Extruded foam manufactured using highly branched ethylene polymers

Abstract

The extruded foam comprises an ethylene-based polymer composition that includes polymerized ethylene-based monomers having hydrocarbon-based molecules having the following formula (I): where n is 3-160 and m is 0-50. [Case 1] JPEG2024500015000029.jpg17170

Description

[Technical Field]

[0001] The embodiments described herein generally relate to extruded polymer foams, and more specifically to extruded polymer foams produced using highly branched ethylene polymers. [Background technology]

[0002] Polymer foams, such as ethylene-based polymer foams, are used in numerous applications as thermal insulation materials and in packaged form. Low-density ethylene-based polymer foams are particularly desirable for use in specific applications because they possess good buffering properties, good dielectric strength and constancy, good water resistance and buoyancy, and good chemical resistance. [Overview of the Initiative]

[0003] As mentioned above, low-density ethylene-based polymer foams can be preferred polymer foams for certain applications. However, certain ethylene-based polymers have been found to function better as a base for foam structures than other ethylene-based polymers. For example, long-chain branched (LCB) ethylene-based polymers have been found to produce high melt strength polymers. However, low density (typically 0.200 g / cm³) 3 When producing extruded foams (less than ), the foaming window of known LCB ethylene-based polymers is relatively small, and it can be difficult to foam LCB ethylene-based polymers.

[0004] Therefore, there is a need for extruded polymer foam products made from ethylene polymers that have improved properties such as improved melt strength, optimized viscosity, and a broader molecular weight distribution compared to conventional extruded ethylene polymer foams. The embodiments of extruded ethylene polymer foams disclosed and described herein address these and other needs of conventional extruded polymer foams.

[0005] Embodiments of this disclosure satisfy these needs by providing, in various embodiments, an extruded foam containing an ethylene polymer comprising a polymerized ethylene monomer having a hydrocarbon molecule having the following formula:

[0006] [ka] In the formula, n is between 3 and 160, and m is between 0 and 50.

[0007] These embodiments and other embodiments are described in more detail in the following "Modes for Carrying Out the Invention". [Modes for carrying out the invention]

[0008] Herein, specific embodiments of the present disclosure are described. These embodiments are provided to ensure that the present disclosure is detailed and complete and to fully convey the scope of the claimed subject matter to those skilled in the art.

[0009] Unless otherwise stated, implied by context, or customary in the art, all parts and percentages are based on weight, all temperatures are in degrees Celsius, and all test methods are current as of the filing date of this disclosure.

[0010] The term "polymer" refers to polymer compounds prepared by polymerizing monomers, whether of the same or different types. Therefore, the general term "polymer" typically encompasses the term "homopolymer," which refers to polymers prepared from only one type of monomer, and the term "copolymer," which refers to polymers prepared from two or more different monomers. As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. Therefore, the general term "interpolymer" includes copolymers or polymers prepared from more than two different types of monomers, such as terpolymers.

[0011] "Ethylene polymer" or "ethylene polymer" or "polyethylene" means a polymer containing units derived from more than 50 mol% of ethylene monomers. This includes ethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene polymers known in the art include, but are not limited to, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), single-site catalyst linear low-density polyethylene (m-LLDPE) including both linear low-density resins and substantially linear low-density resins, medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0012] As used herein, 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.

[0013] As used herein, the term “ethylene / alpha-olefin copolymer” refers to a copolymer having more than 50 mole percent of polymerizable ethylene monomer (based on the total amount of polymerizable monomers) and at least one alpha-olefin.

[0014] 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 atom being bonded to two hydrogen atoms, which polymerize with other such chemical units to form ethylene-based polymer compositions.

[0015] 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 partially or completely homopolymerized or copolymerized in an autoclave or tubular reactor at a pressure exceeding 14,500 psi (100 MPa) using a free radical initiator such as a peroxide (see, for example, U.S. Patent No. 4,599,392, incorporated herein by reference). LDPE resins typically have a viscosity of 0.916 g / cm³. 3 ~0.940g / cm 3 It has a density within the range.

[0016] The term "LLDPE" includes resins produced using the Ziegler-Natta catalyst system, as well as resins produced using single-site catalysts, including but not limited to bismetallocene catalysts (sometimes referred to as "m-LLDPE"), phosphine imines, and bound structure catalysts, and resins produced using post-metallocene molecular catalysts, including but not limited to bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxy ether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene copolymers or homopolymers. LLDPE contains fewer long-chain branches than LDPE and includes substantially linear ethylene polymers as further defined in U.S. Patents 5,272,236, 5,278,272, 5,582,923, and 5,733,155; homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent 3,645,992; heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent 4,076,698; and blends thereof (such as those disclosed in U.S. Patents 3,914,342 or 5,854,045). LLDPE resins can be produced by gas-phase, solution-phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0017] 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 carbon atoms in the double bond is a =CH2 group. Terminal double bonds are located at the ends of polymer chains and / or at branched ends of polymer chains. As used herein, the term “internal alkene group” refers to a 1,2-disubstituted carbon-carbon double bond, where the carbon atoms are in a trans configuration (not a cis configuration). Internal alkene groups are located along the entire length of the polymer chain but not at the ends of the polymer chain or at branched ends along the polymer chain. Terminal and internal alkene groups are measured by infrared spectroscopy (IR).

[0018] As used herein, the term "alkene content" refers to the number of terminal alkene groups plus the number of internal alkene groups present in the polymer chain per 1000 carbon atoms. Alkene content is measured by infrared spectroscopy ("IR").

[0019] The term "HDPE" generally refers to single-site catalysts, including but not limited to Ziegler-Natta catalysts, chromium catalysts, or substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), geometrically constrained catalysts, phosphineimine catalysts, and polyvalent aryloxyether catalysts (typically referred to as bisphenylphenoxy), prepared at a concentration of approximately 0.935 g / cm³. 3 Super ~ maximum approx. 0.980g / cm 3 This refers to polyethylene having a certain density.

[0020] As used herein, the term "hydrocarbon molecule" refers to a chemical component having only carbon atoms and hydrogen atoms.

[0021] The terms “blend” and “polymer blend” refer to a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase-separated. Such a blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and any other method known in the art. A blend is not a laminate, but one or more layers of a laminate may contain a blend. Such a blend may be prepared as a dry blend, or formed in situ (e.g., in a reactor), as a molten blend, or using other techniques known to those skilled in the art.

[0022] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the presence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless otherwise stated. In contrast, the term “consisting essentially of” excludes any other components, processes, or procedures from the scope of any subsequent description, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically described or listed.

[0023] Ethylene-based polymers Ethylene polymer compositions used to produce ethylene polymer foams according to embodiments disclosed and described herein are described in more detail here. The ethylene polymer composition comprises a polymerization product of ethylene monomers and a mixture of hydrocarbon molecules having three or more terminal alkene groups.

[0024] In this embodiment, the ethylene polymer composition is formed by a process involving high pressure (over 100 MPa) and free radical polymerization. An ethylene monomer reacts with a mixture of hydrocarbon molecules having three or more terminal alkene groups to form the ethylene polymer composition. The polymerization process will be discussed in detail below.

[0025] Ethylene-based polymer compositions are polymerization reaction products of ethylene and hydrocarbon molecules having three or more terminal alkene groups. Hydrocarbon molecules have only carbon and hydrogen atoms and have three or more terminal alkene groups. As used herein, the term “hydrocarbon molecule containing three or more terminal alkene groups” (or interchangeably “hydrocarbon molecule”) refers to a chemical component that is a polymer chain composed only of carbon and hydrogen atoms, the polymer chain is branched, has three or more ends, and an alkene group (i.e., hydrocarbon double) bond is present at each end. As used herein, the term “mixture of hydrocarbon molecules” refers to two or more hydrocarbon molecules, at least two of which differ in structure, properties, and / or composition.

[0026] In embodiments, the number of terminal alkene groups present in each hydrocarbon molecule is 3, 5, 7, 8-17, or 18. In further embodiments, the number of terminal alkene groups present in each hydrocarbon molecule is 3-40, 5-40, 10-40, or 12-20. For example, a mixture of hydrocarbon molecules may include a first hydrocarbon molecule having 3 terminal alkene groups and a second hydrocarbon molecule having 12 terminal alkene groups.

[0027] In this embodiment, each hydrocarbon molecule in the mixture has structure I.

[0028] [ka] In the formula, n (number of terminal alkene groups) is 3 to 160, and m (number of internal alkene groups) is 0 to 50. In one or more embodiments, n is from 3, or 5, or 10, or 20, or 30, or 40, and m is from 0, or 10, or 20, or 40, or 50. In embodiments, n is from 3 to 160, or 5 to 100, or 9 to 40, and m is from 0 to 30, or 1 to 20, or 2 to 10.

[0029] In one embodiment, the mixture of hydrocarbon molecules consists of two or more hydrocarbon molecules having structure I.

[0030] [ka] In the formula, n is the number of terminal alkene groups, and m is the number of internal alkene groups. The average n content in a mixture of hydrocarbon molecules is between 9 and 40, and the average m content is between 1 and 10. The "average n content" is calculated by dividing the number-average molecular weight (Mn) of the hydrocarbon molecule by the weight-average molecular weight (Mw), and then multiplying by the fraction of terminal alkene groups. The "average m content" is calculated by dividing the number-average molecular weight (Mn) of the hydrocarbon molecule by the weight-average molecular weight (Mw), and then multiplying by the fraction of internal alkene groups.

[0031] In this embodiment, the mixture of hydrocarbon molecules has the following average n content and average m content (referred to as "n / m", see Structure I of each hydrocarbon molecule): 9-40 / 1-10, or 12-38 / 2-8, or 13-37 / 2-6, or 15-35 / 2-6, or 19 / 3, or 33 / 5.

[0032] In one embodiment, the mixture of hydrocarbon molecules based on structure I has a molecular weight distribution of 1.2 to 20. In one or more embodiments, the mixture of hydrocarbon molecules based on structure I has a molecular weight distribution of 1.2, 1.3, 1.4 to 2, or 5 to 10, or 20. In another embodiment, the mixture of hydrocarbon molecules based on structure I has a molecular weight distribution of 1.2 to 20, or 1.3 to 10, or 1.5 to 5.

[0033] In the embodiment, each hydrocarbon molecule has structure II,

[0034] [ka] In the equation, n is between 3 and 160, m is between 0 and 50, x is between 0 and 160, and y is between 0 and 50. In one or more embodiments, n is 3, or 5, or 10, or 20, or 30, or 40, or 50-60, or 70-80, or 90, or 100, or 110, or 120, or 130, or 140, or 150, or 160; m is 0, or 10, or 20-30, or 40, or 50; x is 0, or 1, or 5, or 10, or 20, or 30, or 40, or 50-60, or 70-80, or 90, or 100, or 110, or 120, or 130, or 140, or 150, or 160; and y is 0, or 1, or 10, or 20-30, or 40, or 50. In this embodiment, n is 3 to 160, or 5 to 150, or 9 to 140, or 9 to 100, or 9 to 50, or 9 to 30; m is 0 to 30, or 1 to 20, or 1 to 10; x is 0 to 160, or 1 to 50, or 1 to 20, or 1 to 10; and y is 0 to 50, or 1 to 20, or 1 to 10.

[0035] The hydrocarbon molecules of structure I and / or structure II described above will henceforth be interchangeably referred to as "branching agents."

[0036] Notation in Structure I and Structure II

[0037] [ka] This represents a cis-alkyl group or a trans-alkyl group with respect to the double bond.

[0038] In the embodiment, a mixture of hydrocarbon molecules having structure I and / or structure II having different molecular weights is used.

[0039] It is understood that the ethylene-based polymer composition may include (i) structure I only, (ii) structure II only, or (iii) a combination of structure I and structure II. According to some embodiments, as used herein, the term “ethylene-based polymer composition” refers to a polymer that is a reaction product of ethylene with structure I and / or structure II.

[0040] In embodiments, the ethylene-based polymer composition comprises, in polymer form, a mixture of 95% by weight, or 96% by weight, or 97% by weight, or 98% to 99% by weight, or 99.5% by weight, or 99.7% by weight, or 99.9% by weight, and an interacting amount of hydrocarbon molecules, or a mixture of 5.0% by weight, or 4.0% by weight, or 3.0% by weight, or 2.0% to 1.0% by weight, or 0.5% by weight, or 0.3% by weight, or 0.1% by weight, or 0.1% by weight, or 5.0% by weight, or 4.0% by weight, or 3.0% by weight, or 2.0% to 1.0% by weight, or 0.5% by weight, or 0.3 In one or more embodiments, the ethylene-based polymer composition contains ethylene in polymer form in an amount of 95.0% to 99.9% by weight, or 96% to 99.8% by weight, or 98% to 99.8% by weight, and a mixture of hydrocarbon molecules is present in an amount of 5.0% to 0.1% by weight, or 4.0% to 0.2% by weight, or 2.0% to 0.2% by weight.

