Ziegler-natta catalyzed polyethylene resins and films incorporating the same

Abstract

To provide a polymer having reduced high density fraction to allow for improvement in optical and abuse properties, such as dart impact, while not suffering a significant trade-off of mechanical strength and tear properties, as well as a blown film comprising the polymer.SOLUTION: There is provided a linear low density polyethylene (LLDPE) polymer. The LLDPE is the polymerized reaction product of ethylene monomer, and C3 to C12 ethylene comonomer. The LLDPE has a density from 0.904 to 0.925 g / cc; a melt index (I2) of 0.5 to 1.5 g / 10 minutes when measured according to ASTM1238 under a load of 2.16 kg at a temperature of 190°C; a melt flow ratio (I10 / I2) of 6.5 to 7.6, wherein I10 is measured according to ASTM1238 at a temperature of 190°C with 10 kg load; and a molecular weight distribution (MWD=Mw / Mn) of 2.5 to 3.6 when measured according to gel permeation chromatography (GPC).SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 855,4 filed May 31, 2019. No. 18, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure generally relate to linear low density polyethylene (LLDPE) compositions. In particular, LLDPE compositions produced from heterogeneous procatalyst compositions, and and films incorporating these LLDPE compositions. [Background technology]

[0003] Olefin-based polymers, such as ethylene-based polymers and propylene-based polymers, are It is produced using various catalysts. It is used in the polymerization process of olefin polymers. The components of such catalysts contribute to the characteristics and properties of such olefin-based polymers. This is an important factor.

[0004] Ethylene-based polymers are manufactured for use in a wide variety of articles. The ethylene polymerization process produces a variety of physical properties that make different resins suitable for use in different applications. In order to produce a wide range of polyethylene resins with desirable properties, Hydrogen can also be added to the reactor. The catalysts for this are typically chromium-based catalysts, Ziegler-Natta catalysts, and / or molecular It may contain a catalyst (either metallocene or non-metallocene). A portion of the reaction mixture containing the formed polyethylene product contains unreacted ethylene and It is removed from the reactor together with one or more optional comonomers. The resulting reaction mixture may be treated to separate the polyethylene product from unreacted reactants. The unreacted reactants are typically recycled back into the reactor. Alternatively, the reaction mixture can be The first reactor may be connected in series to a second reactor, where a second polyethylene Fractions can be generated.

[0005] Conventional polymers produced by Ziegler-Natta catalysts are generally produced by molecular catalysts. This high density fraction is what allows the polymer to be used in some applications. This prevents the desired optical and abuse properties from being achieved. Improved optical and abuse properties, such as dart impact, without incurring a significant trade-off in performance. There is a need for polymers with reduced high density fractions to enable better . Summary of the Invention

[0006] This embodiment provides a reduced mechanical strength and tear resistance without significant tradeoffs in mechanical strength and tear resistance. This resulted in LLDPE polymers with enhanced high density fractions, as well as improved optical and abuse properties. These requirements are met by creating

[0007] According to one embodiment of the present disclosure, a linear low density polyethylene (LLDPE) polymer The blown film is provided containing ethylene monomer and C3- C 12 It is a polymerization reaction product with ethylene comonomer. LLDPE has a viscosity of 0.904-0. Density 925g / cc, temperature 190°C under a load of 2.16kg according to ASTM 1238 When measured, the melt index (I2) is 0.5 to 1.5 g / 10 min. 、 I 10 but 6.5-7.6 measured according to ASTM 1238 at 190°C with a 10 kg load The melt flow ratio (I10 / I2) of In this case, the molecular weight distribution (MWD = Mw / Mn) is 2.5 to 3.6. Copolymer fractions greater than 5% and comonomer content fractions with improved elution mass vs. temperature Total elution mass measured using a fabric (iCCD) curve from 35°C to 95°C The copolymer fraction, defined as the ratio of the mass eluted at a temperature of 0.5 to 8.0%, High density fraction, defined as the ratio of the mass eluted at temperatures above 95°C to the total mass and a soluble fraction of 1.0% to 12.0%, which is 3% of the total mass. the soluble fraction, defined as the proportion of the mass that is eluted at a temperature of 5°C or less, and This includes the short chain branching distribution.

[0008] According to another embodiment of the present disclosure, a linear low density polyethylene (LLDPE) polymer LLDPE is a polymer made from ethylene monomer and C3-C 12 With ethylene comonomer Contains polymerization reaction products. LLDPE has a density of approximately 0.910 to 0.920 g / cc, 19 When measured according to ASTM 1238 at a temperature of 0°C under a load of 2.16 kg, the Melt index (I2) of 7.0 g / 10 min, and I10 of 19 at a 10 kg load Melt flow ratio (I) of 6.5 to 7.5 measured according to ASTM 1238 at a temperature of 0°C LLDPE has a high density fraction of 0.5 to 6.0% and is a soluble solid. Temperature above 95°C for total eluted mass as measured using the iCCD curve of mass vs. temperature The high-density fraction, defined as the proportion of mass eluted within the range of 1.0–3.0%, and the soluble fraction, defined as the proportion of mass eluted within the range of 1.0–3.0%. the ratio of the mass eluted within a temperature range of 35°C or less to the total eluted mass; The soluble fraction is defined as the ratio of the soluble fraction to the high-density fraction of 0.40 to 0.6. 5 and the maximum elution peak height occurs at a temperature above 80°C. In a further embodiment, the LLDPE comprises a cast filler. It can be included in the program. DETAILED DESCRIPTION OF THE INVENTION

