conditions required to achieve LDPE with a high level of branching, and thus high melt elongation may result in a final product with a lower crystallinity and with a higher content of a low molecular weight extractable fraction. Branching agents have been used to increase the level of branching in an LDPE under conditions that maintain desirable polymer properties. However, due to processing limitations, only a limited amount of branching agent may be added, thereby limiting the melt elongation increase that may be achieved, resulting in a rigid article having undesirable mechanical properties, dimensional stability, and / or heat resistance.

[0010] [4] Accordingly, there is a need for modified LDPE rigid articles having relatively higher branching levels corresponding to a relatively higher melt elongation as compared to a LDPE rigid article formed utilizing a branching agent.

[0011] SUMMARY

[0012] [5] The embodiments of the present disclosure meet this need by utilizing thermal crosslinking in the presence of oxygen. This resulted in a thermally cross-linked, ethylene- 86130-WO-PCT / DOW 86130 WO

[0013] 2 based, rigid article having a greater melt elongation (e.g., at least 15% greater) relative to an ethylene-based, rigid article not subjected thermal crosslinking in the presence of oxygen.

[0014] [6] In one embodiment, a thermally cross-linked, ethylene-based, rigid article comprises an ethylene-based polymer formed by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules. Each of the one or more hydrocarbon-based molecules comprises three or more terminal alkene groups. The thermally cross-linked ethylene-based, rigid article, thermally cross-linked in the presence of oxygen, has a greater melt elongation relative to an ethylene-based, rigid article not subjected thermal crosslinking in the presence of oxygen.

[0015] [7] In another embodiment, a process for making thermally cross-linked, ethylenebased, rigid article comprises producing an ethylene-based polymer by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules and crosslinking the ethylene-based polymer with heat in the presence of oxygen to form the thermally cross-linked, ethylenebased, rigid article. Each of the one or more hydrocarbon-based molecules comprises three or more terminal alkene groups. The thermally cross-linked, ethylene-based, rigid article has a greater melt elongation relative to an ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

[0016] [8] Additional features and advantages will be set forth in the detailed description, which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows and the claims.

[0017] [9] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.

[0018] DETAILED DESCRIPTION

[0019]

[0010] Specific embodiments of the present application will now be described. The disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this 86130-WO-PCT / DOW 86130 WO

[0020] 3 disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0021]

[0011] DEFINITIONS

[0022]

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

[0023]

[0013] Ranges may be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0024]

[0014] The terms "comprising", "including", "having”, and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of’ excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of’ excludes any component, step or procedure, not specifically delineated or listed.

[0025]

[0015] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight.

[0026]

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

[0027]

[0017] The term “LDPE” may also be referred to as “high-pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), with the use of free-radical initiators, such as peroxides (see, for example, U.S. Patent No. 4,599,392, which is hereby incorporated by 86130-WO-PCT / DOW 86130 WO

[0028] 4 reference in its entirety). LDPE resins typically have a density in the range of 0.916 g / cm3to 0.930 g / cm3.

[0029]

[0018] The term "hydrocarbon-based molecules comprising three or more terminal alkene groups," (or interchangeably referred to as "hydrocarbon-based molecules") as used herein, refers to a chemical component that is a polymer chain composed of only carbon atoms and hydrogen atoms, the polymer chain being branched and having three or more terminal alkene groups.

[0030]

[0019] The term "mixture of hydrocarbon-based molecules," as used herein, refers to two or more hydrocarbon-based molecules, wherein at least two of the molecules differ in structure, property, and / or composition.

[0031]

[0020] The term “terminal double bond,” as used herein, refers to a double bond between two carbon atoms in a polymer chain, wherein one of the carbons in the double-bond is a =CH? group. Terminal double bonds are located at terminal ends of polymer chains and / or at branched ends of polymer chains.

[0032]

[0021] The term “thermally cross-linked, ethylene-based, rigid article,” as used herein, refers to a rigid article that has been thermally cross-linked in the presence of oxygen.

[0033]

[0022] The terms “crosslinking,” “thermal crosslinking,” and “thermal treatment,” as used herein, refer to crosslinking with heat in the presence of oxygen.

