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    • 专利摘要:
    POLYMER BASED ON ETHYLENE, COMPOSITION AND ARTICLE. The invention provides an ethylene-based polymer comprising the following properties: (A) MWDconv from 7 to 10; and (B) "Normalized LSF" greater than or equal to 9.5.
    公开号:BR112013014809B1
    申请号:R112013014809-8
    申请日:2011-12-02
    公开日:2020-10-27
    发明作者:Teresa Karjala；Lori L Kardos；Wallace W. Yau；Jose Ortega
    申请人:Dow Global Technologies Llc.；
    IPC主号:
    专利说明:

    History of the invention
    [0001] There are many types of polyethylene manufactured and sold today. In particular, two types are manufactured by several suppliers and sold in large quantities. These two types are: linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), produced in the high pressure process by free radical chemistry. However, there is a need for new ethylene-based polymers that can be mixed with other polymers, such as LLDPE, to be used to form films with good optical properties, and that provide increased production rates in expanded film lines.
    [0002] US publication No. 2008/0125553 discloses an ethylene homopolymer or copolymer characterized by having long chain branching and a molecular weight distribution, Mw / Mn, and a GPC-LALLS CDF, which satisfies the following relationship: y = 0, 0663x - 0, 015, where y = GPC-LALLS CDF, ex = Mw / Mn measured by conventional GPC. A line drawn from where the LS chromatograms intersects at a molecular weight of 350,000 and a molecular weight of 1,150,000 has a positive slope. Preferably, the polymer has a melt index between 0.15 and 2000 g / 10 min and has long chain branching. In addition, the invention relates to a polymerization process, initiated via free radicals comprising reacting ethylene, and optionally one or more comonomers, at a high pressure, conveniently between 13,000 psig and 100,000 psig, and at reactor temperatures of 115- 400 ° C, preferably 125-400 ° C, more preferably 140-350 ° C, especially 165-320 ° C, in a reactor system comprising at least one tubular reactor and at least one autoclave reactor. The monomers fed into the reactors are divided into multiple monomer feed streams, and where at least one feed stream in the tubular reactor essentially consists of unreacted monomer.
    [0003] US patent No. 6,407,191 discloses an ethylene homopolymer or copolymer having a density between 0.923 and 0.935 g / cm3, a molecular weight distribution (Mw / Mn) between 3 and 10, and comprising 0 , 10 to 0.50 weight percent of units derived from a compound containing carbonyl group, based on the total weight of homopolymer or copolymer. In addition, the invention relates to a polymerization process, initiated via free radicals for the preparation of medium density ethylene copolymers or polymers comprising reacting ethylene, and optionally, one or more comonomers at a high pressure, conveniently between 1600 and 4000 kg / cm2, and at temperatures of about 150-330 ° C, in a reactor system consisting of at least one autoclave reactor, or a combination of tubular reactors and autoclaves, in the presence of initiators via free radicals and a compound containing carbonyl group. The invention also relates to chain transfer agents "containing carbonyl group" to improve polymer processing and performance properties in flat die applications and extrusion processes.
    [0004] US Patent No. 5,741,861 discloses a resin composition containing 50 to 99 weight percent of component A, which is a copolymer of ethylene and α-olefin, and 1 to 50 weight percent of component B, which is a high pressure low density polyethylene. Component A has the following properties: (a) melt flow rate (MFR) of 2 to 30 g / 10 min, (b) a density of no more than 0.935 g / cm3, and (c) a single peak of elution volume, indicated by an elution curve obtained by fractionation by elution with temperature gradient; the peak corresponding to a temperature within the range of 20 ° C to 85 ° C, and the elution curve satisfying a ratio in which the H / W ratio is not less than one, when H represents the height of the peak, and W represents the elution curve width at half the height of H. Component B has the following properties: (a ') a melt flow rate of 0.1 to 20 g / 10 min, (b') a density of 0m915 at 0.93 g / cm3, (c ') a memory effect (ME) of not less than 1.6, and (d') melt tension (MT) of not less than 1.5 g. The resin composition is used as a laminated material, and is reported to have improved workability ("workability"), and excellent properties with respect to low temperature thermal sealing ability, thermal sealing resistance and hot tackiness. .
    [0005] Low density polyethylene and additional mixtures are disclosed in the following documents: US patent No. 4,511,609, US patent No. 4,705,829, US publication No. 2008/0038533, JP61-241339 (Abstract), JP2005-232227 (Abstract), and in international publications No. WO2010 / 144784 and W02011 / 019563.
    [0006] As discussed above, there is a need for new ethylene-based polymers that can be mixed with other polymers, such as LLDPE, to be used to form films with good optical properties, and that provide increased production rates in film lines expanded. These needs were met by the following inventions. Summary of the invention
    [0007] The invention provides an ethylene-based polymer comprising the following properties: (A) MWDconv from 7 to 10; (B) "Standardized LSF" greater than or equal to 9.5. Brief description of the drawings
    [0008] Figure 1 shows a LS (light scattering) -GPC profile of a comparative LDPE;
    [0009] Figure 2 shows an LS (light scattering) -GPC profile of an inventive LDPE;
    [00010] Figure 3 shows a production system of high pressure low density polyethylene, double recycling, partially closed loop to produce Examples 1-6;
    [00011] Figure 4 shows a block diagram of the process reagent system used to produce Comparative Example 20;
    [00012] Figure 5 shows the temperature profile in the process reagent system for Example 2; and
    [00013] Figure 6 shows the temperature profile in the process reagent system for Comparative Example 20. Detailed Description
    [00014] The invention provides an ethylene-based polymer comprising the following properties: (A) MWDconv from 7 to 10; and (B) "Normalized LSF" greater than or equal to 9.5, preferably greater than or equal to 10.
    [00015] The ethylene-based polymer can comprise a combination of two or more embodiments described herein.
    [00016] In an embodiment, the ethylene-based polymer further comprises (C) a melting index greater than or equal to 1.0 g / 10 min, preferably greater than or equal to 1.3 g / 10 min, more preferably greater or equal to 1.5 g / 10 min.
    [00017] In an incorporation, MWDconv is greater than or equal to 7.2 or greater than or equal to 7.5.
    [00018] In an embodiment, the ethylene-based polymer has a melting index of 1 to 50 g / 10 min, or 1 to 20 g / 10 min, or 1 to 10 g / 10 min, or 1, 5 to 3 g / 10 min.
    [00019] In an incorporation, the ethylene-based polymer is formed in a high pressure polymerization process (P greater than 100 MPa).
    [00020] In an incorporation, the ethylene-based polymer has 7 to 20 MWDconv.
    [00021] In an embodiment, the ethylene-based polymer is a low density polyethylene (LDPE).
    [00022] In an embodiment, the ethylene-based polymer has> 0.1 amyl branch per 1000 carbon atoms, or> 0.5 amyl branch per 1000 carbon atoms, or> 1 amyl branch per 1000 carbon atoms.
    [00023] In an embodiment, the ethylene-based polymer has a density of 0.90 to 0.95 g / cm3, preferably 0.915 to 0.935 g / cm3.
    [00024] In an embodiment, the ethylene-based polymer has a melt strength greater than or equal to 5 cN, or greater than or equal to 6 cN, or greater than or equal to 6.5 cN.
    [00025] In an embodiment, the ethylene-based polymer has a melt strength of 5 to 15 cN.
    [00026] In an incorporation, the ethylene-based polymer has a rheology ratio (V0, l / V100), at 190 ° C, greater than or equal to 18, or greater than or equal to 19.
    [00027] In an incorporation, the ethylene-based polymer has a rheology ratio (V0, l / V100), at 190 ° C, from 10 to 25, or from 10 to 20.