[0041] According to one or more embodiments, the ethylene-based polymer composition has a density of 0.909 g / cc to 0.940 g / cc. In the embodiments, the ethylene-based polymer composition has a density of 0.909 g / cc, or 0.915 g / cc, or 0.920 g / cc to 0.930 g / cc, or 0.935 g / cc, or 0.940 g / cc. In the embodiments, the ethylene-based polymer composition has a density of 0.910 g / cc to 0.940 g / cc, or 0.915 g / cc to 0.935 g / cc, or 0.917 g / cc to 0.930 g / cc, or 0.917 g / cc to 0.926 g / cc.

[0042] In one embodiment, the ethylene-based polymer composition has a melt index (I2) of 0.10 g / 10 min to 200 g / 10 min. In one or more embodiments, the ethylene-based polymer composition has a melt index of 0.1 g / 10 min, or 0.5 g / 10 min, or 1.0 g / 10 min, or 3.0 g / 10 min, or 5.0 g / 10 min, or 10 g / 10 min, or 20 g / 10 min, or 30 g / 10 min, or 40 g / 10 min to 50 g / 10 min, or 60 g / 10 min, 70 g / 10 min, or 75 g / 10 min, or 80 g / 10 min, or 90 g / 10 min, or 100 g / 10 min. In this embodiment, the ethylene-based polymer composition has a melt index of 0.1 g / 10 min to 200 g / 10 min, or 0.1 g / 10 min to 100 g / 10 min, or 0.1 g / 10 min to 80 g / 10 min, or 0.1 g / 10 min to 20 g / 10 min.

[0043] In one embodiment, the ethylene-based polymer composition has a melt index (I2) of 0.1 g / 10 min to 8.0 g / 10 min.

[0044] In an embodiment, the ethylene-based polymer composition has an alkene content of from 0.05 / 1000 carbons, or 0.15 / 1000 carbons, or 0.3 / 1000 carbons, or 0.4 / 1000 carbons to 1.0 / 1000 carbons, or 2.0 / 1000 carbons, or up to 3.0 / 1000 carbons. In one or more embodiments, the ethylene-based polymer composition has an alkene content of from 0.05 / 1000 carbons to 3.0 / 1000 carbons, or from 0.05 / 1000 carbons to 1 / 1000 carbons, or from 0.08 / 1000 carbons to 1 / 1000 carbons.

[0045] In one embodiment, the ethylene-based polymer composition has a melt strength of 0.1 cN to 100 cN and a melt index of 0.1 g / 10 min to 100 g / 10 min.

[0046] In one embodiment, the ethylene-based polymer composition has a G’ value greater than C + Dlog(I2), where C is 185 Pa, D is -90 Pa / log(G / 10 min), I2 is the melt index of the ethylene-based polymer composition, Pa is Pascal (N / m 2 ), and log(g / 10 min) is the logarithm of the melt index of the ethylene-based polymer composition.

[0047] In an embodiment, the ethylene-based polymer composition has a GI200 value of 0 mm 2 / 24.6 cm 3 to 20 mm 2 / 24.6 cm 3 In one or more embodiments, the ethylene-based polymer composition has a GI200 value of 0 mm 2 / 24.6 cm 3 , or 0.05 mm 2 / 24.6 cm 3 , or 0.3 mm 2 / 24.6 cm 3 to 0.7 mm 2 / 24.6 cm 3 , 5 mm 2 / 24.6 cm 3 , or 20 mm 2 / 24.6 cm 3It has a GI200 value. In the embodiment, the ethylene polymer composition is 0 mm 2 24.6cm 3 ~20mm 2 24.6cm 3 , or 0.05 mm 2 24.6cm 3 ~5mm 2 24.6cm 3 , or 0.3mm 2 24.6cm 3 ~0.7mm 2 24.6cm 3 It has a GI200 value.

[0048] In one embodiment, the ethylene-based polymer composition has a density of 0.900 g / cc to 0.940 g / cc and a melt index of 0.1 g / 10 min to 200 g / 10 min. In one or more embodiments, the ethylene-based polymer composition has a density of 0.900 g / cc, or 0.910 g / cc, or 0.920 g / cc to 0.925 g / cc, or 0.930 g / cc, and a melt index of 0.1 g / 10 min, or 2.0 g / 10 min, or 3.0 g / 10 min to 9.0 g / 10 min, or 10 g / 10 min, or 100 g / 10 min. In the embodiment, the ethylene-based polymer composition has a density of 0.900 g / cc to 0.940 g / cc, or 0.910 g / cc to 0.930 g / cc, or 0.917 g / cc to 0.925 g / cc, and a melt index of 0.1 g / 10 min to 200 g / 10 min, or 0.1 g / 10 min to 100 g / 10 min, or 0.1 g / 10 min to 20.0 g / 10 min.

[0049] In one embodiment, the ethylene-based polymer composition has one, some, or all of the following properties: (i) Alkene content of 0.05 / 1000 carbon atoms, or 0.15 / 1000 carbon atoms, or 0.3 / 1000 carbon atoms, or 0.4 / 1000 carbon atoms to 1.0 / 1000 carbon atoms, or 2.0 / 1000 carbon atoms, or 3.0 / 1000 carbon atoms, and / or (ii) Melt strength of 0.1 cN to 100 cN, and melt index of 0.1 g / 10 min to 200 g / 10 min, and / or (iii) A G' value greater than or equal to C + D log(I²) (wherein C is 185 Pa and D is -90 Pa / log(g / 10 min)), and / or (iv) 0.05 mm 2 24.6cm 3 ~20mm 2 24.6cm 3 The GI200 value of, and / or (v) Density of 0.909 g / cc to 0.940 g / cc.

[0050] In one embodiment, the ethylene polymer composition has a relationship Mw(abs) to I2, where Mw(abs) is less than or equal to A + B(I2), (wherein A is 2.65 × 10) 5 The value is g / mol, and B is -8.00 × 10⁻⁶ -3 The formula is (g / mol) / (dg / min) (hereinafter, formula A), and the ethylene polymer composition has a G' to I2 relationship, where G' is (≧)C + Dlog(I2) or greater, C is 185 Pa, and D is -90 Pa / log(g / 10 min) (hereinafter, formula B). In other words, the ethylene polymer of the present invention has an Mw(abs) value smaller than the value from formula A and a G' value larger than the value from formula B.

[0051] In one embodiment, the ethylene polymer composition is low-density polyethylene (LDPE) containing a polymerized mixture of ethylene monomers and hydrocarbon molecules.

[0052] The ethylene-based polymer composition of the present invention is produced via high-pressure polymerization in a reactor. Without being bound by any particular theory, copolymerization of ethylene monomers and a mixture of hydrocarbon molecules is thought to occur through several scenarios. Two possible scenarios are (i) the reaction of the propagating polymer chain (PC) with the terminal alkene groups of the hydrocarbon molecules, followed by further propagation and termination, and (ii) the reaction of the propagating polymer chain (PC) with the internal alkene groups of the hydrocarbon molecules, followed by further propagation and termination.

[0053] Scenario (i)

[0054] [ka] The resulting ethylene-based polymer composition (structure III) has polyethylene chains (LDPE) directly bonded to the hydrocarbon molecule. A single or multiple terminal alkene groups may be attacked by propagation of polymer chains (PCs) leading to the single or multiple LDPEs bonded to the hydrocarbon molecule. In one embodiment, two or more terminal alkene groups undergo copolymerization while the remaining terminal alkene groups remain unreacted.

[0055] Scenario (ii)

[0056] [ka] The resulting ethylene-based polymer composition (structure IV) has two polyethylene chains bonded to the hydrocarbon molecule at internal alkene reaction sites (within the "m" section of the hydrocarbon molecule), which bond to form an LDPE unit. A single or multiple internal alkene groups may be attacked by propagation of polymer chains (PCs) that copolymerize with the hydrocarbon molecule to form one or more LDPE units. In one embodiment, two or more internal alkene groups are reacted while the remaining internal alkene groups remain unreacted. A single internal and / or terminal alkene group or multiple internal and / or external alkene groups may be attacked by propagation of polymer chains (PCs) that copolymerize with the hydrocarbon molecule to form one or more LDPE units. In one embodiment, two or more alkene groups are reacted while the remaining internal alkene groups remain unreacted.

[0057] The in-reactor reaction of the growing polymer chain at the terminal alkene group (Scenario I above), and the subsequent further propagation and termination of the final product, are different from post-reactoral terminal alkene grafting. Post-reactoral terminal alkene grafting is shown below.

[0058] [ka]

[0059] In the post-reaction terminal alkene grafting, the LDPE bonds to the hydrocarbon molecule at the reaction site of the terminal alkene. A separate molecule, usually another LDPE, reacts with the intermediate product to form the resulting ethylene-based polymer composition.

[0060] The final product of the in-reactor reaction of polymer chains grown with internal alkene groups, followed by further propagation and termination (scenario ii above), is different from post-reactor internal alkene grafting. Post-reactor internal alkene grafting is shown below.

[0061] [ka]

[0062] In the subsequent internal alkene grafting reaction, the LDPE bonds to the hydrocarbon molecule at the reaction site of the internal alkene group. A separate molecule, typically another LDPE, reacts with the intermediate product to form the resulting ethylene-based polymer composition.

[0063] In one embodiment, the ethylene-based polymer composition has structure III and / or structure IV as discussed above, and has one, some, or all of the following properties: (i) Alkene content of 0.05 / 1000 carbon atoms, or 0.15 / 1000 carbon atoms, or 0.3 / 1000 carbon atoms, or 0.4 / 1000 carbon atoms to 1.0 / 1000 carbon atoms, or 2.0 / 1000 carbon atoms, or 3.0 / 1000 carbon atoms, and / or (ii) Melt strength of 0.1 cN to 100 cN, and melt index of 0.1 g / 10 min to 200 g / 10 min, and / or (iii) A G' value greater than or equal to C + D log(I²) (wherein C is 185 Pa and D is -90 Pa / log(g / 10 min)), and / or (iv) 0mm 2 24.6cm 3 ~20mm 2 24.6cm 3 The GI200 value of, and / or (v) Densities of 0.909 g / cc to 0.940 g / cc, and melt index of 0.1 g / 10 min to 200 g / 10 min.

[0064] In one embodiment, the ethylene-based polymer composition contains 1.0% to 5.0% by weight of extractable hexane, based on the weight of the ethylene-based polymer composition. In one or more embodiments, the ethylene-based polymer composition contains extractable hexane in 1.0% by weight, or 1.1% by weight, or 1.5% to 2.6% by weight, or 3.5% by weight, or 5.0% by weight. In another embodiment, the ethylene-based polymer composition contains extractable hexane in 1.0% to 4.5% by weight, or 1.1% to 3.5% by weight, or 1.5% to 2.6% by weight.

[0065] In the embodiment, the ethylene-based polymer composition includes a blend component. The blend component is a polymer that does not contain a mixture of hydrocarbon molecules.

[0066] In the embodiment, the blend component is an ethylene-based polymer that does not contain a mixture of hydrocarbon molecules. Non-limiting examples of suitable ethylene-based polymers include ethylene / alpha-olefin copolymers, ethylene / C3-C8 alpha-olefin copolymers, ethylene / C4-C8 alpha-olefin copolymers, and copolymers of ethylene with 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, vinyl trialkoxysilanes, vinyl trialkylsilanes, and any combination thereof).

[0067] In the embodiments, the blend component is an ethylene-based polymer having a density of 0.890 g / cc, or 0.900 g / cc, or 0.905 g / cc, or 0.910 g / cc, or 0.915 g / cc, or 0.917 g / cc to 0.925 g / cc, or 0.930 g / cc, or 0.935 g / cc, or 0.940 g / cc, or 1.05 g / cc. In one or more embodiments, the ethylene-based polymer that is the blend component has a density of 0.900 g / cc to 0.940 g / cc, or 0.905 g / cc to 0.935 g / cc, or 0.910 g / cc to 0.930 g / cc, or 0.915 g / cc to 0.925 g / cc, or 0.917 g / cc to 0.925 g / cc.