[0034]

[0023] EMBODIMENTS

[0035]

[0024] Embodiments of the present disclosure are directed to thermally cross-linked, ethylene-based, rigid articles comprising an ethylene-based polymer formed by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules.

[0036]

[0025] Ethylene-based Polymer

[0037]

[0026] The ethylene-based polymer is the polymerization reaction product of ethylene and one or more hydrocarbon-based molecules. Each hydrocarbon-based molecule comprises three or more terminal alkene groups.

[0038]

[0027] In embodiments, each of the hydrocarbon-based molecules (i.e., one or more of the hydrocarbon-based molecules) may comprise Structure I: 86130-WO-PCT / DOW 86130 WO

[0039] 5

[0040] Structure I

[0041]

[0028] In Structure I, R = H or OH n may be from 3 to 160, such as from 3 to 60, from 3 to 30, from 5 to 160, from 10 to 160, from 20 to 160, from 30 to 160, or from 40 to 160, from 5 to 100, or from 9 to 40; m may be from 0 to 50, such as from 0 to 30, from 1 to 50, from 1 to 40, from 1 to 30, from 1 to 20, from 2 to 20, from 2 to 10, or any subset thereof.

[0042]

[0029] In embodiments, each of the hydrocarbon-based molecules (i.e., one or more of the hydrocarbon-based molecules) may comprise Structure II:

[0043] T”

[0044]

[0030] In Structure II, R = H or OH, n may be from 3 to 160, and m may be from 0 to 50; x may be from 0 to 160, and y may be from 0 to 50. For example, n may be from 3 to 160, such as from 3 to 100, from 3 to 30, from 5 to 160, from 10 to 160, from 20 to 160, from 30 to 160, or from 40 to 160, from 5 to 100, or from 9 to 40; m may be from 0 to 50, such as from 0 to 30, from 1 to 50, from 1 to 40, from 1 to 30, from 1 to 20, from 2 to 20, from 2 to 10, or any subset thereof, x may be from 0 to 160, such as from 0 to 140, from 0 to 120, from 0 to 100, from 0 to 80, from 0 to 60, from 0 to 40, from 0 to 20, from 1 to 20, from 1 to 60, from 1 to 100, from 1 to 160, from 10 to 150, from 20 to 140, from 40 to 120, from 60 to 100, or any subset thereof, y may be from 0 to 40, from 0 to 30, from 0 to 20, from 0 to 10, from 1 to 50, from 5 to 50, from 10 to 60, from 20 to 50, from 30 to 50, from 40 to 50, from 10 to 40, or any subset thereof.

[0045]

[0031] The hydrocarbon-based molecules of Structure I, the hydrocarbon-based molecules of Structure II, and / or the overall mixture of hydrocarbon-based molecules may have a molecular weight distribution (MWD = Mw / Mn) from 1.2 to 20, such as from 1.2 to 10, from 1.2 to 5, from 1.2 to 3, from 1.3 to 20, from 1.4 to 20, from 1.5 to 20, from 2 to 20, from 5 to 20, from 10 to 20, from 2 to 18, from 6 to 16, from 8 to 14, or any subset thereof.

[0046]

[0032] In Structure I and Structure II, it should be understood that the hydrocarbon-based molecules may be random copolymers or block copolymers. The individual monomers may, but 86130-WO-PCT / DOW 86130 WO

[0047] 6 need not, be arranged in the same order as is shown in Structure I and Structure II. Any polymer which includes both the monomers shown in Structure I (and only those two monomers) is defined by Structure I. Any polymer which includes all four of the monomers shown in Structure II (and only those monomers) is defined by structure II, regardless of the order of the monomers.

[0048]

[0033] In embodiments, a mixture of hydrocarbon-based molecules having the Structure I and / or the Structure II, with differing molecular weights, may be used. The mixture of hydrocarbonbased molecules may comprise hydrocarbon-based molecules of Structure I, Structure II, or a combination thereof. Suitable hydrocarbon-based molecules include those described in detail in U.S. Patent Application Publication Number 2022 / 0017666, the entirety of which is incorporated by reference herein; and include polybutadienes available from Nippon Soda Co., Ltd under the names PB B-1000 (polybutadiene with a number average molecular weight (Mn) of 1200 and at least 85% 1,2-vinyl content), and Poly vest 110, available from Evonik Industries (polybutadiene with a number average molecular weight (Mn) of 2600 and only about 1% of 1,2-vinyl content), Polyvest EP MV, available from Evonik Industries (polybutadiene with a number average molecular weight (Mn) of 2000 and only about 61% of 1,2-vinyl content).