    [00028] In an incorporation, the ethylene-based polymer has a delta tangent (tg δ) (measured at 0.1 rad / s) less than or equal to 5, or less than or equal to 4.5.
    [00029] An inventive polymer can comprise a combination of two or more embodiments described herein.
    [00030] The invention also provides a composition comprising an inventive ethylene-based polymer.
    [00031] In an embodiment, the ethylene-based polymer is present in an amount greater than or equal to 10 weight percent, based on the weight of the composition.
    [00032] In an embodiment, the ethylene-based polymer is present in an amount of 10 to 50 weight percent, or 20 to 40 weight percent, based on the weight of the composition.
    [00033] In an embodiment, the composition comprises yet another ethylene-based polymer that differs in one or more properties, such as density, melt index, comonomer, comonomer content, etc., from the inventive ethylene-based polymer. Other suitable ethylene-based polymers include, but are not limited to, DOWLEX polyethylene resins, TUFLIN linear low density polyethylene resins, ELITE enhanced polyethylene resins (all obtainable from The Dow Chemical Company), high density polyethylene (dh 0 , 96 g / cm3), medium density polyethylene (density 0.935 to 0.955 g / cm3), EXCEED polymers and ENABLE polymers (both from ExxonMobil), and LDPE EVA.
    [00034] In an embodiment, the composition further comprises a polymer based on propylene. Suitable propylene-based polymers include propylene homopolymers, propylene / α-olefin interpolymers, and propylene / ethylene interpolymers.
    [00035] In an embodiment, the composition further comprises a heterogeneously branched ethylene / α-olefin interpolymer, and preferably a heterogeneously branched ethylene / α-olefin copolymer. In an embodiment, the heterogeneously branched ethylene / a-olefin interpolymer, and preferably a heterogeneously branched ethylene / a-olefin copolymer has a density of 0.89 to 0.94 g / cm3, or 0.90 to 0, 93 g / cm3. In a further embodiment, the composition comprises 10 to 50 weight percent, or 20 to 40 weight percent of the inventive ethylene-based polymer, based on the weight of the composition.
    [00036] An inventive composition may comprise a combination of two or more embodiments described herein.
    [00037] The invention also provides an article comprising at least one component formed by an inventive composition.
    [00038] In an embodiment, the article is a film.
    [00039] In an embodiment, the film has an opacity of less than 8% and a shrinkage tension in the MD greater than 9 psi.
    [00040] In an incorporation the film has a perforation greater than 180 foot-pounds / inch3.
    [00041] In an embodiment, the film is formed by a composition comprising from 10 to 40 weight percent, or from 20 to 40 weight percent of an ethylene-based polymer and comprising a majority weight percentage of an interpolymer of heterogeneously branched ethylene / a-olefin, each weight percentage calculated based on the weight of the composition. In an additional embodiment, the film has an opacity value (%) of less than 7.5%, preferably less than 7%. In an embodiment, the film has an MD shrinkage tension greater than 9 psi, preferably greater than 10 psi, more preferably greater than 15 psi.
    [00042] The invention provides a process for forming a polymer according to any of the previous embodiments, the process comprising polymerizing ethylene, and optionally at least one comonomer, in a tubular reactor, at an average polymerization temperature greater than or equal to 280 ° C , a polymerization pressure less than 37,000 psi, and in the presence of a chain transfer agent (CTA).
    [00043] An inventive ethylene-based polymer may comprise a combination of two or more embodiments described herein.
    [00044] An inventive composition may comprise a combination of two or more embodiments described herein.
    [00045] An inventive article may comprise a combination of two or more embodiments described herein. An inventive film can comprise a combination of two or more embodiments described herein.
    [00046] An inventive process may comprise a combination of two or more embodiments described herein. Process
    [00047] To produce an inventive ethylene-based polymer, a polymerization process typically initiated by free radicals at high pressure is typically used. Two different types of polymerization processes initiated by free radicals at high pressure are known. In the first type, a stirred autoclave container having one or more reaction zones is used. Typically, the autoclave reactor has several injection points for initiator and monomer feeds, or both. In the second type, a jacketed tube that has one or more reaction zones is used as a reactor. Appropriate, but not limiting, reactor lengths can be from 100 to 3000 m, or from 1000 to 2000 m. For either of the two types of reactors, the start of a reactor zone is typically defined by the side injection of the reaction initiator, ethylene, chain transfer agent (or telomer), comonomer (s), as well as any combination thereof. A high pressure process can be carried out in autoclaves or tubular reactors, each one comprising one or more reaction zones.
    [00048] A chain transfer agent can be used to control molecular weight. In a preferred embodiment, one or more chain transfer agents (CTAs) are added in an inventive polymerization process, typical CTAs that can be used include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, and propanal (propionic aldehyde). In an embodiment, the amount of CTA used in the process is 0.03 to 10 weight percent of the total reagent mixture.
    [00049] The ethylene used for the production of the ethylene-based polymer can be purified ethylene, which is obtained by removing polar components from a continuous recycling stream, or using a reaction system configuration, such that only new ethylene is used for preparing the inventive polymer. It is not typical that purified ethylene is required to prepare the ethylene-based polymer. In such cases, recycling loop ethylene can be used.
    [00050] In an embodiment, the ethylene-based polymer is a polyethylene homopolymer.
    [00051] In another embodiment, the ethylene-based polymer comprises ethylene and one or more comonomers, and preferably a comonomer. Comonomers include, but are not limited to α-olefin comonomers typically having no more than 20 carbon atoms. For example, α-olefin comonomers can have 3 to 10 carbon atoms; or alternatively, α-olefin comonomers can have 3 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-l- pentene. Alternatively, exemplary comonomers include, but are not limited to, C3-C8 α, β-unsaturated carboxylic acids, in particular maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and crotonic acid, derivatives of C3- carboxylic acids C8 α, β-unsaturated, for example, esters of unsaturated C3-Ci5 carboxylic acids, in particular esters of Ci-Ce alkanols, or anhydrides, in particular, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, terciobutyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, terciobutyl acrylate, methacrylic anhydride, maleic anhydride, and itaconic anhydride. In another alternative, exemplary comonomers include, but are not limited to, vinyl carboxylates, for example, vinyl acetate. In another alternative, exemplary comonomers include, but are not limited to, n-butyl acrylate, acrylic acid and methacrylic acid. Additions
    [00052] An inventive composition can comprise one or more additives. Additives include, but are not limited to stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, glidants, flame retardants, processing aids, smoke inhibitors, viscosity controlling agents and non-stick agents. The polymeric composition can comprise, for example, less than 10 percent (of the combined weight) of one or more additives, based on the weight of the inventive polymer.
    [00053] In an embodiment, the polymers of this invention are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168 (Ciba Specialty Chemicals, Glattbrugg, Switzerland). In general, polymers are treated with one or more stabilizers before extrusion or other melt processes. Processing aids, such as plasticizers, include, but are not limited to, phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin oil, and paraffinic, naphthenic and aromatic oils obtained from petroleum refining, and resins raw materials for pitch and oil. Exemplary classes of oils useful as processing aids include white mineral oil such as KAYDOL oil (Chemtura Corp., Middlebury, Conn.) And SHELLFLEX 371 naphthenic oil (Shell Lubricants, Houston, Texas). Another suitable oil is TUFFLO oil (Lyondell Lubricants, Houston, Texas).