[0068] According to the embodiment, the ethylene polymer has a viscosity of 6.0 cN to 30.0 cN, for example, 8.0 cN to 30.0 cN, 10.0 cN to 30.0 cN, 12.0 cN to 30.0 cN, 14.0 cN to 30.0 cN, 16.0 cN to 30.0 cN, 18.0 cN to 30.0 cN, 20.0 cN to 30.0 cN, 22.0 cN to 30.0 cN, 24.0 cN to 30.0 cN, 26.0 cN to 30.0 cN, 28.0 cN to 30.0 cN, 6.0 cN to 28.0 cN, 8.0 cN to 28.0 cN, 10.0 cN to 28.0 cN, 12.0 cN to 28.0 cN, and 14.0 c N~28.0cN, 16.0cN~28.0cN, 18.0cN~28.0cN, 20.0cN~28.0cN, 22.0cN~28.0 cN, 24.0cN~28.0cN, 26.0cN~28.0cN, 6.0cN~26.0cN, 8.0cN~26.0cN, 10.0c N~26.0cN, 12.0cN~26.0cN, 14.0cN~26.0cN, 16.0cN~26.0cN, 18.0cN~26.0 cN, 20.0cN~26.0cN, 22.0cN~26.0cN, 24.0cN~26.0cN, 6.0cN~24.0cN, 8.0cN ~24.0cN, 10.0cN~24.0cN, 12.0cN~24.0cN, 14.0cN~24.0cN, 16.0cN~24.0c N, 18.0cN~24.0cN, 20.0cN~24.0cN, 22.0cN~24.0cN, 6.0cN~22.0cN, 8.0cN ~22.0cN, 10.0cN~22.0cN, 12.0cN~22.0cN, 14.0cN~22.0cN, 16.0cN~22.0c N, 18.0cN~22.0cN, 20.0cN~22.0cN, 6.0cN~20.0cN, 8.0cN~20.0cN, 10.0cN~ 20.0cN, 12.0cN~20.0cN, 14.0cN~20.0cN, 16.0cN~20.0cN, 18.0cN~20.0cN , 6.0cN~18.0cN, 8.0cN~18.0cN, 10.0cN~18.0cN, 12.0cN~18.0cN, 14.0cN~ 18.0cN, 16.0cN~18.0cN, 6.0cN~16.0cN, 8.0cN~16.0cN, 10.0cN~16.0cN, 1 2.0cN~16.0cN, 14.0cN~16.0cN, 6.0cN~14.0cN, 8.0cN~14.0cN, 10.0cN~14.It has melt strengths of 0 cN, 12.0 cN to 14.0 cN, 6.0 cN to 12.0 cN, 8.0 cN to 12.0 cN, 10.0 cN to 12.0 cN, 6.0 cN to 10.0 cN, 8.0 cN to 10.0 cN, and 6.0 cN to 8.0 cN. According to one or more embodiments, the ethylene polymer has a viscosity of 11.0 cN to 14.0 cN, for example, 11.5 cN to 14.0 cN, 12.0 cN to 14.0 cN, 12.5 cN to 14.0 cN, 13.0 cN to 14.0 cN, 13.5 cN to 14.0 cN, 11.0 cN to 13.5 cN, 11.5 cN to 13.5 cN, 12.0 cN to 13.5 cN, 12.5 cN to 13.5 c It has a melting strength of N, 13.0 cN~13.5 cN, 11.0 cN~13.0 cN, 11.5 cN~13.0 cN, 12.0 cN~13.0 cN, 12.5 cN~13.0 cN, 11.0 cN~12.5 cN, 11.5 cN~12.5 cN, 12.0 cN~12.5 cN, 11.0 cN~12.0 cN, 11.5 cN~12.0 cN, or 11.0 cN~11.5 cN.

[0069] In the embodiment, the ethylene-based polymer is heated at 0.1 radians / second (rad / s) for 3,000 Pascal seconds (Pa). * s) ~30,000 Pa * s, for example, 5,000 Pa * s~30,000Pa * s, 8,000 Pa * s~30,000Pa * s, 10,000 Pa * s~30,000Pa * s, 13,000 Pa * s~30,000Pa * s, 15,000 Pa * s~30,000Pa * s, 18,000 Pa * s~30,000Pa * s, 20,000 Pa * s~30,000Pa * s, 23,000 Pa * s~30,000Pa * s, 25,000 Pa * s~30,000Pa * s, 28,000 Pa* s~30,000Pa * s、3,000Pa * s~28,000Pa * s、5,000Pa * s~28,000Pa * s、8,000Pa * s~28,000Pa * s、10,000Pa * s~28,000Pa * s、13,000Pa * s~28,000Pa * s、15,000Pa * s~28,000Pa * s、18,000Pa * s~28,000Pa * s、20,000Pa * s~28,000Pa * s、23,000Pa * s~28,000Pa * s、25,000Pa * s~28,000Pa * s、3,000Pa * s~25,000Pa * s、5,000Pa * s~25,000Pa * s、8,000Pa * s~25,000Pa * s、10,000Pa * s~25,000Pa * s、13,000Pa * s~25,000Pa * s、15,000Pa * s~25,000Pa * s、18,000Pa * s~25,000Pa * s、20,000Pa * s~25,000Pa * s、23,000Pa * s~25,000Pa * s、3,000Pa * s~23,000Pa * s、5,000Pa * s~23,000Pa * s、8,000Pa* s~23,000Pa * s、10,000Pa * s~23,000Pa * s、13,000Pa * s~23,000Pa * s、15,000Pa * s~23,000Pa * s、18,000Pa * s~23,000Pa * s、20,000Pa * s~23,000Pa * s、3,000Pa * s~20,000Pa * s、5,000Pa * s~20,000Pa * s、8,000Pa * s~20,000Pa * s、10,000Pa * s~20,000Pa * s、13,000Pa * s~20,000Pa * s、15,000Pa * s~20,000Pa * s、18,000Pa * s~20,000Pa * s、3,000Pa * s~18,000Pa * s、3,000Pa * s~18,000Pa * s、5,000Pa * s~18,000Pa * s、8,000Pa * s~18,000Pa * s、10,000Pa * s~18,000Pa * s、15,000Pa * s~18,000Pa * s、3,000Pa * s~15,000Pa * s、5,000Pa * s~15,000Pa * s、8,000Pa * s~15,000Pa * s、10,000Pa* s~15,000Pa * s, 13,000 Pa * s~15,000Pa * s, 3,000 Pa * s~13,000Pa * s, 5,000 Pa * s~13,000Pa * s, 8,000 Pa * s~13,000Pa * s, 10,000 Pa * s~13,000Pa * s, 3,000 Pa * s~10,000Pa * s, 5,000 Pa * s~10,000Pa * s, 8,000 Pa * s~10,000Pa * s, 3,000 Pa * s~8,000Pa * s, 5,000 Pa * s~8,000Pa * s, or 3,000 Pa * s~5,000Pa * Viscosity of s (V 0.1 ) has.

[0070] In the embodiment, the ethylene-based polymer is subjected to a pressure of 200 Pa at 100 rad / s. * s~800Pa * s, for example, 250 Pa * s~800Pa * s, 300Pa * s~800Pa * s, 350Pa * s~800Pa * s, 400Pa * s~800Pa * s, 450Pa * s~800Pa * s, 500Pa * s~800Pa * s, 550Pa * s~800Pa * s, 600Pa * s~800Pa * s, 650Pa* s~800Pa * s、700Pa * s~800Pa * s、750Pa * s~800Pa * s、200Pa * s~750Pa * s、250Pa * s~750Pa * s、300Pa * s~750Pa * s、350Pa * s~750Pa * s、400Pa * s~750Pa * s、450Pa * s~750Pa * s、500Pa * s~750Pa * s、550Pa * s~750Pa * s、600Pa * s~750Pa * s、650Pa * s~750Pa * s、700Pa * s~750Pa * s、200Pa * s~700Pa * s、250Pa * s~700Pa * s、300Pa * s~700Pa * s、350Pa * s~700Pa * s、400Pa * s~700Pa * s、450Pa * s~700Pa * s、500Pa * s~700Pa * s、550Pa * s~700Pa * s、600Pa * s~700Pa * s、650Pa * s~700Pa * s、200Pa * s~650Pa * s、250Pa* s~650Pa * s、300Pa * s~650Pa * s、350Pa * s~650Pa * s、400Pa * s~650Pa * s、450Pa * s~650Pa * s、500Pa * s~650Pa * s、550Pa * s~650Pa * s、600Pa * s~650Pa * s、200Pa * s~600Pa * s、250Pa * s~600Pa * s、300Pa * s~600Pa * s、350Pa * s~600Pa * s、400Pa * s~600Pa * s、450Pa * s~600Pa * s、500Pa * s~600Pa * s、550Pa * s~600Pa * s、200Pa * s~550Pa * s、250Pa * s~550Pa * s、300Pa * s~550Pa * s、350Pa * s~550Pa * s、400Pa * s~550Pa * s、450Pa * s~550Pa * s、500Pa * s~550Pa * s、200Pa * s~500Pa * s、250Pa * s~500Pa * s、300Pa* s~500Pa * s, 350Pa * s~500Pa * s, 400Pa * s~500Pa * s, 450Pa * s~500Pa * s, 200 Pa * s~450Pa * s, 250 Pa * s~450Pa * s, 300Pa * s~450Pa * s, 350Pa * s~450Pa * s, 400Pa * s~450Pa * s, 200 Pa * s~400Pa * s, 250 Pa * s~400Pa * s, 300Pa * s~400Pa * s, 350Pa * s~400Pa * s, 200 Pa * s~350Pa * s, 250 Pa * s~350Pa * s, 300Pa * s~350Pa * s, 200 Pa * s~300Pa * s, 250 Pa * s~300Pa * s, 200 Pa * s~250Pa * Viscosity of s (V 100 ) has.

[0071] In the embodiment, the ethylene-based polymer is 8.0 to 50.0, for example, 10.0 to 50.0, 15.0 to 50.0, 20.0 to 50.0, 25.0 to 50.0, 30.0 to 50.0, 35.0 to 50.0, 40.0 to 50.0, 45.0 to 50.0, 8.0 to 45.0, 10.0 to 45.0, 15.0 to 45.0, 20.0 to 45.0, 25.0 to 45.0, 30.0 to 45.0, 35.0 to 45.0, 40.0 to 45.0, 8.0 to 40.0, 10.0 to 40.0, 15.0 to 40.0, 20.0 to 40.0, 25.0 to Viscosity ratios (V) for 40.0, 30.0~40.0, 35.0~40.0, 8.0~35.0, 10.0~35.0, 15.0~35.0, 20.0~35.0, 25.0~35.0, 30.0~35.0, 8.0~30.0, 10.0~30.0, 15.0~30.0, 20.0~30.0, 25.0~30.0, 8.0~25.0, 10.0~25.0, 15.0~25.0, 20.0~25.0, 8.0~20.0, 10.0~20.0, 15.0~20.0, 8.0~15.0, 10.0~15.0, 8.0~10.0 0.1 / V 100 ) has.

[0072] In one or more embodiments, the ethylene-based polymer is measured by gel permeation chromatography (GPC) to a range of 3.0-25.0, e.g., 4.0-25.0, 6.0-25.0, 8.0-25.0, 10.0-25.0, 12.0-25.0, 14.0-25.0, 16.0-25.0, 18.0-25.0, 20.0-25.0, 22.0-25.0, 24.0-25.0, 3.0-24.0, 4.0-24.0, 6.0-24.0, 8.0-24.0, 10. 0-24.0, 12.0-24.0, 14.0-24.0, 16.0-24.0, 18.0-24.0, 20.0-24.0, 22.0-24.0, 3.0-22.0, 4.0-22.0, 6.0-22.0, 8.0-22.0, 10.0-22.0, 12.0-22.0, 14.0-22.0, 16.0-22.0, 18.0-22.0, 20.0-22.0, 3.0-20.0, 4.0-20.0, 6.0-20.0 8.0~20.0, 10.0~20.0, 12.0~20.0, 14.0~20.0, 16.0~20.0, 18.0~20.0, 3.0~18.0, 4.0~18.0, 6.0~18.0, 8.0~18.0, 10.0~18.0, 12.0~18.0, 14.0~18.0, 16.0~18.0, 3.0~16.0, 4.0~16.0, 6.0~16.0, 8.0~16.0, 10.0~16.0, 12.0~16 It has a molecular weight distribution (MWD) of 0, 14.0-16.0, 3.0-14.0, 4.0-14.0, 6.0-14.0, 8.0-14.0, 10.0-14.0, 12.0-14.0, 3.0-12.0, 4.0-12.0, 6.0-12.0, 8.0-12.0, 10.0-12.0, 3.0-10.0, 4.0-10.0, 6.0-10.0, 8.0-10.0, 3.0-8.0, 6.0-8.0, and 3.0-6.0.

[0073] In the embodiment, the blended components have a melt index (I2) of 0.1 to 200 g / 10 min.

[0074] In this embodiment, the blend component is high-density polyethylene (HDPE).

[0075] In this embodiment, the blend component is linear low-density polyethylene (LLDPE).