[0049]

[0034] In embodiments, the ethylene-based polymer may comprise, in polymerized form, from 95 wt% to 99.95 wt%, from 95 wt% to 99.90 wt%, from 96 wt% to 99.95 wt%, from 96 wt% to 99.90 wt%, from 97 wt% to 99.95 wt%, from 97 wt% to 99.90 wt%, from 98 wt% to 99.95 wt%, from 98 wt% to 99.90 wt%, or any subset thereof, of ethylene, and a reciprocal amount of the mixture of hydrocarbon-based molecules, or from 0.05 wt% to 5 wt%, from 0.05 wt% to 4 wt%, from 0.05 wt% to 3 wt%, from 0.05 wt% to 2 wt%, from 0.1 wt% to 5 wt%, from 0.1 wt% to 4 wt%, from 0.1 wt% to 3 wt%, from 0.1 wt% to 2 wt%, from 0.5 wt% to 5 wt%, from 0.5 wt% to 4 wt%, from 0.5 wt% to 3 wt%, from 0.5 wt% to 2 wt%, from 1 wt% to 5 wt%, from 1 wt% to 4 wt%, from 1 wt% to 3 wt%, from 1 wt% to 2 wt%, or any subset thereof. Weight percent is based on total weight of the ethylene-based polymer.

[0050]

[0035] In embodiments, the ethylene-based polymer may have a density from 0.910 g / cc to 0.940 g / cc, from 0.910 g / cc to 0.935 g / cc, from 0.910 g / cc to 0.930 g / cc, from 0.910 g / cc to 0.925 g / cc, from 0.914 g / cc to 0.940 g / cc, from 0.914 g / cc to 0.935 g / cc, from 0.914 g / cc to 0.930 g / cc, from 0.914 g / cc to 0.925 g / cc, or any subset thereof.

[0051]

[0036] In embodiments, the ethylene-based polymer may have a melt index (h), prior to thermal crosslinking, from 0.05 g / 10 min to 200 g / 10 min, from 0.05 g / 10 min to 150 g / 10 min, from 0.05 g / 10 min to 100 g / 10 min, from 0.05 g / 10 min to 50 g / 10 min, from 0.05 g / 10 min to 10 g / 10 min, 86130-WO-PCT / DOW 86130 WO

[0052] 7 from 0.10 g / 10 min to 200 g / 10 min, from 0.10 g / 10 min to 150 g / 10 min, from 0.10 g / 10 min to 100 g / 10 min, from 0.10 g / 10 min to 50 g / 10 min, from 0.10 g / 10 min to 10 g / 10 min, from 0.15 g / 10 min to 200 g / 10 min, from 0.15 g / 10 min to 150 g / 10 min, from 0.15 g / 10 min to 100 g / 10 min, from 0.15 g / 10 min to 50 g / 10 min, from 0.15 g / 10 min to 10 g / 10 min, from 0.25 g / 10 min to 200 g / 10 min, from 0.25 g / 10 min to 150 g / 10 min, from 0.25 g / 10 min to 100 g / 10 min, from 0.25 g / 10 min to 50 g / 10 min, from 0.25 g / 10 min to 10 g / 10 min, from 1 g / 10 min to 200 g / 10 min, from 1 g / 10 min to 150 g / 10 min, from 1 g / 10 min to 100 g / 10 min, from 1 g / 10 min to 50 g / 10 min, from 1 g / 10 min to 10 g / 10 min, from 5 g / 10 min to 200 g / 10 min, from 5 g / 10 min to 150 g / 10 min, from 5 g / 10 min to 100 g / 10 min, from 5 g / 10 min to 50 g / 10 min, from 5 g / 10 min to 10 g / 10 min, from 10 g / 10 min to 200 g / 10 min, from 10 g / 10 min to 150 g / 10 min, from 10 g / 10 min to 100 g / 10 min, from 10 g / 10 min to 50 g / 10 min, from 20 g / 10 min to 200 g / 10 min, from 20 g / 10 min to 150 g / 10 min, from 20 g / 10 min to 100 g / 10 min, from 20 g / 10 min to 50 g / 10 min, from 20 g / 10 min to 10 g / 10 min, from 30 g / 10 min to 200 g / 10 min, from 30 g / 10 min to 150 g / 10 min, from 30 g / 10 min to 100 g / 10 min, from 30 g / 10 min to 50 g / 10 min, from 30 g / 10 min to 10 g / 10 min, from 40 g / 10 min to 200 g / 10 min, from 40 g / 10 min to 150 g / 10 min, from 40 g / 10 min to 100 g / 10 min, from 40 g / 10 min to 50 g / 10 min, or any subset thereof.