    [00054] Combinations and mixtures of the inventive polymer with other polymers can be prepared. Suitable polymers for mixing with the inventive polymer include natural and synthetic polymers. Exemplary polymers for mixing include propylene-based polymers (impact-modified polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers), various types of ethylene-based polymers, including LDPE via high pressure free radicals, LLDPE Ziegler-Natta, metallocene PE, including multiple reactor PE ("reactor mixtures" of Ziegler-Natta and metallocene PE, such as products disclosed in USP 6,545,088 (Kolthammer, et al.), 6,538,070 (Cardwell , et al.), 6,566,446 (Parikh, et al.), 5,844,045 (Kolthammer, et al.), 5,869,575 (Kolthammer, et al.), and 6,448,341 (Kolthammer, et al.) ), ethylene / vinyl acetate (EVA) copolymer, ethylene / vinyl alcohol copolymer, polystyrene, impact modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes . Homogeneous polymers, such as elastomers and olefinic plastomers, copolymers based on propylene and ethylene (for example, polymers obtainable under the trade name of plastomers and elastomers VERSIFY (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Company) can also be useful as components in mixtures comprising the inventive polymer). applications
    [00055] The polymers of this invention can be used in a variety of conventional thermoplastic fabrication processes to produce useful articles, including, but not limited to, single or multilayer films; molded articles, such as blow-molded, injection-molded, or rotational molded articles; coatings; fibers; and woven and non-woven cloths.
    [00056] An inventive polymer can be used in a variety of films, including, but not limited to laminating films, transparent shrink films, bonding shrink films, leak-drawn films, silage films, stretched cover, sealants, and diaper liners.
    [00057] An inventive polymer is also useful in other direct end-use applications. An inventive polymer can be used in wire and cable coating operations, in sheet extrusion for vacuum molding applications, and forming molded articles, including the use of injection molding, blow molding, or rotational molding processes.
    [00058] Other applications suitable for the inventive polymers include fibers and elastic films; soft-touch products, such as furniture handles; gaskets and profiles; automotive interior profiles and parts; foam products (both open cell and closed cell); impact modifiers for other thermoplastic polymers, such as high density polyethylene, or other olefinic polymers; cover lining; and floors.
    [00059] When used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term polymer includes the term homopolymer (used to refer to polymers prepared from a single type of monomer, with the understanding that traces of impurities may be incorporated in the polymeric structure) and the term interpolymer defined below.
    [00060] When used herein, the term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. This generic term includes copolymers (used to refer to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.
    [00061] When used herein, the term "ethylene-based polymer" refers to a polymer that comprises a majority amount of polymerized ethylene monomer (based on the weight of the polymer) and, optionally, can contain at least one comonomer .
    [00062] When used herein, the term "ethylene / ocoolefin interpolymer" refers to an interpolymer which comprises, in polymerized form, a majority weight percentage of ethylene monomer (based on the weight of the interpolymer), and at least one ocoolefin.
    [00063] When used herein, the term "ethylene / ocoolefin copolymer" refers to a polymer comprising, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copolymer), and a ocoolefin, as the only two types of monomers.
    [00064] When used herein, the term "propylene-based polymer" refers to a polymer that comprises a majority amount of polymerized propylene monomer (based on the weight of the polymer) and, optionally, can contain at least one comonomer .
    [00065] When used herein, the term "composition" includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed by the materials of the composition.
    [00066] When used herein, the term "mixture" or "polymeric mixture" refers to a mixture of two or more polymers. Such a mixture may or may not be miscible (not separated at the molecular level). Such a mixture may or may not be a separate phase. Such a mixture may or may not contain one or more domain configurations, determined by electronic transmission spectroscopy, light scattering, X-ray scattering, and other methods known in the art.
    [00067] The terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed herein. In order to avoid any doubt, all compositions claimed herein through the use of the term "comprising" may include any additive, adjuvant, or additional compound, whether polymeric or different, unless otherwise stated. In contrast, the term "consisting essentially of" excludes any other component, step or procedure from the scope of any subsequent recitation, except those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically described or listed. Testing methods Density
    [00068] Samples were prepared for density measurements according to ASTM D 4703-10. The samples were pressed at 190 ° C for five minutes at 68 MPa. The temperature was maintained at 190 ° C for more than five minutes and then the pressure was increased to 207 MPa for three minutes. This was followed by maintenance for one minute at 21 ° C and 207 MPa. Measurements were performed up to a maximum of 1 hour of sample pressing using ASTM D792-08, Method B. melting index
    [00069] Melt index, or I2, was measured according to ASTM D 1238-10, Condition 190 ° C / 2.16 kg, and reported in grams eluted for 10 minutes. 10 was measured according to ASTM D 1238, Condition 190 ° C / 10 kg, and reported in grams. Nuclear magnetic resonance (C NMR)
    [00070] Samples were prepared by adding approximately 3 g of 50/50 mixture of tetrachloroethane-d2 / ortho-dichloro-benzene, containing 0.025M Cr (AcAc) 3 for "0.25 to 0.40 g" of sample of polymer, in a 10 mm NMR tube. Oxygen is removed from the sample by placing the tubes open in a nitrogen atmosphere for at least 45 minutes. The samples are dissolved and homogenized by heating the tube and its contents to 150 ° C, using a heating block and thermal blower. Each dissolved sample is visually inspected to ensure homogeneity. The samples are thoroughly mixed immediately before analysis and are not allowed to cool before insertion into the heated NMR sample holders.
    [00071] All data is collected using a 400 MHz Bruker spectrometer. Data is acquired using a six-second pulse repeat delay, 90 ° rotation angles, and inverse restricted decoupling with a 125 ° sample temperature Ç. All measurements are obtained from rotation samples in locked mode. Samples are allowed to stay in thermal equilibrium for seven minutes before data acquisition. Chemical NMR shifts from C are referred to internally as the EEE triad at 30.0 ppm. The "C6 +" value is a direct measure of C6 + branches in LDPE, where long branches are not distinguished from "chain terminations". The "32.2 ppm" peak is used, representing the third carbon at the end of all six or more carbon chains or branches to determine the "C6 +" value. Cast resistance
    [00072] The melt strength measurements were performed on a RHEOTENS 71.97 by Gõettfert (Gõettfert Inc., Rock Hill, SC), fixed to a capillary rheometer RHEOTESTER 2000 by Gõettfert. The fused sample (about 10 to 30 g) was fed with a GHEettfert RHEOTESTER 2000 capillary rheometer equipped with a flat (180 °) inlet angle of 30 mm in length, 2 mm in diameter, and an aspect ratio (length / diameter) of 15. After equilibrating the samples at 190 ° C for 10 minutes, the plunger was operated at a constant plunger speed of 0.265 mm / s. The standard test temperature was 190 ° C. The sample was pulled uniaxially by a set of accelerated rolling cylinders, located 100 mm below the die, with an acceleration of 2.4 mm / s2. Traction force was recorded as a function of the compensation speed of the rolling cylinders. Melt strength was reported as the plateau strength (cN) before breaking the row. The following conditions were used in the melt strength measurements: piston speed = 0.265 mm / s; wheel acceleration = 2.4 mm / s2; capillary diameter = 2.0 mm; capillary length = 30 mm; and cylinder diameter = 12 mm. Dynamic mechanical spectroscopy (DMS)
    [00073] Resin samples were molded by compression into "1 inch by 3 mm thick" circular plates at 176.7 ° C (350 ° F) for 5 minutes at a pressure of 1500 psi in air. The compression molded samples were removed from the press and allowed to cool in air at room temperature.