[0076] In this embodiment, the blend component is low-density polyethylene (LDPE).

[0077] In one or more embodiments, the blend component is an ethylene / alpha-olefin copolymer. In the embodiments, the alpha-olefin of the blend component is a C3-C8 alpha-olefin or a C4-C8 alpha-olefin.

[0078] In one or more embodiments, the blended component is one or more copolymers of ethylene and the following comonomers: acrylates, (meth)acrylic acid, (meth)acrylic acid esters, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, monoesters of maleic acid, diesters of maleic acid, vinyl trialkoxysilanes, vinyl trialkylsilanes, and any combination thereof.

[0079] Process for producing ethylene-based polymers A process for producing the ethylene-based polymer compositions disclosed and described herein is described herein. The process comprises reacting ethylene monomers in the presence of a mixture of hydrocarbon molecules having three or more terminal alkene groups in a polymerization reactor under free radical polymerization conditions and at a pressure exceeding 100 MPa. The process comprises forming the ethylene-based polymer composition.

[0080] In the embodiment, polymerization is carried out in a reactor configuration comprising at least one tubular reactor or at least one autoclave reactor.

[0081] In the embodiment, polymerization is carried out in a reactor configuration including at least one tubular reactor.

[0082] In the embodiment, polymerization is carried out in a reactor configuration including at least one autoclave reactor.

[0083] In the embodiment, the ethylene monomer is polymerized in the presence of at least 2 moles ppm (based on the total amount of monomer in the reaction feed) of an additive mixture of hydrocarbon molecules.

[0084] In this embodiment, the polymerization pressure is 100 MPa or higher.

[0085] In this embodiment, polymerization is carried out at at least one polymerization pressure between 100 MPa and 360 MPa.

[0086] In the embodiment, polymerization is carried out at at least one temperature between 100°C and 380°C.

[0087] According to one or more embodiments, highly branched ethylene polymer compositions are produced using a high-pressure free radical-initiated polymerization process. Two different types of high-pressure free radical-initiated polymerization processes are known. In the first process type, a stirred autoclave reactor having one or more reaction zones is used. The autoclave reactor typically has several injection points for initiators or monomer feeds, or both. In the second process type, a jacketed tube is used as the reactor, which has one or more reaction zones. Preferred but not limited reactor lengths may be 100 to 3000 meters (m), or 1000 to 2000 meters. The start of the reaction zone in both types of reactors is typically defined by a side injection of a reaction initiator, ethylene, chain transfer agent (or telomer), comonomer, or any combination thereof. The high-pressure process can be carried out in an autoclave reactor or tubular reactor having one or more reaction zones, or in a combination of autoclave reactors and tubular reactors, each containing one or more reaction zones.

[0088] In the embodiment, the initiator is injected before the reaction zone where free radical polymerization will be induced.

[0089] In one or more embodiments, a conventional chain transfer agent (CTA) is used to control the molecular weight.

[0090] In embodiments, one or more conventional CTAs are added to the polymerization process. Non-limiting examples of CTAs include propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMobil Chemical Co.), and isopropanol. In embodiments, the amount of CTA used in the process is 0.01% to 10% by weight of the total reaction mixture.

[0091] In the embodiment, the process includes a process recycling loop to improve conversion efficiency.

[0092] In one or more embodiments, polymerization is carried out in a tubular reactor as described in International Patent Application PCT / US12 / 059469 (International Publication No. 2013059042(A1)), filed on 10 October 2012. This patent application describes a multizone reactor that describes alternative locations for supplying fresh ethylene to control the ethylene-to-CTA ratio and thus control polymer properties. As described in International Patent Application PCT / US12 / 064284 (filed on 9 November 2012) (International Publication No. 2013078018(A2)), fresh ethylene monomer is added simultaneously at multiple locations to achieve a desired ratio of ethylene monomer to chain transfer. Similarly, the addition of fresh CTA is carefully selected to control polymer properties. To achieve a desired CTA-to-ethylene monomer ratio, fresh CTA is added simultaneously at multiple locations. Similarly, the addition points and amounts of fresh branching agent described in this application are controlled to control gel formation while maximizing the desired properties of improved melt strength and performance in the application in question. Fresh branching agent is added simultaneously at multiple locations to achieve the desired branching agent-to-ethylene monomer ratio. The use of branching agents and / or coupling agents to broaden the molecular weight distribution and increase the polymer's melt strength imposes further requirements on the distribution of CTA and branching agent along the reactor system to achieve the desired changes in product properties, minimizing or avoiding potential adverse effects such as gel formation, reactor fouling, and process instability, and minimizing the amount of branching agent used.

[0093] In the embodiment, polymerization takes place in at least one tubular reactor. In a multi-reactor system, an autoclave reactor precedes the tubular reactor. The point and amount of addition of fresh ethylene, fresh CTA, and fresh branching agent are controlled to achieve a desired ratio of CTA to ethylene monomer and branching agent to ethylene monomer in the feed to the reaction zone and / or in the reaction zone.

[0094] In the embodiment, the branching agent is supplied directly to the reaction zone via a compression step or directly to the feed to the reaction zone. The selection of the reaction and / or feed point to the reaction zone depends on several factors, including, but not limited to, the solubility of the polyene in pressurized ethylene and / or the solvent, the condensation of the polyene in pressurized ethylene, and / or fouling due to premature polymerization of the branching agent in a preheater used to heat the contents of the reactor before the injection of the initiator.

[0095] In this embodiment, the branching agent is supplied directly to the reaction zone or directly to the feedstock for the reaction zone.

[0096] In one or more embodiments, the branching agent is added at the entrance to the reaction zone, before or simultaneously with the addition of the free radical initiator. In another embodiment, the branching agent is added before the initiator to allow for good dispersion of the polyene.

[0097] In this embodiment, the branching agent is supplied only to reaction zone 1.

[0098] In this embodiment, a larger amount (by mass) of branching agent is added to reaction zone 1 compared to the amount (by mass) of polyene that is added to the subsequent reaction zone.

[0099] In one embodiment, the ethylene supplied to the first reaction zone is 10 to 100 percent of the total ethylene supplied for polymerization. In one or more embodiments, the ethylene supplied to the first reaction zone is 20 to 80 percent, further 25 to 75 percent, further 30 to 70 percent, and further 40 to 60 percent of the total ethylene supplied for polymerization.

[0100] In the embodiments, the process is carried out in a reactor configuration comprising at least one tubular reactor. In one or more embodiments, the maximum temperature in each reaction zone is 150°C to 360°C, further 170°C to 350°C, and further 200°C to 340°C.

[0101] In this embodiment, the polymerization pressure at the first inlet of the reactor is 100 MPa to 360 MPa, further 150 MPa to 340 MPa, and further 185 MPa to 320 MPa.

[0102] In one or more embodiments, the ratio of "concentration of CTA in the feed relative to reaction zone i" to "concentration of CTA in the feed added to reaction zone 1" is 1 or greater.

[0103] In this embodiment, the ratio of "concentration of CTA in the feed relative to reaction zone i" to "concentration of CTA in the feed added to reaction zone 1" is less than 1, further less than 0.8, further less than 0.6, and further less than 0.4.

[0104] In this embodiment, the number of reaction zones is in the range of 3 to 6.

[0105] Non-limiting examples of ethylene monomers used in the production of ethylene-based polymer compositions include purified ethylene obtained by removing polar components from a loop recycling stream or by using a reaction system configuration, so that only fresh ethylene is used to produce the polymer of the present invention. Further examples of ethylene monomers include ethylene monomers from the recycling loop.

[0106] In embodiments, the ethylene-based polymer composition comprises an ethylene monomer, a mixture of hydrocarbon molecules (structure I or structure II), and one or more comonomers, preferably one comonomer. Non-limiting examples of suitable comonomers include α-olefins, acrylates, carbon monoxide, methacrylates, (meth)acrylic acid, monoesters of maleic acid, diesters of maleic acid, anhydrides, vinyl acetate, vinyl propionate, vinyltrialkoxysilanes, and vinyltrialkylsilanes (each having 20 or fewer carbon atoms). The α-olefin comonomer has 3 to 10 carbon atoms, or alternatively, α-olefin comonomers have 4 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene.

[0107] In the embodiment, the ethylene polymer composition comprises an ethylene monomer and at least one hydrocarbon molecule (structure I or structure II) as the sole monomer unit.

[0108] In embodiments, a free radical initiator is used to produce the ethylene-based polymer composition of the present invention. Non-limiting examples of organic peroxides include cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals, t-butylperoxypivalates, di-t-butyl peroxides, t-butylperoxyacetates, t-butylperoxy-2-hexanoates, and combinations thereof. In one or more embodiments, these organic peroxy initiators are used in an amount of 0.001% to 0.2% by weight, based on the weight of the polymerizable monomer.

[0109] In the embodiment, the initiator is added to at least one reaction zone of polymerization, and the initiator has a "half-life temperature in 1 second" greater than 255°C or greater than 260°C.

[0110] In one or more embodiments, such initiators are used at a peak polymerization temperature of 320°C to 350°C.

[0111] In embodiments, the initiator comprises at least one peroxide group incorporated into the ring structure. Non-limiting examples of initiators include TRIGONOX301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane) and TRIGONOX311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane) (both available from Akzo Nobel), as well as HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane) available from United Initiators.

[0112] In one or more embodiments, the configuration of the tubular reactor includes 3 to 5 reaction zones, with fresh ethylene supplied to the front of the tubular reactor and recycled ethylene supplied to the sides of the tubular reactor. Fresh CTA is supplied to the sides of the tubular reactor. A mixture of hydrocarbon molecules is supplied to the front of the tubular reactor, and a mixture of hydrocarbon molecules is supplied directly after the tubular reactor has been preheated.

[0113] In embodiments, the ethylene-based polymer composition comprises a mixture of hydrocarbon molecules which are structural isomers of ethylene monomer and polybutadiene and / or have different terminal groups (structure III or structure IV), and one or more comonomers, preferably one comonomer. Non-limiting examples of suitable comonomers include α-olefins, acrylates, carbon monoxide, methacrylates, (meth)acrylic acid, monoesters of maleic acid, diesters of maleic acid, anhydrides, vinyl acetate, vinyl propionate, vinyltrialkoxysilanes, and vinyltrialkylsilanes (each having 20 or fewer carbon atoms). The α-olefin comonomer has 3 to 10 carbon atoms, or alternatively, α-olefin comonomers have 4 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene.

[0114] [ka] In the formula, m (the number of both cis-internal alkene groups and trans-internal alkene groups) is between 3 and 90, and the value of m is greater than the value of n (m>n). In further embodiments, m>n, m is between 3 and 90, and n is between 0 and 5, or m is between 6 and 60, and n is between 0 and 5, or m is between 9 and 50, and n is between 1 and 4.

[0115] [ka] In the formula, n is between 1 and 20, and m is between 10 and 90.

[0116] Ethylene-based polymer foam According to embodiments disclosed and described herein, the ethylene polymer compositions described above are combined with one or more foaming components to produce an ethylene polymer foaming composition, and therefore an ethylene polymer foam. Such foaming components include, but are not limited to, foaming agents, bubble nucleating agents, permeability modifiers or stability control agents, and other additives, which are described in more detail below.

[0117] According to one embodiment, the ethylene-based polymer foaming composition comprises an ethylene-based polymer composition and one or more of a foaming agent, a bubble nucleating agent, a permeability modifier or stability control agent, and other additives. According to one or more embodiments, the ethylene-based polymer composition may be present in amounts of 70.0% to 99.5% by weight, 75.0% to 98.0% by weight, 80.0% to 95.0% by weight, or 85.0% to 92.0% by weight, based on the total weight of the ethylene-based polymer foaming composition.According to the embodiment, the ethylene-based polymer composition is based on the total weight of the ethylene-based polymer foaming composition and is in an amount of 92.5% to 97.5% by weight, for example, 93.0% to 97.5% by weight, 93.5% to 97.5% by weight, 94.0% to 97.5% by weight, 94.5% to 97.5% by weight, 95.0% to 97.5% by weight, 95.5% to 97.5% by weight, 96.0% to 97.5% by weight, 96.5% to 97.5% by weight, 97.0% to 97.5% by weight, and 92.5% by weight. ~97.0wt%, 93.0wt%~97.0wt%, 93.5wt%~97.0wt%, 94.0wt%~97.0wt%, 94.5wt%~97.0wt%, 95.0wt%~97.0wt%, 95.5wt%~97.0wt%, 96.0 Weight% ~ 97.0%, 96.5% ~ 97.0%, 92.5% ~ 96.5%, 93.0% ~ 96.5%, 93.5% ~ 96.5%, 94.0% ~ 96.5%, 94.5% ~ 96.5%, 95 .0wt%~96.5wt%, 95.5wt%~96.5wt%, 96.0wt%~96.5wt%, 92.5wt%~96.0wt%, 93.0wt%~96.0wt%, 93.5wt%~96.0wt%, 94.0wt%~96.0wt% , 94.5% to 96.0% by weight, 95.0% to 96.0% by weight, 95.5% to 96.0% by weight, 92.5% to 95.5% by weight, 93.0% to 95.5% by weight, 93.5% to 95.5% by weight, 94.0% to 95.5% by weight It can exist in quantities of %, 94.5% by weight to 95.5% by weight, 95.0% by weight to 95.5% by weight, 92.5% by weight to 95.0% by weight, 93.0% by weight to 95.0% by weight, 93.5% by weight to 95.0% by weight, 94.0% by weight to 95.0% by weight, 94.5% by weight to 95.0% by weight, 92.5% by weight to 94.0% by weight, 93.0% by weight to 94.0% by weight, 93.5% by weight to 94.0% by weight, 92.5% by weight to 93.5% by weight, and 92.5% by weight to 93.0% by weight.