[0053]

[0037] In embodiments, the ethylene-based polymer may have an alkenes content from

[0054] 0.05 / 1000 carbons to 3.0 / 1000 carbons, from 0.05 / 1000 carbons to 2.0 / 1000 carbons, from

[0055] 0.05 / 1000 carbons to 1.0 / 1000 carbons, from 0.15 / 1000 carbons to 3.0 / 1000 carbons, from

[0056] 0.15 / 1000 carbons to 2.0 / 1000 carbons, from 0.15 / 1000 carbons to 1.0 / 1000 carbons, from

[0057] 0.3 / 1000 carbons to 3.0 / 1000 carbons, from 0.3 / 1000 carbons to 2.0 / 1000 carbons, from

[0058] 0.3 / 1000 carbons to 1.0 / 1000 carbons, from 0.4 / 1000 carbons to 3.0 / 1000 carbons, from

[0059] 0.4 / 1000 carbons to 2.0 / 1000 carbons, from 0.4 / 1000 carbons to 1.0 / 1000 carbons, or any subset thereof.

[0060]

[0038] In embodiments, the ethylene-based polymer may be a low density polyethylene comprising, in polymerized form, ethylene monomer and the hydrocarbon-based molecules.

[0061]

[0039] The ethylene-based polymer is produced via in-reactor high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules. An exemplary process of making the ethylene-based polymer is described in International Patent Application Publication No. WO 2020 / 112873, which is incorporated herein by reference in its entirety. 86130-WO-PCT / DOW 86130 WO

[0062] 8

[0063]

[0040] In an embodiment, the ethylene-based polymer composition includes a blend component. The blend component is a polymer that does not include the mixture of the hydrocarbon-based molecules.

[0064]

[0041] In an embodiment, the blend component is an ethylene-based polymer that does not include the mixture of the hydrocarbon based molecules. Nonlimiting examples of suitable ethylene-based polymers include only ethylene based polymers like, for example, LDPE or HDPE, 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: (meth)acrylic acid, (meth)acrylic ester, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, mono esters of maleic acid, diesters of maleic acid, vinyl trialkoxysilane, vinyl trialkyl silane, and any combination thereof.

[0065]

[0042] Thermally Cross-linked, Ethylene-based, Rigid Articles

[0066]

[0043] A rigid article made from low density polyethylene is typically known for its flexibility and lower density compared to other types of polyethylene. Examples of rigid articles include, but not limited to, juice / honey containers, trays, lids, toys, and prosthetics.

[0067]

[0044] As described herein, the thermally cross-linked, ethylene-based, rigid article may have a greater melt elongation relative to the ethylene-based, rigid article not subjected thermal crosslinking in the presence of oxygen.

[0068]

[0045] In embodiments, the melt elongation of the of the thermally cross-linked, ethylenebased rigid article may be at least 15% greater, at least 30% greater, at least 45% greater, at least 60% greater, or even at least 75% greater than the ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

[0069]

[0046] In embodiments, the melt elongation of the thermally cross-linked, ethylene-based rigid article may be at least 10 mN, at least 25 mN, or even at least at least 50 mN greater than the ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

[0070]

[0047] In embodiments, the thermally cross-linked, ethylene-based, rigid article may have a melt elongation greater than or equal to 20 mN, greater than or equal to 40 mN, greater than or equal to 60 mN, greater than or equal to 80 mN, or even greater than or equal to 90 mN.