    [00074] A frequency scan at constant temperature was performed using an Advanced Rheometric Expansion System (ARES) rheometer, obtained from TA Instruments, equipped with 25 mm (diameter) parallel plates, in purging of nitrogen. The sample was placed on the plate and allowed to melt for five minutes at 190 ° C. The plates were then brought up to an opening of 2 mm, the sample trimmed, and the test started after a delay of five minutes, to allow temperature equilibrium. The tests were performed at 190 ° C over a frequency range of 0.1 to 100 rad / s. The amplitude of deformation was constant at 10%. The voltage response was analyzed in terms of amplitude and phase, from which were calculated: the storage module (G '), loss module (G "), the complex module (G *), the dynamic viscosity of molten (η *) and tg (Ô) or tg (delta), viscosity at 0.1 rad / s (V0, l), viscosity at 100 rad / s (V100), and viscosity ratio (V0, l / V100), triple detector gel permeation chromatography (TDGPC) - conventional GPC, light scattering GPC, and gpcBR
    [00075] For the GP techniques used here (conventional GPC, light scattering GPC, and gpcBR) a triple detector gel permeation chromatography system (GPC-3D or TDGPC) was employed. This system consists of a Waters Model 150C high temperature chromatograph (Milford, Mass.) (Other suitable high temperature GPC instruments include those from Polymer Laboratories (Shropshire, UK; Model 210 and Model 220) equipped with a spreader detector. 2-angle light (LS) Model 2040 from Precision Detectors (Amherst, Mass.), an IR4 infrared detector from Polymer Char (Valencia, Spain), and a Viscotek 150R 4 capillary (DP) solution viscometer (Houston, Texas)).
    [00076] A GPC these last two independent detectors and at least one of the standard detectors is sometimes referred to as "GPC-3D" or "TDGPC", while the term "GPC" alone generally refers to conventional GPC. Data collection is performed using Viscotek's TriSEC software, version 3, and a DM400 4-channel Viscotek data manager. The system is also equipped with a solvent degassing device in the Polymer Laboratories (Shropshire, UK) line.
    [00077] The eluent from the GPC column set flows through each of the detectors arranged in series, in the following order: LS detector, IR4 detector, then DP detector. The systematic approach for determining multidetector displacements was made in a manner consistent with that published by Balke, Mourey, et al. (Mourey & Balk, Chromatography Polym. Chapter 12, (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)), optimizing triple detector log results (Mw and intrinsic viscosity) using a broad polystyrene pattern, as outlined in the section on light scattering GPC (LS) below, in Equation (5) of the following paragraph.
    [00078] Appropriate high temperature GPC columns, such as 30 cm long Shodex HT803 13 micron columns, or four 30 cm Polymer Labs columns of several 20 micron pore size (LS) can be used MixA, Polymer Labs). Here, LS MixA columns were used. The sample carousel compartment is operated at 140 ° C and the column compartment is operated at 150 ° C. The samples are prepared in a concentration of "0.1 g of polymer in 50 ml of solvent". The chromatographic solvent and the sample preparation solvent is 1,2,4-trichlorobenzene (TCB) containing 200 ppm 2,6-ditherciobutyl-4-methyl phenol (BHT). The solvent is sprayed with nitrogen. The polymeric samples are gently stirred at 160 ° C for four hours. The injection volume is 200 | 1L. The flow rate through the GPC is fixed at 1 mL / min. Conventional GPC
    [00079] For conventional GPC, the IR4 detector is used, and the GPC column set is calibrated by operating 21 polystyrene standards of narrow molecular weight distribution. The molecular weight (Mw) of the standards ranges from 580 g / mol to 8,400,000 g / mol, and the standards are contained in 6 "cocktail" mixtures. Each standard mixture has at least a dozen separation between individual molecular weights. Standard mixtures are purchased from Polymer Laboratories. Polystyrene standards are prepared in "0.025 g in 50 ml of solvent" for molecular weights greater than or equal to 1,000,000 g / mol, and in "0.05 g in 50 ml of solvent" for molecular weights less than 1,000. 000 g / mol. The polystyrene standards are dissolved at 80 ° C, with gentle agitation, for 30 minutes. Mixtures of narrow patterns are used first, and in order to decrease maximum molecular weight component to minimize degradation. The maximum molecular weights of polystyrene standard are converted to polyethylene molecular weight using Equation (1) (as described in Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968)):
    where M is the molecular weight of polyethylene or polystyrene (as indicated), and B is equal to 1.0. Those of ordinary skill in the art know that A can be in the range of about 0.38 to about 0.44, and is determined at the time of calibration using a wide polyethylene standard, as outlined in the section on GPC scattering. light (LS) below in Equation (5) of the next paragraph. The use of this polyethylene calibration method to obtain molecular weight values, such as the molecular weight distribution (MWD or Mw / Mn) and related statistics, is defined here as the modified method and Williams and Ward. The number average molecular weight, the weight average molecular weight and the average z-molecular weight are calculated from the following equations.


    Light scattering GPC (LS)
    [00080] For the LS GPC, the PDI 2040 model 2040 Precision Detector was used. Depending on the sample, for the purposes of calculation, the 15 ° or 90 ° angle of the light scattering detector is used. Here the 15 ° angle was used.
    [00081] Molecular weight data are obtained in a manner consistent with that published by Zimm) Zimm, B.H., Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The overall injected concentration used in determining the molecular weight is obtained from the mass detector area, and from the mass detector constant derived from a linear polyethylene homopolymer, or from one of the known weight average molecular weight polyethylene standards. The calculated molecular weights are obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index coefficient, dn / dc, of 0.104. Generally, the mass detector response and the light scattering constant should be determined from a linear pattern with a molecular weight in excess of about 50,000 g / mol. Viscometer calibration can be performed using the methods described by the manufacturer, or alternatively using the published values of appropriate linear standards such as Standardized Reference Materials (SEM) 1475a (obtainable from the National Institute of Standard Reference Materials (NIST)). It is assumed that the chromatographic concentrations are low enough to eliminate treatment of 2nd virial coefficient effects (concentration effects on molecular weight).
    [00082] With GPC-3D, the absolute weight average molecular weight ("Mw, abs") is determined using equation (5) below, using the "maximum area" method for greater accuracy and precision. The "LS Area" and the "Cone Area." are generated by the combination of chromatograph / detectors.

    [00083] For each LS profile (for example, see Figures 1 and 2), the x-axis (Log MWcc-CPC) is determined, where cc refers to the conventional calibration curve, as follows. First, the polystyrene standards (see above) are used to calibrate the retention volume in "log MWPS". Then, Equation 1 (Mpoiietiieno = A x (Mpoiiestireno) B) is used to convert "log MWPS" into "log MWPE". The "MWPE log" scale serves as the x-axis for the LS profiles of the experimental section (log MWPE is equal to the log MW (cc-GPC)). The x-axis for each LS profile is the LS detector response normalized by the injected sample mass. Initially, molecular weight and intrinsic viscosity are determined for a standard linear polyethylene sample, such as SEM 1475a or equivalent, using conventional calibrations ("cc") for both molecular weight and intrinsic viscosity as a function of volume elution.