[0118] foaming agent Suitable blowing agents for use in forming the extruded ethylene-based polymer foaming compositions and foams of the embodiments are typically physical blowing agents, which are made of the same material as the escaping gas, for example, CO2, or chemical blowing agents that generate the escaping gas. In one or more embodiments, two or more physical or chemical blowing agents may be used, and both physical and chemical blowing agents may be used.

[0119] Examples of physical blowing agents used in embodiments include any naturally occurring atmospheric material, such as vapor at the temperature and pressure at which the foam emerges from the die used to form the extruded ethylene-based polymer foam. The physical blowing agent may be introduced as a gas, supercritical fluid, or liquid (i.e., injected into the polymer material). According to embodiments, the physical blowing agent may be introduced as a supercritical fluid or liquid, such as being introduced as a liquid. The physical blowing agent used depends on the properties required in the resulting foam article. Other factors considered when selecting a blowing agent include its toxicity, vapor pressure profile, ease of handling, and solubility in relation to the polymer material used. Non-flammable, non-toxic, and non-ozone-depleting blowing agents are preferred because they are easier to use, pose fewer environmental and safety concerns, and generally have lower solubility in thermoplastic polymers. A non-limiting example of a suitable physical blowing agent is C 1~6 Hydrocarbons, such as acetylene, propane, propene, n-butane, butene, butadiene, isobutane, isobutylene, cyclobutane, cyclopropane, ethane, methane, ethene, isomers of pentane, pentene, cyclopentane, pentene, pentadiene, hexane, cyclohexane, hexene, and hexadiene, C 1~5 Organic halogens, C 1~6 Alcohol, C 1~6 Ether, C 1~5 Ester, C 1~5Examples include amines, alcohols, ammonia, nitrogen, carbon dioxide, argon, water, neon, helium, and combinations thereof. In embodiments, the physical blowing agent is one or more of n-butane, isobutane, n-pentane, isopentane, neopentane, carbon dioxide, ethanol, and 1,1-difluoroethane (HFC-152a).

[0120] In embodiments, a chemical blowing agent is used to generate one or more physical blowing agents by thermal decomposition in the process. Examples of chemical blowing agents include (but are not limited to) azodicarbonamide, azodiisobutyronitrile, barium azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, and benzenesulfonhydrazide, 4,4-oxybenzenesulfonyl semicarbazide, as well as p-toluenesulfonyl semicarbazide, trihydrazinotriazine, and mixtures of citric acid and sodium bicarbonate. Examples of chemical blowing agents are various products sold under the trade name Safoam® (products of Reedy International; Reedy Chemical Foam).

[0121] The total amount of blowing agent used depends on conditions such as the extrusion process conditions during mixing, the blowing agent used, the composition of the extruded product, and the desired density of the foamed article. In this specification, the extruded product (foamed composition) is defined as comprising a blowing agent, an ethylene-based polymer composition, and any additives. A physical blowing agent (e.g., isobutane) may be present in amounts of 0.5 to 30% by weight, or 2 to 25% by weight, or 5 to 20% by weight, or 8 to 15% by weight, depending on the specific embodiment, based on the total weight of the ethylene-based polymer foamed composition. Approximately 1 to approximately 15 lb / ft 3 For a foam having a density of , the extruded material, in embodiments, contains about 18 to about 1% by weight of a blowing agent. In embodiments, 1% to 10% of a blowing agent may be used.

[0122] The blowing agent used in the embodiments includes isobutane. In one or more embodiments, the blowing agent includes isobutane in a total composition of 100% by weight or less, for example, less than 99% by weight, less than 98% by weight, less than 97% by weight, less than 96% by weight, or less than 97% by weight of isobutane. In embodiments, the blowing agent is a blend containing isobutane and CO2. In one or more embodiments, the blowing agent blend contains 5% to 95% by weight of isobutane and 5% to 95% by weight of CO2.

[0123] According to the embodiments disclosed and described herein, the blowing agent is added as an additive to the ethylene polymer composition, meaning that the blowing agent is not a component of the ethylene polymer composition. In a non-limiting example, if there are 100 grams of ethylene polymer composition and the additive includes 10% by weight of the blowing agent, then 10 grams of the blowing agent are added (100 grams × 10%). In another non-limiting example, if there are 150 grams of ethylene polymer composition and the additive includes 5% by weight of the blowing agent, then 7.5 grams of the blowing agent are added (150 grams × 5%).

[0124] According to the embodiment, the foaming agent may be added as an additive to the ethylene polymer composition such that it produces an amount of 1% to 5% by weight, for example, 2% to 5% by weight, 3% to 5% by weight, 4% to 5% by weight, 1% to 4% by weight, 2% to 4% by weight, 3% to 4% by weight, 1% to 3% by weight, 2% to 3% by weight, or 1% to 2% by weight, based on the total weight of the ethylene polymer foaming composition.

[0125] Bubble nucleating agent According to one or more embodiments, a nucleating agent or a combination of such agents may be used for advantages such as control of bubble formation and morphology. The nucleating agent or bubble size control agent may be any conventional or useful nucleating agent. The amount of nucleating agent used depends on the desired bubble size, the selected blowing agent blend, and the desired foam density. The nucleating agent is generally added in an amount of about 0.01 to about 20% by weight of the ethylene-based polymer composition.

[0126] Some intended nucleating agents include inorganic materials (in small particle form) such as clay, talc, silica, and diatomaceous earth. Other intended nucleating agents include organic nucleating agents that decompose or react at the heating temperature in the extruder to release gases such as carbon dioxide, water, and / or nitrogen. An example of an organic nucleating agent is a combination of an alkali metal salt of a polycarboxylic acid with a carbonate or bicarbonate. Some examples of alkali metal salts of polycarboxylic acids include, but are not limited to, monosodium salt of 2,3-dihydroxybutanediic acid (commonly referred to as sodium bitartrate), monopotassium salt of butanediic acid (commonly referred to as potassium hydrogen succinate), trisodium and tripotassium salts of 2-hydroxy-1,2,3-propanetricarboxylic acid (commonly referred to as sodium citrate and potassium citrate, respectively), and disodium salt of ethanediic acid (commonly referred to as sodium oxalate), or polycarboxylic acids such as 2-hydroxy-1,2,3-propanetricarboxylic acid. Some examples of carbonates or bicarbonates include, but are not limited to, sodium carbonate, sodium bicarbonate, potassium carbonate, and calcium carbonate.

[0127] Mixtures of different nucleating agents are intended to be included in foam articles according to the embodiments disclosed and described herein. Some more desirable nucleating agents include talc, crystalline silica, and stoichiometric mixtures of citric acid and sodium bicarbonate (stoichiometric mixtures having concentrations of 1 to 100 percent when the carrier is a suitable polymer such as polyethylene). Talc or other nucleating agents may be added in carrier or powder form.

[0128] According to the embodiment, the bubble nucleating agent is added as part of the ethylene-based polymer composition. For example, if 2% by weight of the bubble nucleating agent is present, the ethylene-based polymer composition may include, for example, 98% by weight of the ethylene-based polymer and 2% by weight of the bubble nucleating agent.

[0129] In the embodiment, the bubble nucleating agent is present in amounts of 0.1% to 2.0% by weight, based on the total weight of the ethylene-based polymer composition, for example, 0.5% to 2.0% by weight, 1.0% to 2.0% by weight, 1.5% to 2.0% by weight, 0.1% to 1.5% by weight, 0.5% to 1.5% by weight, 1.0% to 1.5% by weight, 0.1% to 1.0% by weight, 0.5% to 1.0% by weight, and 0.1% to 0.5% by weight.

[0130] According to one or more embodiments, the nucleating agent is an inorganic nucleating agent. In the embodiments, the inorganic nucleating agent is selected from the group consisting of clay, talc, silica, and diatomaceous earth.

[0131] Permeability modifier or stability control agent Gas permeators or stability control agents may be used in embodiments to help prevent or suppress foam collapse. Suitable stability control agents for use in embodiments include partial esters of long-chain fatty acids and polyols, saturated higher alkylamines, saturated higher fatty acid amides, as described in U.S. Patent No. 3,644,230 (which is incorporated herein by reference in whole), full esters of higher fatty acids, such as those described in U.S. Patent No. 4,214,054 (which is incorporated herein by reference in whole), and combinations thereof as described in U.S. Patent No. 5,750,584 (which is incorporated herein by reference in whole).

[0132] Desired fatty acid partial esters as stability control agents include members of a common class known as surfactants or surfactants. One exemplary class of surfactants is a partial ester of a fatty acid having 12 to 18 carbon atoms and a polyol having 3 to 6 hydroxyl groups. In embodiments, the partial ester of the polyol component of the stability control agent and the long-chain fatty acid is glycerol monostearate, glycerol distearate, or a mixture thereof. Other gas permeators or stability control agents may be used in the present invention to help prevent or suppress foam collapse.

[0133] According to the embodiments, the penetrating modifier or stability control agent is added as part of the ethylene polymer composition. For example, if 2% by weight of the penetrating modifier or stability control agent is present, the ethylene polymer composition may include, for example, 98% by weight of the ethylene polymer and 2% by weight of the penetrating modifier or stability control agent.

[0134] In the embodiments, the penetrating agent or stability control agent is present in amounts up to 2.0% by weight, for example, 0.2% to 2.0% by weight, 0.5% to 2.0% by weight, 1.0% to 2.0% by weight, 0.1% to 1.5% by weight, 0.5% to 1.5% by weight, 1.0% to 1.5% by weight, 0.1% to 1.0% by weight, 0.5% to 1.0% by weight, and 0.1% to 0.5% by weight.

[0135] In one or more embodiments, the foaming component comprises a penetrating modifier containing glycerol monostearate. According to the embodiments, the penetrating modifier containing glycerol monostearate is present in an amount of 1% to 5% by weight based on the total weight of the ethylene-based polymer composition.

[0136] additives According to the embodiment, fillers, colorants, antistatic agents, conductive additives, light and heat stabilizers, antioxidants, acid scavengers, flame retardants, processing aids, extrusion aids, and foaming additives can be used in the production of foamed articles. These optional components include, but are not limited to, calcium carbonate, titanium dioxide powder, polymer particles, hollow glass spheres, and polymer fibers such as polyolefin-based staple monofilaments.

[0137] For example, additives include wetting agents, flame retardants, surfactants, antistatic agents, anti-adhesion agents, wax-based dispersions, pigments, neutralizing agents, thickeners, compatibilizers, glossing agents, rheological modifiers, biocides, fungicides, reinforcing fibers, and other additives known to those skilled in the art. It should be understood that the embodiments of foam articles disclosed and described herein include, in other embodiments, additives that may be advantageous for product stability during and after the manufacturing process, as well as additive-free examples.

[0138] Suitable additives include fillers such as clay, talc, titanium dioxide, zeolite, organic or inorganic particles containing powdered metals, carbon fibers, silicon nitride fibers, steel wire or mesh, and organic or inorganic fibers containing nylon or polyester coatings, nanoparticles, and clay; tackifiers, oil extenders containing paraffin oil or naphthenic oil; and other natural and synthetic polymers, including other polymers according to embodiments of the present disclosure.

[0139] The foams described above may contain processing oils, plasticizers, and processing aids. Rubber processing oils with specific ASTM designations and paraffinic, naphthenic, or aromatic processing oils are all suitable for use. Generally, 0 to 150 parts, more preferably 0 to 100 parts, and most preferably 0 to 50 parts of processing oils, plasticizers, and / or processing aids are used per 100 parts of total polymer. Higher amounts of oil may tend to improve the processing of the resulting product at the expense of some physical properties. Additional processing aids include conventional waxes, fatty acid salts such as calcium stearate or zinc stearate, glycol-containing (poly)alcohols, glycol ether-containing (poly)alcohol ethers, (poly)esters containing (poly)glycol esters, and metal salts thereof, particularly Group 1 or Group 2 metal or zinc salt derivatives.