[0071]

[0048] While not wishing to be bound by theory, relatively greater melt elongation is indicative of enhanced mechanical properties, dimensional stability, and heat resistance. For example, higher melt elongation may indicate better molecular alignment and packing during 86130-WO-PCT / DOW 86130 WO

[0072] 9 the molding process, leading to improved mechanical properties, such as tensile strength, impact resistance, and rigidity. Moreover, rigid articles may need to maintain their shape and dimensions under various conditions. Increased melt elongation may help in achieving a better dimensional stability, reducing warping and deformation. Furthermore, rigid applications may rely on materials that can withstand higher temperatures without losing structural integrity. Increased melt elongation may contribute to better heat resistance, making the material more suitable for demanding environments.

[0073]

[0049] One skilled in the art should appreciate that melt index (I2) correlates to melt elongation, lower melt index (I2) corresponding to greater the melt elongation. However, while not wishing to be bound by theory, after a given thermal crosslinking, the melt index (I2) of the thermally cross-linked, ethylene-based, rigid article may begin to increase.

[0074]

[0050] The thermally cross-linked, ethylene-based, rigid article may comprise molded articles, such as blow molded, injection molded, or rotomolded articles.

[0075]

[0051] Process for Making Thermally Cross-linked, Ethylene-based, Rigid Articles

[0076]

[0052] In embodiments, a process for making a thermally cross-linked, ethylene-based, rigid article comprises producing an ethylene-based polymer and crosslinking the ethylene-based polymer with heat in the presence of oxygen to form the thermally cross-linked, ethylenebased, rigid article.

[0077]

[0053] The ethylene-based polymer may be produced by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules, as described herein.

[0078]

[0054] In embodiments, the crosslinking may comprise heating the ethylene-based polymer in the presence of oxygen. Heat and oxygen helps to promote crosslinking of available double bonds, thereby achieving the desired increase in melt elongation. In embodiments, the ethylene-based polymer may be formed into an article (e.g., compression molded) prior to thermal treatment. In embodiments, the crosslinking may occur in ambient air (i.e. 21% oxygen). In embodiments, the crosslinking may occur in little to no light, such as in a dark convection oven.

[0079]

[0055] The duration, temperature, and oxygen presence of the thermal treatment are dependent on each other. Additionally, these properties may help to achieve desired properties. 86130-WO-PCT / DOW 86130 WO

[0080] 10

[0081]

[0056] In embodiments, the crosslinking may occur at a temperature greater than or equal to 40 °C, greater or equal to 60 °C, greater or equal to 80 °C, or even greater or equal to 100 °C.

[0082]

[0057] In embodiments, the crosslinking may occur for a duration greater than or equal to 10 minutes, greater than or equal to 20 minutes, greater than or equal to 30 minutes, or even greater or equal to 60 min.

[0083]

[0058] In embodiments, the crosslinking does not include any additional reagents or catalysts, such as silane or peroxide crosslinker.

[0084]

[0059] TEST METHODS

[0085]

[0060] Melt elongation

[0086]

[0061] “Melt elongation,” as used herein, refers to the measure of the maximum tension applied to a polymer in a melted state, before the polymer breaks. Melt elongation is measured using a GOTTFERT D-Melt instrument (GOTTFERT Werkstoff-Prufmaschinen GmbH, SiemensstraBe 2, 74722 Buchen, Germany). A molten polymer strand is extruded 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)) using a weighted piston. The extrudate is pulled through 2 free spinning rollers onto a drum driven by a stepper motor which is ramped over a velocity range during the analysis. The force of the polymer strand pulling up on the force sensor platform mounted tension roller is recorded by the integrated control computer. From a curve fitting function of the acquired force data, the final reported melt elongation value is determined based on a constant velocity ratio of the polymer strand speed versus the die exit speed. Measurement results are reported as melt elongation in milli-Newton (mN). After the melt elongation measurement, the melt index measurement at ASTM conditions as described below is performed with the same charge.

[0087]

[0062] Melt Index

[0088]

[0063] The terms "melt index," or “h,” as used herein, refer to the measure of how easily a thermoplastic polymer flows when in a melted state. Melt index (H) 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).

[0089]

[0064] EXAMPLES 86130-WO-PCT / DOW 86130 WO

[0090] 11

[0091]

[0065] By way of example, and not limitation, some embodiments of the present disclosure will not be described in detail by the following examples.