    [00084] In the low molecular weight region of the GPC elution curve, the presence of a significant peak that is known to be caused by the presence of antioxidants or other additives, will cause an excessively low estimate of the numerical average molecular weight (Mn) of the polymer sample, to give an excessively high estimate of the sample polydispersity, defined as Mw / Mn, where Mw is the weight average molecular weight. Therefore, the true molecular weight distribution of the polymer sample can be calculated from the GPC elution excluding this extra peak. This process is commonly described as a peak withdrawal characteristic in data processing procedures in liquid chromatographic analyzes. In this process, this additive peak is removed from the GPC elution curve before performing the sample molecular weight calculation from the GPC elution curve. gpcBR branching index by triple detector GPC (GPC-3D)
    [00085] The branching index of gpcBR is determined by first calibrating the light scattering, viscosity and concentration detectors, as previously described. The baselines are then subtracted from the light scattering, viscosity and concentration chromatograms. Then, the integration windows are adjusted to ensure the integration of the entire low molecular weight retention volume range in the light scattering and viscometer chromatograms that indicate the presence of the detectable polymer in the refractive index chromatogram. Linear polyethylene standards are then used to establish the Mark-Houwink constants of polyethylene and polystyrene. After obtaining the constants, the two values are used to construct two conventional linear reference calibrations for polyethylene molecular weight and intrinsic polyethylene viscosity as a function of elution volume, as shown in Equations (6) and (7):


    [00086] The gpcBR branching index is a robust method for characterizing long chain branching, as described in Yau, Wallace W., "Examples of Using 3D-GPC-TREF for Polyolefin Characterization", Macromol. Symp., 2007, 257, 29-45. The index avoids the "slice by slice" GPC-3D calculations traditionally used in determining g 'values and branch frequency calculations, in favor of detector areas of the entire polymer. From the GPC-3D data, it is possible to obtain the absolute weight average molecular weight of sample mass (Mw, abs) by the light scattering detector (LS) using the peak area method. The method avoids the "slice by slice" ratio of the light scattering detector signal to the concentration detector signal, as required in traditional g 'determination.
    [00087] With GPC — 3D, the intrinsic viscosities of samples are also obtained independently using Equation (8). The area calculation in Equations (5) and (8) offers more precision because, as a global sample area, it is much more sensitive to variation caused by detector noise and GPC-3D adjustments in the baseline and limits of integration. Most importantly, the peak area calculation is not affected by the detector volume shifts. Similarly, the intrinsic (IV) viscosity of a high precision sample is obtained by the area method shown in Equation (8):
    where DPi represents the differential pressure signal monitored directly from the viscometer on the line.
    [00088] To determine the gpcBR branching index, the light scattering elution area of the sample polymer is used to determine the molecular weight of the sample. The viscosity detector elution area of the sample polymer is used to determine the intrinsic viscosity (IV or [η]) of the sample.
    [00089] Initially, the molecular weight and intrinsic viscosity of a standard linear polyethylene sample, such as SRM 1475a or equivalent, are determined using conventional calibrations ("cc") for both molecular weight and intrinsic viscosity as a function of elution volume, by Equations (2) and (9):

    [00090] Equation (10) is used to determine the gpcBR branching index:
    where [η] is the measured intrinsic viscosity, [ηlcc is the intrinsic viscosity of the conventional calibration, Mw is the measured weight average molecular weight, and Mw, cc is the weight average molecular weight of the conventional calibration. The weighted average molecular weight by light scattering (LS) using Equation (5) is commonly referred to as the "absolute weighted average molecular weight" or Mw, abs. The Mw, cc of Equation (2) using the conventional GPC molecular weight calibration curve ("conventional calibration") is often referred to as "polymer main chain molecular weight", "conventional weight average molecular weight", and LIW , GPC •
    [00091] All statistical values with the subscript "cc" are determined using their respective elution volumes, the corresponding conventional calibration described above, and the concentration (Ci). Unsubscribed values are values measured based on the mass detector, LALLS, and viscometer areas. The KPE value is iteratively adjusted, until the linear reference sample has a measured gpcBR value of zero. For example, the final values of oc and log K for gpcBR determination in this particular case are 0.725 and -3.355, respectively, for polyethylene, and, respectively, 0.722 and -3.993, for polystyrene.
    [00092] Once the values of K and a have been determined using the procedure discussed above, the procedure is repeated using branched samples. Branched samples are analyzed using the final Mark-Houwink constants as the best "cc" calibration values and applying Equations (2) - (9).
    [00093] The interpretation of gpcBR is easy to understand. For linear polymers, gpcBR calculated from Equation (8), will be close to zero, since the values measured by LS and viscometry will be close to the conventional calibration standard. For branched polymers, gpcBR will be greater than zero, especially with high levels of long chain branching, because the measured molecular weight of the polymer will be greater than the calculated Mw, cc, and the calculated IVCC will be greater than the measured polymer IV. In fact, the gpcBR value represents the partial IR change due to the effect of molecular size contraction as the result of polymer branching. A gpcBR value of 0.5 or 2.0 would mean a contraction effect of IV molecular size at the level of 50% and 200%, respectively, against a linear polymer molecule of equivalent weight.
    [00094] For these particular examples, the advantage of using gpcBR compared to traditional "index g" and branching frequency calculations is due to the higher precision of gpcBR. All parameters used in the gpcBR index determination are obtained with good precision and are not adversely affected by the low response of the GPC-3D detector at high molecular weight of the concentration detector. Errors in the calibration of detector volume also do not affect the accuracy of the gpcBR index determination. Representative calculation of "normalized LSF" - Inventive and Comparative
    [00095] Figures 1 and 2 show a GPC elution profile of the "normalized concentration" LS detector response for Comparative Example 7 and Example 1, respectively. The quantities that affect the "normalized LSF" value are defined with the help of Figures 1 and 2. In the graphs, the x-axis is the logarithmic value of the molecular weight (MW) by conventional GPC calculation, or MW cc-GPC. The y-axis is the LS detector response, normalized to be equal to the sample concentration, measured by the peak area of the concentration detector (not shown). The specific characteristics of the LS elution profile are captured in a window defined by two "log-MW" limits shown in Figures 1 and 2. The lower limit corresponds to an Ml value of 400,000 g / mol, and the upper limit corresponds to a M2 value of 1,400,000 g / mol.
    [00096] The vertical lines of these two MW limits intersect the LS elution curve at two points. A line segment is drawn connecting these two intersection points. The height of the LS signal at the first intersection (log Ml) gives the amount Sl. The height of the LS signal at the second intersection (log M2) gives the quantity S2. The area under the LS elution curve, within the two MW limits gives the amount Area B. Comparing the LS curve with the line segment connecting the two intersections, it may be part of the segmented area that is above the line segment (see A2 in Figures 1 and 2, defined as a negative value) or below the line segment (as Al in Figures 1 and 2, defined as a positive value). The sum of Al and A2 gives the quantity Area A, the total area of A. This total Area A can be calculated as the difference between Area B and the area below the line segment. The validity of this approach can be verified by the following two equations (note that A2 is negative as shown in Figures 1 and 2). Since (Area below the line segment) = (Area B) + A2 + Al = (Area B), therefore (Area A) = (Area B) - (Area below the line segment).
    [00097] The steps of calculating the "normalized LSF" quantity are illustrated with three examples (Comparative Example 7, Example 1, and Comparative Example 20) shown in Tables 1 to 3.
    [00098] Step 1, "Slope F" is calculated in Table 1, using the following two equations: Slope_value = [(LS2-LS1) / LS2] d log M (Equation 11) Slope F = a slope function = ( inclination_value) absolute +0.1 (Equation 12)
    [00099] Step 2, "Area F" and "LSF" are calculated in Table 2, using the following two equations: Area F = an area function = (A / B) absolute +0.1 (Equation 13) where , A / B = (Area A) / (Area B) LSF = log (Area F x F slope) +2.5 (Equation 14)
    [000100] Step 3, "Normalized LSF" is finally calculated in Table 3, using the following equation: "Normalized LSF" = 12 * (cc-GPC Mw / Mn) / LSF (Equation 15) Table 1: Calculation of " slope F "
    Table 2: Calculation of "Area F" and "LSF"
    Table 3: Calculation of "normalized LSF"
    Film testing
    [000101] The following physical properties were measured on films described in the experimental section.
    [000102] Total (global) opacity and internal opacity: Internal opacity and total opacity were measured according to ASTM D 1003-07. Internal opacity was obtained by combining the index of refraction using mineral oil (1-2 teaspoons), which was applied as a coating on each surface of the film. HAZEGARD PLUS (BYK-Gardne USA, Columbia, MD) was used for testing. In each test, five samples were examined, and an average was recorded. The sample dimensions were "6 inches x 6 inches".