[0140] In conventional TPO, TPV, and TPE applications, carbon black is a useful additive for UV absorption and stabilization properties. Typical examples of carbon black include ASTM N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, and N991. These carbon blacks have iodine absorption in the range of 9–145 g / kg and an average pore volume in the range of 10–150 cm³ / 100 g. Generally, smaller particle sizes of carbon black are used where cost considerations allow. For many such applications, these polymers and their blends require little to no carbon black, thereby allowing for significant design flexibility, including or excluding alternative pigments.

[0141] In one or more embodiments, the foam may be impregnated with conductive carbon black by, for example, impregnating the foam with an aqueous dispersion of conductive carbon black containing a binder, or impregnating the foam with a styrene-butadiene binder containing conductive carbon, or wetting ethylene-based foam particles with a binder and conductive carbon black and then molding them into a desired configuration, or adding conductive carbon black to an ethylene-based prepolymer and then foaming it.

[0142] The compositions according to the embodiments disclosed herein may also contain anti-ozone agents or antioxidants known to those skilled in the art of rubber chemistry. The anti-ozone agent may be a physical protectant, such as a waxy material that comes to the surface and protects the component from oxygen or ozone, or it may be a chemical protectant that reacts with oxygen or ozone. Suitable chemical protectants include styrene-phenols, butylated octyl-phenols, butylated di(dimethylbenzyl)phenols, p-phenylenediamines, butylation reaction products of p-cresol and dicyclopentadiene (DCPD), polyphenol antioxidants, hydroquinone derivatives, quinolines, diphenylene antioxidants, thioester antioxidants, and blends thereof. Some representative product names for such products include WINGSTAY® S antioxidant, POLYSTAY® 100 antioxidant, POLYSTAY® 100AZ antioxidant, POLYSTAY® 200 antioxidant, WINGSTAY® L antioxidant, WINGSTAY® LHLS antioxidant, WINGSTAY® K antioxidant, WINGSTAY® 29 antioxidant, WINGSTAY® SN-1 antioxidant, and IRGANOX® antioxidant. In some applications, the antioxidants and anti-ozone agents used will be non-contaminating and non-mobile.

[0143] To provide additional stability against UV light, hindered amine light stabilizers (HALS) and UV absorbers may also be used. Suitable examples include TINUVIN® 123, TINUVIN® 144, TINUVIN® 622, TINUVIN® 765, TINUVIN® 770, and TINUVIN® 780, available from Ciba Specialty Chemicals, and CHEMISORB® T944, available from Cytex Plastics, Houston Tex., USA. Lewis acids may be included in addition to HALS compounds to achieve superior surface quality, as disclosed in U.S. Patent No. 6,051,681. Other embodiments may include, for example, heat stabilizers such as IRGANOX® PS 802 FL.

[0144] For some compositions, an additional mixing process may be used to pre-disperse heat stabilizers, antioxidants, anti-ozone agents, carbon black, UV absorbers, and / or light stabilizers to form a masterbatch, from which a polymer blend may then be formed.

[0145] In some embodiments, additives may also include processing aids such as stearate and stearic acid, fragrances, algae inhibitors, antimicrobial and antifungal agents, flame retardants and halogen-free flame retardants, and slip and adhesion inhibitors. Other embodiments may include PDMS to reduce the abrasion resistance of the polymer. The adhesion of the polymer may also be improved by the use of adhesion promoters, or by functionalization or coupling of the polymer with organosilanes, polychloroprene (neoprene), or other grafting agents.

[0146] According to the embodiment, the additive is added as part of the ethylene-based polymer composition. For example, if 2% by weight of the additive is present, the ethylene-based polymer composition may include, for example, 98% by weight of the ethylene-based polymer and 2% by weight of the additive.

[0147] The total amount of these additives is 0% to 10% by weight of the ethylene polymer composition, for example, based on the total weight of the ethylene polymer composition, 1% to 10% by weight, 2% to 10% by weight, 3% to 10% by weight, 4% to 10% by weight, 5% to 10% by weight, 6% to 10% by weight, 7% to 10% by weight, 8% to 10% by weight, 9% to 10% by weight, 0% to 9% by weight, 1% to 9% by weight, 2% to 9% by weight, 3% to 9% by weight, 4% to 9% by weight, 5% to 9% by weight, 6% to 9% by weight, 7% to 9% by weight, 8% to 9% by weight, 0% to 8% by weight, 1% to 8% by weight, 2% to 8% by weight, 3% to 8% by weight, 4% to 8% by weight, 5% to 8% by weight %, 6% to 8% by weight, 7% to 8% by weight, 0% to 7% by weight, 1% to 7% by weight, 2% to 7% by weight, 3% to 7% by weight, 4% to 7% by weight, 5% by weight 7% by weight, 6% to 7% by weight, 0% to 6% by weight, 1% to 6% by weight, 2% to 6% by weight, 3% to 6% by weight, 4% to 6% by weight, 5% to 6% by weight, 0% by weight It can exist in amounts of %~5% by weight, 1%~5% by weight, 2%~5% by weight, 3%~5% by weight, 4%~5% by weight, 0%~4% by weight, 1%~4% by weight, 2%~4% by weight, 3%~4% by weight, 0%~3% by weight, 1%~3% by weight, 2%~3% by weight, 0%~2% by weight, 1%~2% by weight, and 0%~1% by weight.

[0148] Foaming process The foam products (sheets, tubes, plates, etc.) according to the embodiments disclosed herein may include one or more layers as desired. The foam articles may be produced in any manner such that at least one foam layer is obtained. The foam layers described herein may be produced by pressurized melting methods such as extrusion. The extruder may be a tandem, single-screw extruder, twin-screw extruder, etc. The extruder may comprise a multilayer annular die, a flat film die and a feed block, such as the multilayer feed block disclosed in U.S. Patent No. 4,908,278, which is incorporated herein by reference in its entirety, and a multi-vane or multi-manifold die such as a three-vane die available from Cloeren, Orange, Tex. The foamy composition may also be produced by combining a chemical blowing agent and a polymer at a temperature below the decomposition temperature of the chemical blowing agent, and then foaming it. In some embodiments, the foam may be co-extruded with one or more barrier layers.

[0149] One method for producing the foam described herein is by using an extruder as described above. In this case, a foaming composition or mixture (such as an ethylene-based polymer, filler, or blowing agent, if desired) is extruded. As the foaming composition or mixture exits the extruder die and is exposed to pressure reduction, escaping gases nucleate, forming bubbles within the polymer to produce a foamed article. The foaming composition has a low density (typically 0.200 g / cm³) before exiting the extruder die. 3 In the case of extruded foams (below a certain temperature), they are cooled to the so-called "foaming temperature".

[0150] The foams formed by the methods described above can be crosslinked using peroxide curing agents and, in some embodiments, other curing agents that constitute a thermally activated curing system. The thermally activated curing system can include at least one based on peroxide or sulfur or epoxy. The thermally activated curing system can be combined with other components during processing to provide crosslinking of the foam. In some embodiments, the foam can be crosslinked using a radiation-induced curing system. Radiation-activated curing can include at least one of e-beam irradiation and gamma radiation. Radiation-activated curing can be carried out, in some embodiments, after the formation of the foam by the methods described above. In some embodiments, the foam can be crosslinked by silanization of one or more polymers before or during foam extrusion, followed by crosslinking of the resulting foam (generally by aging under wet conditions). A silanol condensation catalyst is generally incorporated into the foaming composition to effect silane crosslinking.

[0151] One advantage of using the ethylene-based polymers of the invention according to the embodiments disclosed and described herein is that they provide a high melt strength of conventional highly branched ethylene-based polymers (resulting from a relatively increased width of the molecular weight distribution, also known as the polydispersity index, due to efficient cooling of the foaming composition before exiting the extruder die), as well as a wide foaming temperature window. As used herein, a "foaming temperature window" is the temperature at which an ethylene-based polymer can be made into a foam. For example, at low temperatures, semi-crystalline polymers can experience a "freezing" where the crystalline structure still exists and they themselves would exist as solid (unexpanded) domains in the foam article. At high temperatures, the viscosity of the polymer is not suitable for foaming. It should be understood that it becomes difficult to control the temperature so that proper foaming is achieved if the foaming window is too narrow. According to embodiments, the ethylene-based polymers disclosed and described herein have a foaming temperature window of 101 °C to 120 °C, or 103 °C to 117 °C, or 105 °C to 115 °C, or 108 °C to 113 °C.

[0152] Those skilled in the art will understand that other methods for manufacturing the foams disclosed herein may also be used.

[0153] Properties of the Ethylene Polymer Foam The ethylene polymer foams according to the embodiments disclosed and described herein can be closed-cell foams, which means that 80% or more of the cells are independent, for example, more than 85% of the cells are independent, more than 90% of the cells are independent, or more than 95% of the cells are independent. The closed-cell content is measured by subtracting the continuous-cell content from 100% in any conventionally known manner. The continuous-cell content can be measured by any known method as described above.

[0154] In one or more embodiments, the density of the ethylene polymer foam is less than or equal to 0.20 grams per cubic centimeter (g / cc), for example, less than 0.18 g / cc, less than 0.16 g / cc, less than 0.14 g / cc, less than 0.12 g / cc, or less than 0.10 g / cc.According to one or more embodiments, the density of the ethylene-based foam is from 0.01 g / cc to 0.20 g / cc, for example, from 0.02 g / cc to 0.20 g / cc, from 0.04 g / cc to 0.20 g / cc, from 0.06 g / cc to 0.20 g / cc, from 0.08 g / cc to 0.20 g / cc, from 0.10 g / cc to 0.20 g / cc, from 0.12 g / cc to 0.20 g / cc, from 0.14 g / cc to 0.20 g / cc, from 0.16 g / cc to 0.20 g / cc, from 0.18 g / cc to 0.20 g / cc, from 0.01 g / cc to 0.18 g / cc, from 0.02 g / cc to 0.18 g / cc, from 0.04 g / cc to 0.18 g / cc, from 0.06 g / cc to 0.18 g / cc, from 0.08 g / cc to 0.18 g / cc, from 0.10 g / cc to 0.18 g / cc, from 0.12 g / cc to 0.18 g / cc, from 0.14 g / cc to 0.18 g / cc, from 0.01 g / cc to 0.16 g / cc, from 0.02 g / cc to 0.16 g / cc, from 0.04 g / cc to 0.16 g / cc, from 0.06 g / cc to 0.16 g / cc, from 0.08 g / cc to 0.16 g / cc, from 0.10 g / cc to 0.16 g / cc, from 0.12 g / cc to 0.16 g / cc, from 0.14 g / cc to 0.16 g / cc, from 0.01 g / cc to 0.14 g / cc, from 0.02 g / cc to 0.14 g / cc, from 0.04 g / cc to 0.14 g / cc, from 0.06 g / cc to 0.14 g / cc, from 0.08 g / cc to 0.14 g / cc, from 0.10 g / cc to 0.14 g / cc, from 0.12 g / cc to 0.14 g / cc, from 0.01 g / cc to 0.12 g / cc, from 0.02 g / cc to 0.12 g / cc, from 0.04 g / cc to 0.12 g / cc, from 0.06 g / cc to 0.12 g / cc, from 0.08 g / cc to 0.12 g / cc, from 0.10 g / cc to 0.12 g / cc, from 0.01 g / cc to 0.10 g / cc, from 0.02 g / cc to 0.10 g / cc, from 0.04 g / cc to 0.10 g / cc, from 0.06 g / cc to 0.10 g / cc, from 0.08 g / cc to 0.10 g / cc, from 0.01 g / cc to 0.08 g / cc, from 0.02 g / cc to 0.08 g / cc, from 0.04 g / cc to 0.08 g / cc, from 0.06 g / cc to 0.08 g / cc, from 0.01 g / cc to 0.06 g / cc, from 0.02 g / cc to 0.06 g / cc, from 0.04 g / cc to 0.06 g / cc, from 0.01 g / cc to 0.04 g / cc.

[0155] Test method Melt Index The melt index of the polymer sample is I2 (or I2) and I 10 (or I10) were measured according to ASTM D-1238 (Method B) at 190°C and loads of 2.16 kg and 10 kg, respectively. These values ​​were reported in units of g / 10 min. Fractions of polymer samples were determined by collecting the product polymer from the reactor producing that particular fraction or portion of the polymer composition. For example, the first polyethylene fraction could be recovered from the reactor producing the lower-density, higher-molecular-weight component of the polymer composition. The polymer solution was dried under vacuum before melt index measurement.