[0092]

[0066] Materials

[0093]

[0067] Polybutadiene (B-1000) was supplied from Nippon Soda, Co.

[0094]

[0068] Polymerization

[0095]

[0069] Comparative Polymer CP

[0096]

[0070] For Comparative Polymer CP, the polymerization was carried out in a tubular reactor with three reaction zones. In each reaction zone, pressurized water was used for cooling and / or heating the reaction medium, by circulating water through the jacket of the reactor. The inlet-pressure was 222 MPa. Each reaction zone had one inlet and one outlet. Each inlet stream consisted of the outlet stream from the previous reaction zone and / or an added ethylene-rich feed stream. The non-converted ethylene and other gaseous components in the reactor outlet were recycled through a high-pressure recycle and a low-pressure recycle and were compressed and distributed through a booster and a primary and a hyper (secondary) compressors. Organic peroxides (tert-butyl peroxy-2-ethyl hexanoate and di-tert-butyl peroxide) were fed into each reaction zone. Propionaldehyde (PA) was used as a chain transfer agent (CTA) and it was present in each reaction zone inlet, originating from the low- pressure and high-pressure recycle flows. The fresh PA was added only to the second and third reactions zones in the ratio equivalent to 0.8 and 0.2, respectively. Fresh ethylene was directed towards the first reaction zone.

[0097]

[0071] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with the aid of the pressurized water. At the outlet of reaction zone 1, the reaction medium was further cooled by injecting cold, ethylene-rich feed and the reaction was re-initiated by feeding an organic peroxide system. This process was repeated at the end of the second reaction zone to enable further polymerization in the third reaction zone. The polymer was extruded and pelletized (about 30 pellets per gram), using a single screw extruder at a melt temperature around 230-250°C. The weight ratio of the ethylene-rich feed streams to the three reaction zones was 1.00:0.80:0.20. The internal process velocity was approximately 12.5, 9, and 11 m / sec, respectively, for the first, second, and third reaction zones.

[0098]

[0072] Inventive Polymer IP 86130-WO-PCT / DOW 86130 WO

[0099] 12

[0100]

[0073] For Inventive Polymer IP, the polymerization was carried out in a tubular reactor with three reaction zones, as discussed above with respect to Comparative Polymer CP. All process conditions were the same as the Comparative Polymer CP, except for Inventive Polymer IP, polybutadiene was added to the first zone.

[0101]

[0074] Compression Molding

[0102]

[0075] Inventive Article IA made from Inventive Polymer IP and Comparative Article CA made from Comparative Polymer CP, having varying thicknesses (0.5 mm, 1 mm, and 2 mm), were formed with a Dr. Collin P300P / M compression molding press. A PTFE coated stainless-steel mold including a cutout of 10 cm x 7 cm was used for all thicknesses. The polymer was spread out evenly in the cutout. To prevent sticking of sample material to the cover plates, PTFE glass fabric sheet (non-adhesive; thickness 0.13 mm) was used. The following temperature profile was applied: (1) 3 min at 130 °C with no pressure; (2) 1 min at 130 °C with high pressure (15 MPa); and (3) quench cool under high pressure (15 MPa) to room temperature.

[0103]

[0076] Thermal Crosslinking

[0104]

[0077] Inventive Articles IA1-3 and Comparative Articles CAI and CA2 were heated in a dark convection oven at 100 °C in ambient conditions for 24 hours. The oven was the UT 6060 model of Heraeus Instruments, with valve to control air flow fully open. The articles were introduced in an aluminum bucket and placed in the center of the oven. Note, that Inventive Pellets IP and Comparative Pellets CP were not subjected to thermal treatment.

[0105]

[0078] Referring now to Table 1, the melt elongation and the melt index (h) of the articles, after thermal treatment, and pellets are shown. The melt elongation increase (in percentage and change) and the melt index (h) change of Inventive Articles IA1-IA3 as compared to Inventive Pellets IP and Comparative Articles CA1-CA2 as compared to Comparative Pellets CP are also shown. 86130-WO-PCT / DOW 86130 WO

[0106] 13

[0107]

[0079] Table 1

[0108]

[0080] As shown in Table 1, Inventive Articles IA1-IA3, thermally cross-linked, ethylenebased, rigid articles, had greater melt elongations as compared Polymer Pellet EPl, ethylenebased, rigid articles not subjected to thermal crosslinking.