    [000103] 45 ° brightness: ASTM D2457-08 (average of five "10 inch x 10 inch" film samples).
    [000104] Clarity: ASTM D 1746-09 (average of five "10 inch x 10 inch" film samples).
    [000105] 2% elastic modulus - MD (machine direction) and CD (transversal direction): ASTM D 882-10 (average of five film samples in each direction; each "1 inch x 6 inch" sample ).
    [000106] Elmendorf tear strength on MD and CD: ASTM D 1922-09 (average of 15 film samples in each direction; each "3 inch x 2.5 inch" crescent shaped sample).
    [000107] Tensile strength in MD and CD: ASTM D 882-10 (average of five film samples in each direction; each sample "1 inch x 6 inches").
    [000108] Dart impact resistance: ASTM D 1709-09 (minimum of 20 drops to reach 50% failure; typically ten "10 inch x 36 inch" strips).
    [000109] Puncture resistance: Perforation was measured on an INSTRON Model 4201 with the SINTEC TESTWORKS software version 3.10. The specimen size was "6 inches x 6 inches" and 4 measurements were taken to determine an average drilling value. The film was conditioned for 40 hours after film production, and at least 24 hours in an ASTM controlled laboratory (23 ° C and 50% relative humidity). A "100 pound" load cell with a 4-inch diameter round specimen clamp was used. The drill rig is a stainless steel ball "1/2 inch in diameter" (on a 2.5 "rod) with a" maximum travel length of 7.5 inches ".
    [000110] There was no meter length, and the probe was as close as possible, but it did not touch the specimen. The probe was adjusted by raising the probe until it touched the specimen. Then, the probe was gradually lowered until it did not touch the specimen. Then, the plunger was set to zero. Considering the maximum travel distance, the distance would be approximately 0.10 inch. The plunger speed was 10 inches / min. The thickness was measured in the middle of the specimen. The thickness of the film, the distance traveled by the plunger, and the maximum load were used to determine the perforation by the software. After each specimen, the drilling probe was cleaned using "KIM-WIPE".
    [000111] Contraction stress: Contraction stress was measured according to the method described in Y. Jin, T. Hermel-Davidock, T. Karjala, M. Demirors, J. Wang, E. Leyva, and D. Allen , "Shrink Force Measurement of Low Shrink Force Films," SPE ANTEC Proceedings, p. 1264 (2008). The shrinkage stress of film samples was measured by a gradual temperature rise test that was performed on a dynamic mechanical analyzer RSA-III (TA Instruments, New Castle, DE) with fixed film accessory. The "12.7 mm wide" and "63.5 mm long" film samples were cut from the film sample, in the machine direction (MD) or in the transverse direction (CD), for testing. The thickness of the film was measured by a DIGIMATIC ABSOLUTE indicator from Mitutoyo (model C112CEXB). This indicator had a maximum measurement range of 12.7 mm, with a resolution of 0.001 mm. The average of three thickness measurements, at different locations in each film sample, and the sample width, were used to calculate the film cross-sectional area (A), in which "A = width x thickness" of the film sample. film that was used in the film shrink test. For measurement, a standard TA Instruments film tension fixture was used. The RSA-II oven was equilibrated at 25 ° C, for at least 30 minutes, before zeroing the opening and the axial force. The initial opening has been adjusted to 20 mm. Then, the film sample was fixed on both the upper and lower fixed accessories. Typically, measurements for MD require only one layer film. Since the contraction stress in the CD direction is typically low, two or four layers of film are stacked together for each measurement to improve the signal-to-noise ratio. In such a case, the thickness of the film is the sum of all layers. In this work, a single layer was used in the MD direction and two layers were used in the CD direction. After the film reached the initial temperature of 25 ° C, the upper fixed accessory was manually raised or slightly decreased to obtain an axial force of -1.0 g. This was to ensure that there was no excessive arching or stretching of the film at the start of the test. Then the test started. A constant gap of fixed accessory was maintained throughout the measurement.
    [000112] The gradual rise in temperature started at a rate of 90 ° C / min, from 25 ° C to 80 ° C, followed by a rate of 20 ° C / min, from 80 ° C to 160 ° C. During the gradual rise from 80 ° C to 160 ° C, when the film contracted, the contraction force, measured by the force transducer, was recorded as a function of the temperature for further analysis. The difference between the "maximum force" and the "baseline value before the start of the peak contraction force" is considered the shrink force (F) of the film. The shrinkage stress of the film is the ratio of the shrinkage force (F) to the cross-sectional area (A) of the film. Experimental Preparation of inventive polymers based on ethylene and comparative polymers
    [000113] When discussing and comparing process conditions, process conditions can be referred to by their product designation (for example, process conditions for producing the product of Example 1 can be referred to as "the process of Example 1") . Examples 1 to 6 are produced in the same process reaction system. Figure 3 is a simple block diagram of the process reaction system used to produce the aforementioned examples.
    [000114] In Figure 3, the process reaction system is a production system of low pressure polyethylene at high pressure, double recycling and partially closed cycle. The process reaction system comprises a new ethylene feed conduit [1]; a primary blower / compressor "BP", a hyper compressor "Hiper", and a three zone tube. The tubular reactor consists of a first feeding zone; a first peroxide initiator conduit [3] connected to a first source of peroxide initiator [11]; a second peroxide initiator conduit [4] connected to the second source of peroxide initiator [12]; and a third peroxide initiator conduit [5] connected to the second source of peroxide initiator [12]. Cooling jackets (using high pressure water) are mounted around the outer shell of the tubular reactor and preheater. The tubular reactor also consists of a "HPS" high pressure separator; a high pressure recycling line [7]; a low pressure separator "LPS"; a low pressure recycling line [9]; and a chain transfer agent (CTA) feeding system 13.
    [000115] The tubular reactor also comprises three reaction zones marked by the location of the peroxide injection points. The first reaction zone feed is connected to the front of the tubular reactor, and feeds a portion of the process fluid to the first reaction zone. The first reaction zone starts at the injection point # 1 [3], and ends at the injection point # 2 [4]. The first peroxide initiator is connected to the tubular reactor at the injection point # 1 [3]. The second reaction zone starts at the injection point # 2 [4]. The second reaction zone ends at the injection point # 3 [5]. The third reaction zone starts at the injection point # 3 [5]. For all examples, 100 percent of ethylene and ethylene recycles are directed to the first reaction zone, via the conduit [1] of the first reaction zone feed. This is referred to as a tubular gas reactor all over the front.
    [000116] Figure 4 is a simple block diagram of the process reaction system used to produce Comparative Example 20. In Figure 4, the process reaction system is a high pressure low density polyethylene production system, double recycling and partially closed cycle. The process reaction system comprises a new ethylene feed conduit [1]; a primary blower / compressor "BP", a hyper compressor "Hiper", and a three zone tube. The tubular reactor consists of a first feeding zone; a first peroxide initiator conduit [3] connected to a first source of peroxide initiator 10; a second peroxide initiator conduit [4] connected to the second peroxide initiator source 11; a "HPS" high pressure separator; a high pressure recycling line [6]; a low pressure separator "LPS"; a low pressure recycling line [8]; and a chain transfer agent (CTA) feeding system [12]. Cooling liners (using high pressure water) are mounted around the outer shell of the tubular reactor and preheater.
    [000117] The tubular reactor also comprises three reaction zones marked by the location of the peroxide injection points. The first reaction zone feed is connected to the front of the tubular reactor, and feeds a portion of the process fluid to the first reaction zone. The first reaction zone starts at the injection point # 1 [3], and ends at the injection point # 2 [4]. The first peroxide initiator is connected to the tubular reactor at the injection point # 1 [3]. The second reaction zone starts at the injection point # 2 [4].