[0156] Melt strength As used herein, the term “melt strength” refers to a measure of the maximum tension that can be applied to a molten polymer before it breaks. Melt strength is measured at 190°C using Goettfert Rheotens 71.97 (Goettfert Inc., Rock Hill, SC). A Goettfert Rheotester 2000 capillary rheometer, 30 mm long and 2 mm in diameter, with a flat inlet angle (180 degrees), is fed into the molten sample (25–50 grams). The sample is fed into a barrel (L=300 mm, diameter=12 mm), compressed, and allowed to melt for 10 minutes, after which it is melted at a constant piston speed of 0.265 mm / sec (this is equivalent to 38.2 seconds at a given die diameter). -1 The extruded material is extruded at a rate equivalent to the wall shear rate. The extruded material passes through a wheel of rheoten located 100 mm below the die exit, at a rate of 2.4 millimeters per square second (mm / second). 2The strand is pulled downward by the wheel at an accelerating speed of ). The force acting on the wheel (measured in centinewtons, cN) is recorded as a function of the wheel's velocity (mm / sec). The sample is repeated at least twice until the two curves of force (cN) as a function of strand velocity (mm / sec) coincide. The curve showing the highest velocity at the time of strand severance is then reported. The melting strength is reported in cN as the plateau force before the strand is severed.

[0157] density Polymer samples for density measurement were prepared according to ASTM D4703. Within one hour of sample pressurization, measurements were performed according to ASTM D792, Method B.

[0158] The density of the foam was measured according to ASTM D-1622-88, and the result was kilograms per cubic meter (kg / m³) at 25°C. 3 ) or reported in grams per cubic centimeter (g / cc).

[0159] Gel permeation chromatography (GPC) The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column compartment to 150°C. The columns used were four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns and a 20 μm pre-column. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0160] The GPC column set was calibrated using 21 polystyrene standards with narrow molecular weight distributions ranging from 580 to 8,400,000, placed in six "cocktail" mixtures with at least a 10-fold gap between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared using 0.025 grams in 50 ml of solvent for molecular weights greater than 1,000,000, and 0.05 grams in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 degrees Celsius for 30 minutes with gentle stirring. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Formula 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0161]

number

[0162] A quintic polynomial was used to fit the respective polyethylene equivalent calibration points. A slight adjustment (approximately 0.375 to 0.445) was made for A to correct the column resolution and band expansion effect so that the linear homopolymer polyethylene standard material could be obtained at 120,000 Mw.

[0163] The total plate count of the GPC column set was performed using decane (prepared at 0.04 g in 50 ml of TCB and dissolved for 20 minutes with gentle agitation). Plate count (Equation 2) and symmetry (Equation 3) were measured using 200 microliter injections according to the following formulas.

[0164]

number

[0165]

Number

[0166] The sample was prepared semi-automatically using PolymerChar "Instrument Control" software, with 2 mg / ml as the target weight of the sample. Through the PolymerChar high-temperature autosampler, the solvent (containing 200 ppm of BHT) was added to a vial with a septum cap that had been sparged with nitrogen in advance. The sample was dissolved at 160 °C for 2 hours under "low-speed" shaking.

[0167] The calculations of Mn(GPC), Mw(GPC), and Mz(GPC) were based on the PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve of point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4 to 6.

[0168]

Number

[0169] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (apparent flow rate) for each sample by RV matching the respective decane peak in the sample (RV(FM sample)) with that of the decane peak in the narrow standard calibration (RV(FM calibrated)). It was then assumed that any temporal changes in the decane marker peak corresponded to a linear shift in the flow rate (effective flow rate) throughout the run. To facilitate the highest accuracy of RV measurement of the flow rate marker peak, a least-squares fitting routine was used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak location. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as shown in Equation 7. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne® software. An acceptable flow rate correction is one in which the effective flow rate should be within + / - 0.5% of the apparent flow rate. Effective flow rate = Apparent flow rate * (RV(FM calibrated) / RV(FM sample)) (Equation 7)

[0170] Triple Detector GPC (TDGPC) The chromatography system, analytical conditions, column set, column calibration, and conventional molecular weight moment calculations and distributions were performed according to the methods described in Gel Permeation Chromatography (GPC).

[0171] Regarding the determination of viscometer and light scattering detector offsets from an IR5 detector, a systematic method for determining multiple detector offsets was implemented 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, the results of triple detector logs (MW and IV) from a broad homopolymer polyethylene standard (Mw / Mn>3) were optimized for the results of narrow standard column calibration from a narrow standard calibration curve.

[0172] Absolute molecular weight data were obtained using PolymerChar GPCOne® software in a format 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 one of a suitable linear polyethylene homopolymer or a polyethylene standard material with a known weight-average molecular weight. The molecular weight calculated (using GPCOne®) was obtained using the light scattering constant and the refractive index concentration coefficient of 0.104, dn / dc, 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 linear standard materials having a molecular weight greater than approximately 50,000 g / mol. Viscometer calibration (determined using GPCOne®) can be achieved using the method described by the manufacturer, or alternatively, by using published values ​​of suitable linear standard materials such as Standard Reference Material (SRM) 1475a (available from the National Institute of Standards and Technology, NIST). The viscometer constant (obtained using GPCOne®) is calculated by relating the specific viscosity area (DV) and injected mass of the calibration standard to its intrinsic viscosity. The chromatographic concentration is assumed to be low enough to eliminate the second viral coefficient effect (concentration effect on molecular weight).

[0173] Absolute weight average molecular weight (MW) (Abs)The mass recovered from the mass constant and the mass detector (IR5) area are divided by the light scattering (LS) area-integrated chromatogram (factored by the light scattering constant) (using GPCOne®). The molecular weight and intrinsic viscosity response are linearly extrapolated at the edge of the chromatogram where the signal-to-noise ratio is low (using GPCOne®). The other respective moments are Mn (Abs) and Mz (Abs) This is calculated according to the following equations 8-9.

[0174]

number

[0175] GPCBR branch index obtained by triple detector GPC (3D-GPC) The gpcBR branching index is determined by first calibrating the light scattering, viscosity, and concentration detectors, as described above. The baseline is then subtracted from the light scattering, viscometer, and concentration chromatograms. Next, an integration window is set to ensure integration of the entire low molecular weight retention volume range of the light scattering and viscometer chromatograms that indicate the presence of detectable polymers from the infrared (IR5) chromatogram. Then, the Mark-Houwink constants for polyethylene and polystyrene are established using linear polyethylene standards. After obtaining the constants, a conventional calibration method using two linear references for polyethylene molecular weight and polyethylene intrinsic viscosity as functions of elution volume is constructed using the two values, as shown in equations (10) and (11).

[0176]

number

[0177] In 3D-GPC, the intrinsic viscosity of the sample is also obtained separately using equation (8). Area calculations in equations (5) and (8) provide higher accuracy because, as a whole sample area, they are far less affected by detector noise at the baseline and integration limit and variations caused by 3D-GPC settings. More importantly, the peak area calculation is unaffected by the detector volume offset. Similarly, the intrinsic viscosity (IV) of the sample can be obtained with high accuracy by the area method shown in equation (12).

[0178]

number

[0179] To determine the gpcBR branching index, the molecular weight of the sample is determined using the light scattering elution area of ​​the sample polymer. The intrinsic viscosity (IV or [η]) of the sample is determined using the elution area of ​​a viscosity detector for the sample polymer.

[0180] First, the molecular weight and intrinsic viscosity of a linear polyethylene standard sample, such as SRM1475a or its equivalent, are determined using conventional calibration ("conventional calibration, cc") for both molecular weight and intrinsic viscosity as functions of elution, according to equations (2) and (13).

[0181]

number

[0182]

number

[0183] All statistical values ​​with the subscript "cc" are determined using the respective elution amount, the corresponding conventional calibration described above, and the concentration (Ci). Values ​​without a subscript are measurements based on the mass detector, LALLS, and viscometer area. K PE The value of is adjusted iteratively 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 for polyethylene and 0.722 and -3.993 for polystyrene, respectively. These polyethylene coefficients were then entered into Equation 13.

[0184] Once the K and α values ​​are determined using the previously discussed procedure, the procedure is repeated using branched samples. The branched samples are analyzed using the final Mark-Houwink constant obtained from the linear reference as the optimal "cc" calibration value.

[0185] The interpretation of gpcBR is straightforward. For linear polymers, the values ​​measured by LS and viscometers are close to the conventional calibration standard, so the gpcBR calculated from equation (14) will be close to zero. For branched polymers, the measured polymer molecular weight will be higher than the calculated Mw and cc, and the calculated IVcc will be higher than the measured polymer IV, so gpcBR will be greater than zero, especially if the level of long-chain branching is high. In fact, the gpcBR value represents the fractional change in IV due to the molecular size contraction effect resulting from polymer branching. A gpcBR value of 0.5 or 2.0 means a molecular size contraction effect of IV at levels of 50% and 200%, respectively, relative to the equivalent weight of linear polymer molecules.

[0186] In these specific embodiments, the advantage of using gpcBR compared to conventional "g' index" and branching frequency calculations lies in the higher accuracy of gpcBR. All parameters used in determining the gpcBR index are obtained with high accuracy 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 gpcBR index determination. Fourier transform infrared analysis

[0187] The determination of the amount of terminal (vinyl) and internal (or trans) double bonds per 1000 carbon atoms is performed by Fourier transform infrared analysis (FTIR). Sample films used for FTIR analysis, approximately 250–300 microns thick, were compressed by pressing approximately 0.5 g of sample pellets in a Carver hydraulic press equipped with a heated platen set to 190°C. The levels of terminal and internal alkenes were measured following a procedure similar to that outlined in ASTM method D6248.

[0188] Dynamic rheological analysis Dynamic vibration shear measurements were performed on a TA Instruments strain-controlled rheometer ARES / ARES-G2 using a 25 mm diameter stainless steel parallel plate at a temperature of 190°C and 10% strain, yielding 0.1 rad s. -1 ~100 rad s -1 This procedure is performed over a range of rads to determine the melt flow characteristics of the ethylene-based polymer. V0.1 and V100 are 0.1 and 100 rads, respectively. -1 This is the viscosity, (V0.1 / V100 is a measure of shear viscosity characteristics).

[0189] DSC crystallinity Differential scanning calorimetry (DSC) can be used to measure the crystallinity of polymer samples at a given temperature over a wide range of temperatures. In this example, tests were performed using a TA Model Q1000 DSC (TA Instruments, New Castle, DE) equipped with an RCS (refrigerated cooling system) cooling accessory and an autosampler module. A nitrogen purge gas flow of 50 mL / min was used during the test. The resin was compressed into a 3 mm thick, 1 inch circular plaque at 350°C for 5 minutes under a pressure of 1500 psi in air. The sample was then removed from the compressor, placed on a counter, and allowed to cool to room temperature (approximately 25°C). 3–10 mg samples of the cooled material were cut into 6 mm diameter discs, weighed, placed in a lightweight aluminum pan, and crimped shut. The thermal behavior of the samples was then tested.

[0190] The thermal behavior of the sample was determined by raising and lowering the sample temperature and creating a response-to-temperature profile. To remove previous thermal history, the sample was first rapidly heated to 180°C and held isothermally for 3 minutes. Next, the sample was cooled to -40°C at a cooling rate of 10°C / min and held at -40°C for 3 minutes. Subsequently, the sample was heated to 150°C at a heating rate of 10°C / min. The cooling curve and the second heating curve were recorded. The measured value is the peak melting temperature (T m ), peak crystallization temperature (T c ), heat of fusion (H f (J / g) and the calculated crystallinity percentage of the polyethylene sample using the following formula 1.

[0191]

number

[0192] Heat of fusion (H f The peak melting temperature is reported from the second thermal curve. The peak crystallization temperature was measured from the cooling curve.

[0193] foam continuous cell content The open-cell content of the foam is measured in a specific gravity bottle according to ASTM D2856-94 and reported as a percentage from 0% to 100%. The open-cell content is also measured from the penetration height of the red water when the foam specimen is immersed in a beaker containing red water. The procedure is as follows: (a) Cut the foam sample into 100 mm long specimens; (b) Mark a line 50 mm from one end of each specimen; (c) Immerse the foam specimen in a beaker of red water, maintaining a constant length of 50 mm below the water surface for a constant time of 1 minute; (d) Remove the foam specimen from the water and wipe off any surface liquid; (e) Using a blade, slice the foam in half along its length; (f) Inspect the inner surface of the foam specimen exposed by slicing to determine how far the water penetrated upwards. A higher penetration height of the colored water indicates a higher open-cell content (as a qualitative measurement).