[0109]

[0081] As also shown in Table 1, Inventive Articles IA1-IA3, thermally cross-linked, ethylene-based, rigid articles, had greater melt elongation increases, in terms of change, as compared to Comparative Articles CAI and CA2, thermally cross-linked, ethylene-based, rigid articles lacking polybutadiene.

[0110]

[0082] While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.

Claims

86130-WO-PCT / DOW 86130 WOCLAIMS1. A thermally cross-linked, ethylene-based, rigid article comprising: an ethylene-based polymer formed by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules, each of the one or more hydrocarbon-based molecules comprising three or more terminal alkene groups, wherein the thermally cross-linked ethylene-based, rigid article, thermally cross-linked in the presence of oxygen, has a greater melt elongation relative to an ethylene-based, rigid article not subjected thermal crosslinking in the presence of oxygen.

2. The thermally cross-linked, ethylene-based, rigid article of claim 1, wherein each of the one or more hydrocarbon-based molecules comprise Structure I:Structure Iwherein R = H or OH, n is from 3 to 160, and m is from 0 to 50.

3. The thermally cross-linked, ethylene-based, rigid article of claims 1 or 2, wherein each of the one or more hydrocarbon-based molecules comprise Structure II:wherein R = H or OH, n is from 3 to 160, and m is from 0 to 50, x is from 0 to 160, and y is from 0 to 50.

4. The thermally cross-linked, ethylene-based, rigid article of claims 2 or 3, wherein a mixture of the one or more hydrocarbon-based molecules based on Structures I or II has a molecular weight distribution (MWD = Mw / Mn) from 1.2 to 20.86130-WO-PCT / DOW 86130 WO155. The thermally cross-linked, ethylene-based, rigid article of any one of claims 1-4, wherein the ethylene-based polymer has an alkenes content from 0.05 / 1000 carbons to 3.0 / 1000 carbons.

6. The thermally cross-linked, ethylene-based, rigid article of any one of claims 1-5, wherein the ethylene-based polymer is a low density polyethylene comprising, in polymerized form, ethylene monomer and the one or more hydrocarbon-based molecules.

7. The thermal cross-linked, ethylene-based, rigid article of any one of claims 1-6, wherein the melt elongation of the thermally cross-linked, ethylene-based rigid article is at least 15% greater than the ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

8. The thermally cross-linked, ethylene-based, rigid article of any one of claims 1-7, wherein the melt elongation of the thermally cross-linked, ethylene-based rigid article is at least 10 mN greater than the ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

9. The thermally cross-linked, ethylene-based, rigid article of any one of claims 1-8, wherein the melt elongation of the thermally cross-linked, ethylene-based rigid article is greater than or equal to 20 mN.

10. A process for making a thermally cross-linked, ethylene-based, rigid article comprising: producing an ethylene-based polymer by high pressure (greater than or equal to 100 MPa and less than or equal to 400 MPa), free-radical polymerization of ethylene and one or more hydrocarbon-based molecules, each of the one or more hydrocarbon-based molecules comprising three or more terminal alkene groups; and crosslinking the ethylene-based polymer with heat in the presence of oxygen to form the thermally cross-linked, ethylene-based, rigid article, wherein the thermally cross-linked, ethylene-based, rigid article has a greater melt elongation relative to an ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.86130-WO-PCT / DOW 86130 WO1611. The process of claim 10, wherein the crosslinking does not include silane or peroxide crosslinker.

12. The process of claim 10 or claim 11, wherein the crosslinking occurs at a temperature greater than or equal to 40 °C.

13. The process of any one of claims 10-12, wherein the crosslinking occurs for a duration greater than or equal to 1 hour.

14. The process of any one of claims 10-13, wherein the melt elongation of the thermally cross-linked, ethylene-based rigid article is at least 15% greater than the ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

15. The process of any one of claims 10-14, wherein the melt elongation of the thermally cross-linked, ethylene-based rigid article is at least 10 mN greater than the ethylene-based, rigid article not subjected to thermal crosslinking in the presence of oxygen.

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