    [000118] For Comparative Example 20, 100 percent of ethylene and ethylene recycles are directed to the first reaction zone, via the conduit [1] of the first reaction zone feed. This is referred to as a tubular gas reactor all over the front.
    [000119] For all inventive examples and for comparative example, a mixture containing t-butyl peroxy-2-ethylhexanoate (TBPO), ditherciobutyl peroxide (DTBP), terciobutyl pivalate peroxy, and a solvent is used of isoparaffinic hydrocarbon (boiling range> 179 ° C; for example, ISOPAR E) as the mixture of initiators for the first injection point. For injection points # 2 and # 3, a mixture containing only DTBP, TBPO, and the isoparaffinic hydrocarbon solvent is used. The reactor tube process conditions used to prepare Examples 1-6 and Comparative Example 20 are given in Tables 4 and 6. Table 5 lists some chain transfer agents and their "Cs" values.
    [000120] For Examples 1, 2, 4, 5, and 6 and for Comparative Example 20 propylene was used as the CTA. Propylene is injected into the ethylene stream in the discharge drum of the first stage blower. The composition of the CTA feed for the process is adjusted to control the melting index of the product. For Example 3, isobutane was used as the CTA.
    [000121] For Examples 1-6, the reactor pressure was between 34,700 and 36.00 psig. It was found that the low global reactor pressure (33,000-36,000 psig), in combination with a high average reactor temperature (> 300 ° C) and the CTA (for example, propylene), produced LLDPEs with very wide and low MWD densities.
    [000122] Figures 5 and 6 show the temperature profiles of Example 2 and Comparative Example 20, and the reaction zones with respect to peroxide injections. The refrigerant temperature is that of the cooling fluid used to cool the reaction zones. The cooling fluid is fed against current to the reactor. Several cooling zones are used to cool each reaction zone. Temperatures are measured entering and leaving each cooling zone. The reactor temperature measurement (y-axis) is made inside the reactor along the length of the reactor. Each reaction temperature represents the reaction temperature at that point in the reactor. The x-axis shows the junction between tubes, and the y-axis is the temperature for the reaction and for the boiling water. Thermocouples were used to measure the downward reaction temperature in the tube during production. The reaction peaks for each zone were controlled by adjusting peroxide flows for each of the reaction zones. The maximum temperatures were then used to help control the MED / density of the product.
    [000123] The activity of the different CTAs used can be described by a chain transfer constant, in which higher values of the chain transfer constant represent much more active CTAs. The method for determining Cs, and Cs values, is contained in G.A. Mortimer, "Chain Transfer in Ethylene Polymerization", J. Polymer Science: Part A-1, volume 4, pages 881-900 (1966). As discussed above, the Cs for some common CTAs are shown in Table 5. In an embodiment, the CTA has a Cs value (1360 atm, 130 ° C) from 0.001 to 0.070, preferably from 0.005 to 0.060, more preferably from 0.008 to 0.050, and even more preferably from 0.010 to 0.020 (see Mortimer mentioned above).
    [000124] Tables 7-10 contain characterization data for the Examples (inventive polymers) and the Comparative Examples (comparative polymers). Tables 7 and 8 show the melt index, density, melt strength, and DMS data of the Examples and Comparative Examples, respectively. The Examples cover a melt index range of 1.65-2.56, a density range of 0.9185-0.9216 g / cm3, a melt strength range of 6.9-9.6, and a viscosity ratio range of 15.1-20.4. Table 8 shows a wide range of comparative examples. In general, at a comparable melt index, comparative examples tend to be higher in density, lower in melt strength, and have lower viscosity ratios.
    [000125] Tables 9 and 10 contain the melt index, TD-GPC properties, density and CTA type of the Examples and Comparative Examples, respectively. The Examples tend to have a greater molecular weight distribution Mw / Mn, a greater normalized LSF, and a greater gpcBR than the Comparative Examples. These combined characteristics result in an ethylene-based polymer with increased melt strength, decreased shearability and improved processability, as indicated by a higher viscosity ratio (V0, l / V100, at 190 ° C), and as discussed below, increased film production in an expanded film line. Likewise, it has been found that the broader Mw / Mn of the inventive polymers, in combination with standardized LSF, and a larger gpcBR, can be used in "linear low density polymer rich mixes (LLDPE)" to form films that have unexpectedly low opacity.
    Table 5: Chain transfer constant (Cs) measured at 1360 atm and 130 ° C for CTA *
    * GA Mortimer, "Chain Transfer in Ethylene Polymerization", J. Polymer Science: Part A, volume 4, pages 881-900 (1966). Table 6: Tube processing conditions used to prepare Ex. 1-6 and Ex. Comp. 20.
    * The average of the maximum temperatures. ** BW = "boiling water". 42/55 Table 7: Melt index (I2), density, melt strength (MS), and DMS data at 190 ° C of the Examples. 44/55
    Viscosity ratio = [Viscosity 0.1 rad / s] / Viscosity 1UU Note: Vis c. = Table 8: melt index (I2), density, melt strength (MS), and DMS 190 ° C data from Comparative Examples.
    Table 9: melting index, GPC-TD related properties, density, and CTA of Comparative Examples.
    aPeak of antioxidant (AO) removed consisting of 2,000 ppm IRGANOX 1-1010 per peak withdrawal characteristic described in the GPC light scattering (LS) section. bMARFLEX 5755 (Chevron Phillips Company LP); CWESTLAKE EF403 (Westlake Chemical); dLUPOLEN 3220F (Lyondell Basell); eLDPE LD105.3 from ExxonMobil. 45/55 Table 10: melt index, GPC-TD related properties, density, and CTA of Examples.

    [000126] Table 11 shows the branching results for Examples, Comparative Examples and LLDPE 1. The amyl or C5 group is unique for LDPE. LLDPE 1, used in film experiments, contains octene, resulting in elevated levels of C6 +. Table 11: Branch results given in branches per 1000C by 13C NMR of Examples, Comparative Examples, and LLDPE 1 (discussed in the Formulations section).
    ND = not detected. Formulations
    [000127] Expanded films are prepared and physical properties measured with eight different LDPEs and one LLDPE. The LLDPE used, LLDPE 1, had a melting index (MI or I2) equal to 1.0 g / 10 min, density of 0.920 g / cm3 and produced by Ziegler-Natta catalysis. The films were prepared with 0-6 by weight, 20% by weight, 30% by weight, 70% by weight, and 100% by weight of the respective LDPE, based on the weight of LDPE and LLDPE 1 Polymers were used at ethylene base (LDPEs) in film samples: Examples 1, 4-6, and Comparative Examples 3, 20, and 21.
    [000128] Each formulation was composed in a MAGUIRE gravimetric mixer. In each formulation, a polymer processing aid (PPA) was added. PPA was added in 1.125-6 wt. Of standard mix, based on the total weight of the formulation. The standard PPA mix (CKAC-19, obtainable from Ingenia Polymers) contained 8% by weight of DYNAMAR FX-5920A in polyethylene conveyor.