[0194] Number of bubbles and bubble size As used herein, the terms “bubble count” or “average bubble count” refer to the number of bubble wall intersections over a specified length. The bubble count of a foam composition is measured over a specified length by performing up to 10 measurements per foam specimen and calculating the average per specified length (i.e., “average bubble count”).

[0195] As used herein, the terms “bubble diameter” or “average bubble diameter” are measures of the dimensions of foam bubbles. Bubble diameter is determined by dividing the average number of bubbles by a given length and multiplying the result by 1.62, which is an established geometric factor for this purpose disclosed in Cellular Polymers, Vol, 21, No. 3, 165-194 (2002). Bubble diameter (i.e., average bubble diameter) is measured according to ASTM D3576-77 and reported in millimeters (mm). [Examples]

[0196] The following examples illustrate the features of the present disclosure, but are not intended to limit the scope of the present disclosure. The performance of embodiments of the multilayer films described herein was analyzed in the following experiments.

[0197] Ethylene-based polymers used in Examples 1-6 The ethylene-based polymers according to the embodiments disclosed and described herein were formed by the following process.

[0198] Polymerization was carried out in a tubular reactor having three reaction zones. Polybutadiene PB-1000 ("Additive A") was added to the first zone. In each reaction zone, pressurized water was used to cool and / or heat the reaction medium by circulating this water through the reactor jacket. The inlet pressure was 231 MPa, and the pressure drop across the entire tubular reactor system was approximately 30 MPa. Each reaction zone had one inlet and one outlet. Each inlet flow consisted of the outlet flow from the previous reaction zone and / or a feed flow rich in the added ethylene. Unconverted ethylene and other gaseous components at the reactor outlet were recycled by high-pressure and low-pressure recycling, and compressed and distributed by boosters, primary and hyper (secondary) compressors. Organic peroxides (tert-butylperoxy-2-ethylhexanoate and di-tert-butylperoxide) were supplied to each reaction zone. Propylene was used as a chain transfer agent (CTA) and was present at the entrances of each reaction zone, derived from the low-pressure and high-pressure recycling flows. Fresh ethylene was directed to the first reaction zone.

[0199] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with pressurized water. At the outlet of reaction zone 1, the reaction medium was further cooled by injecting a cold (55°C-60°C) ethylene-rich feed, and the reaction was restarted by supplying an organic peroxide system. This process was repeated at the end of reaction zone 2 to enable further polymerization in reaction zone 3. The polymer was extruded and pelletized (approximately 30 pellets per gram) using a single-screw extruder at a melting temperature of approximately 230°C-250°C. The weight ratio of the ethylene-rich feed stream to the three reaction zones was 1.00:0.60:0.40. The internal process rates were approximately 12.5, 9, and 11 m / sec in the first, second, and third reaction zones, respectively. The flow rate of additive A to zone 1 was 30.5 kg / hour. The ethylene conversion rate was 27.7%. Additional process conditions are provided in Table 1 below.

[0200] [Table 1]

[0201] [Table 2]

[0202] Comparative ethylene polymer used in Comparative Example 1 For Comparative Example 1, ethylene polymers were produced in a high-pressure free radical-initiated polymerization process using jacketed tubes as reactors, at a pressure exceeding 30,000 psig, with four reaction zones controlled at peak temperatures above 275°C. Each reaction zone used a mixture of varying amounts of free radical initiators, such as tert-butyl peroxypivalate (PIV), tert-butyl peroxy-2-ethylhexanoate (TPO), tert-butyl peroxyacetate (TPA), and di-tert butyl peroxide (DTBP), to control the reactor temperature. Each initiator was added independently to each reaction zone. Zone 1 was supplied with a PIV / TPO / TPA / DTBP mixture at a flow rate of 4.3 kg / hour; Zone 2 with a PIV / TPO / TPA / DTBP mixture at a flow rate of 6.9 kg / hour; Zone 3 with a PIV / TPO / TPA / DTBP mixture at a flow rate of 3.1 kg / hour; and Zone 4 with a PIV / TPO / TPA / DTBP mixture at a flow rate of 1.3 kg / hour. Propionaldehyde was used as a chain transfer agent (CTA). The melt index of the product was controlled by adjusting the concentration of CTA supplied to this process. The ethylene used for the production of ethylene-based polymers may be fresh ethylene without any recirculated loop ethylene, or a mixture of fresh ethylene feed and process recirculated loop flow.

[0203] The ethylene polymer used in Comparative Example 1 has a narrower MWD than the ethylene polymer used in Example 1 (as shown in Tables 2 and 3, 6.29 is compared to 9.01). In addition, the gpcBr of the ethylene polymer used in Example 1 is 2.63, while the gpcBr of the ethylene polymer used in Comparative Example 1 is only 2.0. Therefore, the ethylene polymer used in Example 1 has significantly more long-chain branches than the ethylene polymer used in Comparative Example 1.

[0204] [Table 3]

[0205] Table 4 below shows the differences in various properties between the ethylene-based polymers of Examples 1-6 and the ethylene-based polymer of Comparative Example 1.

[0206] [Table 4]

[0207] Preparation of ethylene polymer foam articles Ethylene-based polymer foams were prepared from the ethylene-based polymers described above using the following process.

[0208] Next, a foam was prepared using an ethylene-based polymer. The foam composition was prepared in a tandem extrusion system having a mixing extruder and a cooled extruder supplied by the mixing extruder. The mixing extruder was a co-rotating twin-screw extruder with a 34 mm diameter screw specially configured to ensure good mixing of the polymer composition and the blowing agent while forming the foamable composition. The mixing extruder was operated at a screw speed of 55 rpm and a set temperature of 180°C across all zones.

[0209] The cooled extruder was a single-screw extruder with a 40 mm diameter screw. The barrel and die temperatures of the cooled extruder were controlled between four zones using a separate oil heater. Zones 1 and 2 were operated at set temperatures of 129°C and 116°C, respectively. The set temperature of Zone 3 was the foaming temperature of the foamed composition. The cooled extruder was operated at a screw speed of 22 rpm. A 3 mm diameter rod die was attached to the end of the cooled extruder. The die temperature was maintained at 125°C.

[0210] The components of the polymer composition were dry-blended and then fed into the inlet of a mixing extruder through a solid metering feeder. Once complete melting of the polymer components was achieved, a blowing agent (isobutane) was injected into the mixing extruder at a rate of 20 L / D using a positive displacement pump (dual-piston HPLC pump). The polymer flow rate was maintained at 36 grams per minute (g / min). The residence time of the process from the addition of the solid components to the extruder inlet to the outlet die was 12 minutes.

[0211] As shown in Table 6, foams of different compositions and densities were produced under various processing conditions.

[0212] HS-E01 is a masterbatch of glycerol monostearate (GMS), a permeability modifier in LDPE carrier resins. It is available from Polyvel Inc. and has the following properties: GMS content 50%, alpha-mono content 90%, white color, melt index 320 g / 10 min, and softening point 70°C.

[0213] Mistron Vapor R is a talc with a median particle size of 2.2 μm and is available from Imerys Talc.

[0214] The component parts for each of Examples 1-6 (Ex1-Ex6) and Comparative Example 1 (CE1) are shown in Table 6 below.

[0215] [Table 5]

[0216] For each of CE1 and Ex1-Ex6, GMS was present in the polymer composition at an amount of 1% by weight, and isobutane was present in the foaming composition at an amount of 9% by weight.

[0217] Preferably, closed-cell foams with different densities were produced under various processing conditions, and samples were collected for characterization (Table 6).

[0218] In Comparative Example 1, "freezing" occurred at 112°C (1.2°C above the peak crystalline melting point of the polymer), as evidenced by the solid fragments in the foam composition passing through the die.

[0219] In the cases of Ex1 to Ex6, "freezing" did not occur at the low temperature of 108.3°C (0.5°C above the peak crystalline melting point of the polymer). Furthermore, this polymer exhibited a wide foaming temperature window (108°C to 113°C). These are useful attributes for extrusion foaming, minimizing scrap generation. In addition, thanks to the relatively high polydispersity index (PDI) and greater shear reduction of this polymer, less shear heating and better cooling are expected, preferably, in commercial (large-scale) extrusion foaming lines. Moreover, the relatively high melt strength of the ethylene-based polymer according to the embodiments disclosed and described herein is a desirable property for bubble stability during melt expansion (foaming). The present invention may provide the following embodiments. [1] Extruded foam, The ethylene polymer composition includes a polymerized ethylene monomer having a hydrocarbon molecule having the following formula: [ka] An extruded foam in which n is between 3 and 160 and m is between 0 and 50. [2] The extruded foam according to [1], wherein the extruded foam further comprises up to 2% by weight of a penetrating modifier based on the total weight of the ethylene polymer composition. [3] The extruded foam according to [1] above, wherein the permeability modifier comprises glycerol monostearate. [4] The extruded foam according to any one of the above [1] to [3], wherein the extruded foam contains an additive selected from a nucleating agent, an antistatic agent, a pigment, a filler, or a combination thereof. [5] The extruded foam according to any one of the above [1] to [4], wherein the extruded foam contains a nucleating agent. [6] The extruded foam according to [5], wherein the extruded foam contains 0.1% to 2.0% by weight of a nucleating agent based on the total weight of the ethylene polymer composition. [7] The extruded foam according to any one of the above [1] to [6], wherein the extruded foam has a density of 0.2 g / cc or less. [8] The extruded foam according to any one of the above [1] to [7], wherein the extruded foam has a density of 0.01 g / cc to 0.10 g / cc. [9] The extruded foam according to any one of the above [1] to [8], wherein the extruded foam is a closed-cell foam.

[10] The extruded foam according to any one of the above [1] to [8], wherein the extruded foam is produced using a blowing agent comprising one or more of isobutane, carbon dioxide, or a mixture thereof.

[11] The extruded foam according to

[10] above, wherein the blowing agent is isobutane.

[12] The extruded foam according to any one of the above [1] to

[11] , wherein the ethylene-based polymer has a molecular weight distribution of 3.0 to 25.0.

[13] The extruded foam according to any one of the above [1] to

[12] , wherein the ethylene-based polymer has a melt strength of 6.0 cN to 30.0 cN at a speed of 100 mm / second.

[14] The extruded foam according to any one of the above [1] to

[13] , wherein the ethylene-based polymer has a melt strength of 11.0 cN to 14.0 cN at a rate of 200 mm / second.

[15] The ethylene-based polymer has a viscosity ratio (V) of 8.0 to 50.0. 0.1 / V 100 An extruded foam according to any one of the above [1] to

[14] , having )

Claims

1. Extruded foam, The ethylene polymer composition includes a polymerized ethylene monomer having a hydrocarbon molecule having the following formula: 【Chemistry 1】 In the formula, n is between 3 and 160, and m is between 0 and 50. The ethylene-based polymer has a viscosity ratio of 15.0 to 50.0 (V 0.1 / V 100), The ethylene-based polymer, when measured by gel permeation chromatography, has a molecular weight distribution (Mw / Mn) of 8.0 to 25.

0. The ethylene-based polymer is an extruded foam having a melt strength of 10.0 cN to 30.0 cN.

2. The extruded foam according to claim 1, wherein the extruded foam further comprises up to 2% by weight of a permeable modifier based on the total weight of the ethylene-based polymer composition.

3. The extruded foam according to claim 1, wherein the permeable modifier comprises glycerol monostearate.

4. The extruded foam according to any one of claims 1 to 3, wherein the extruded foam contains an additive selected from a nucleating agent, an antistatic agent, a pigment, a filler, or a combination thereof.

5. The extruded foam according to any one of claims 1 to 4, wherein the extruded foam comprises a bubble nucleating agent.

6. The extruded foam according to claim 5, wherein the extruded foam contains 0.1% to 2.0% by weight of a nucleating agent based on the total weight of the ethylene-based polymer composition.

7. The extruded foam according to any one of claims 1 to 6, wherein the extruded foam has a density of 0.2 g / cc or less.

8. The extruded foam according to any one of claims 1 to 7, wherein the extruded foam has a density of 0.01 g / cc to 0.10 g / cc.

9. The extruded foam according to any one of claims 1 to 8, wherein the extruded foam is a closed-cell foam.

10. The extruded foam according to any one of claims 1 to 8, wherein the extruded foam is produced using a blowing agent comprising one or more of isobutane, carbon dioxide, or a mixture thereof.

11. The extruded foam according to claim 10, wherein the foaming agent is isobutane.

12. The extruded foam according to any one of claims 1 to 12, wherein the ethylene-based polymer has a melt strength of 6.0 cN to 30.0 cN at a speed of 100 mm / second.

13. The extruded foam according to any one of claims 1 to 13, wherein the ethylene-based polymer has a melt strength of 11.0 cN to 14.0 cN at a speed of 200 mm / second.

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