    [000129] LLDPE 1 was also used as LDPE in films prepared in maximum yield. All samples were prepared with 80% by weight of DOWLEX 2045G and 20% by weight of LDPE. The LDPEs used in determining maximum film yield were as follows: Examples 1, 4-6, and Comparative Examples 3, 6, and 22. Film production
    [000130] One layer expanded films are prepared in an 8 inch matrix with "Davis Standard Barrier II screw" made of polyethylene. External cooling by an air ring and internal bubble cooling were used. Table 12 shows the general expanded film parameters used to produce each expanded film. The temperatures are the temperatures closest to the pellet loading funnel (Drum 1), and in ascending order, when the polymer was extruded through the matrix (melting temperature). Table 12: Manufacturing conditions for expanded films for films
    Film production to determine maximum rate of expanded film production
    [000131] Film samples are prepared at a controlled rate and at a maximum rate. The controlled rate was 350 pounds / h, which is equal to the production rate of 13.9 pounds / h / inch of matrix circumference. The matrix diameter used for maximum production experiments was an 8 inch matrix, so for the controlled rate, as an example, the conversion between "pound / hr" and "pound / hour / inch" of matrix circumference, is shown in Equation 16. Similarly, such an equation can be used for other rates, such as the maximum rate, replacing the maximum rate in Equation 16 to determine the "pound / hour / inch" of matrix circumference. Pound / hour / inch of matrix circumference = (350 pound / h) / (8 * π) = 10 (Equation 16)
    [000132] The maximum rate for a given sample was determined by increasing the production rate to the point where bubble stability was the limiting factor. The extruder profile was maintained for both samples (standard rate and maximum rate), however, the melting temperature was higher for the maximum rate samples, due to the increased shear rate with higher engine speed (rpm, revolutions per minute). The maximum bubble stability was determined by considering the bubble at the point where it would not remain seated in the air ring, and then a sample was collected. The bubble cooling was adjusted by adjusting the air ring and maintaining the bubble. This was considered to be the maximum production rate while still maintaining bubble stability. Film properties
    [000133] Tables 13-15 show the film results for films produced at the standard rate of 350 lb / h at 20%, 30%, and 70% LDPE. From Tables 13-15, both internal opacity and total opacity are low, brightness is high, and the shrinkage stress in MD and CD is high for the Examples when purchased with the Comparative Examples. Table 13 shows that for a "mixture of 20% LDPE", the total opacity and internal opacity are low, the perforation is high, and the contraction stress in MD is high for the average of the Inventive Formulations (each containing an inventive polymer), when compared to Comparative Formulations (each containing a comparative polymer). Table 14 shows that for a "mixture of 30% LDPE" the dart A and contraction stress in MD are both high for the average of the Inventive Formulations when compared with the Comparative Formulations. Table 15 shows that for a "mixture of 70% LDPE", the internal opacity, perforation, and contraction stress in MD are all high for the average of the Inventive Formulations when compared to the Comparative Formulations. Overall, the Inventive Examples show improved performance for lower opacity, higher tenacity (perforation, dart) and higher contraction stress when compared to Comparative Examples.
    [000134] Tables 16 and 17 describe the maximum rate data, and the film properties of these samples. Table 16 shows that the Examples have high maximum production rates, and that these production rates are similar to that of a much lower melt index LDPE (Comparative Example 6 - Formulation 23). Table 16 shows that for a "20% blend of LDPE", the maximum production performance of Inventive Example 4 (Formulation 25), at "1.75 melt index" is surprisingly similar to that of an LDPE index of much lower melting (melting index 0.64 - Comparative Example 6). The Inventive Sample 4 also has better opacity, brightness, and rupture in MD. Table 17 shows for a "mixture of 20% LDPE" at maximum production, that the opacity is low and the gloss is high for Inventive Formulations (each containing an inventive polymer) when compared to Comparative Formulations (each containing a comparative polymer). In general, Inventive Formulations have improved performance of lower opacity, greater tenacity (perforation, dart), greater contraction stress, and greater maximum production at the bubble stability limit, in a similar melting index, when compared to Comparative Formulations. Table 13: Film Properties of Formulations # 1-7 of 80% LLDPE 1/20% LDPE - prepared in 2 milliliters at a standard rate of 350 pounds / h (8 "matrix). 51/55

    Table 15: Film properties of Formulations # 8-14 of 30% LLDPE 1/70% LDPE and IOO-Ó LLDPE 1 - prepared in 2 millipoles at a standard rate of 350 pounds / h (8 "matrix) .
    Table 16: Production at maximum rate at the bubble stability limit of Formulations 23-30.
    Table 17; Film properties of samples prepared in production at maximum rate at the bubble stability limit of Formulations 23-30.
    权利要求:
    Claims (13)
    [0001]
    1. Polymer based on ethylene, characterized by the fact that it comprises the following properties: (A) MWDconv from 7 to 10; (B) "Standardized LSF" greater than or equal to 9.5, as determined by gel permeation chromatography (GPC); and the ethylene-based polymer has a rheology ratio (V0.1 / V100), at 190 ° C, from 10 to 25, as determined by dynamic mechanical spectroscopy (DMS); and (C) a melting index greater than or equal to 1.0 g / 10 min, according to ASTM D 1238-10, Condition 190 ° C / 2.16 kg.
    [0002]
    2. Ethylene-based polymer, according to claim 1, characterized by the fact that it is formed in a high pressure polymerization process (P greater than 100 MPa).
    [0003]
    3. Ethylene-based polymer, according to claim 1, characterized by the fact that it is a low density polyethylene (LDPE).
    [0004]
    4. Ethylene-based polymer, according to claim 1, characterized by the fact that it has> 0.1 amyl branching per 1000 carbon atoms, as determined by gpcBR in triple detector GPC (GPC-3D).
    [0005]
    5. Ethylene-based polymer according to claim 1, characterized by the fact that it has a density of 0.90 to 0.95 g / cm3, according to ASTM D 4703-10.
    [0006]
    6. Ethylene-based polymer according to claim 1, characterized by the fact that it has a melt resistance of 5 to 15 cN, when performed on a RHEOTENS 71.97 by Gõettfert, fixed to a capillary rheometer RHEOTESTER 2000, equipped with a flat entry angle (180 °) in length of 30 mm, diameter of 2 mm, and an aspect ratio of 15.
    [0007]
    7. Composition, characterized by the fact that it comprises the ethylene-based polymer, as defined in claim 1.
    [0008]
    8. Composition according to claim 7, characterized in that it also comprises a heterogeneously branched ethylene / alpha olefin interpolymer.
    [0009]
    Composition according to claim 7, characterized in that the ethylene-based polymer is present in an amount greater than or equal to 10 weight percent, based on the weight of the composition.
    [0010]
    10. Article, characterized by the fact that it comprises at least one component formed by the composition as defined in claim 7.
    [0011]
    11. Article, according to claim 10, characterized by the fact that it is a film.
    [0012]
    12. Article, according to claim 11, characterized by the fact that the film has an opacity of less than 8% and a shrinkage tension in the MD greater than 9 psi, as determined by ASTM D 882-10 (machine direction).
    [0013]
    13. Article, according to claim 11, characterized by the fact that the film has a perforation greater than 180 foot-pounds / inch3, as determined in an INSTRON Model 4201 with the SINTEC TESTWORKS software version 3.10.
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    同族专利:
    公开号 | 公开日
    US8822601B2|2014-09-02|
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    EP2651987A1|2013-10-23|
    KR20130140110A|2013-12-23|
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    CA2821248A1|2012-06-21|
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    WO2012082393A1|2012-06-21|
    KR101845119B1|2018-04-03|
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    EP2651987B1|2016-09-21|
    CA2821248C|2019-01-08|
    US20130261265A1|2013-10-03|
    SG191149A1|2013-07-31|
    JP2017101251A|2017-06-08|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-02-27| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-06-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-08-25| B09X| Decision of grant: republication|
    2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201061424386P| true| 2010-12-17|2010-12-17|
    US61/424,386|2010-12-17|
    PCT/US2011/062991|WO2012082393A1|2010-12-17|2011-12-02|Ethylene-based polymers and processess to make the same|
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