[0009] Certain embodiments of the present application will now be described. However, the present disclosure may be modified to suit different The present disclosure may be embodied in various forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are not intended to be limiting unless expressly stated, and are not intended to be limiting unless otherwise specified. This disclosure is provided to fully convey the principles of the present invention to those skilled in the art.

[0010] definition The term "polymer" refers to a group of monomers, whether of the same or different types. It refers to a polymer compound prepared by polymerizing The general terms are "homopolymer" and "copolymer" or "interpolymer". A homopolymer is usually a polymer prepared from only one type of monomer. Copolymers and interpolymers are usually made up of two or more different polymers. It is used to refer to polymers prepared from monomers that are the same as those in the copolymers. The general terms interpolymer and interpolymer refer to three or more different types of polymers, such as terpolymers. This includes polymers prepared from monomers of the formula:

[0011] "Polyethylene" or "ethylene-based polymer" means a polymer that is greater than 50 mole percent ethylene It is understood that the term "polymer" refers to a polymer containing units derived from a monomer. Contains a monopolymer or copolymer (meaning units derived from two or more comonomers) Common forms of polyethylene known in the art include low density polyethylene. Low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (U LDPE), very low density polyethylene (VLDPE), linear and substantially linear Single-site catalyzed linear low-density polyethylene (m-LLD) containing both methyl methacrylate and methyl methacrylate. PE), medium density polyethylene (MDPE), and high density polyethylene (HDPE) Examples include:

[0012] The term "LDPE" stands for "high pressure ethylene polymer" or "highly branched polymer." The polymer is sometimes referred to as "ethylene" and is prepared by free radical initiators such as peroxides. By using It can be partially or completely homopolymerized or copolymerized in a clave or tubular reactor. (See, for example, U.S. Pat. No. 6,229,629, incorporated herein by reference) No. 8,916,667, U.S. Pat. No. 8,871,887, U.S. Pat. No. 8,822,60 See U.S. Patent No. 1, U.S. Patent No. 9,228,036, and U.S. Patent No. 9,765,160. LDPE resins typically have a density of 0.915 to 0.935 g / cm 3 in the range of It has density.

[0013] The term "LLDPE" includes those made using a Ziegler-Natta catalyst system. Resins produced using bismetallocene catalysts ("m-LLDPE"), as well as resins containing bismetallocene catalysts ("m-LLDPE"), Synthetic LDPEs, including metallocene-LLDPEs and constrained geometry catalysts Resins made using Glucite catalysts, as well as resins made using post-metallocene molecular catalysts LLDPE includes resins made from linear, substantially linear, or non-linear It includes homogeneous polyethylene copolymers or homopolymers. E, containing chain branches not as long as those of U.S. Pat. No. 5,272,236, U.S. Pat. No. 8,272, U.S. Pat. No. 5,582,923, and U.S. Pat. No. 5,773,155 Substantially linear ethylene polymers as further defined in U.S. Pat. No. 3,645,992 homogeneously branched linear ethylene polymer compositions such as those in U.S. Pat. No. 4,077,079; Heterogeneously branched ethylene glycols, such as those prepared according to the process disclosed in US Pat. No. 6,698, are also suitable. ethylene polymers, and / or their derivatives (such as those disclosed in US 3,914,342) The LLDPE resin may be any type of resin known in the art. The reactor or reactor configuration may be used to carry out gas phase, liquid phase, or slurry polymerization, or any of the foregoing. It can be made by any combination.

[0014] The term "MDPE" refers to a polyethylene having a density of 0.926 to 0.945 g / cc. "MDPE" refers to polyethylene, typically produced using chromium or Ziegler-Natta catalysts. Using, but not limited to, bis-metallocene catalysts and constrained geometry catalysts The catalyst is prepared using a single-site catalyst containing

[0015] The term "HDPE" refers to polyethylene having a density greater than about 0.945 g / cc. These generally refer to catalysts that are Ziegler-Natta, chromium, or not limited to these. Prepared with single-site catalysts, including but not limited to bismetallocene and constrained geometry catalysts will be done.

[0016] The term "ULDPE" refers to a polypropylene (PU) material with a density between 0.880 and 0.909 g / cc. These generally refer to ethylene, including but not limited to Ziegler-Natta catalysts. , single-site catalysts, including bismetallocene catalysts and constrained geometry catalysts, and post-metallocene catalysts. As used herein, "propylene-based polymers" are prepared with talocene molecular catalysts. The term "propylene copolymer" refers to a copolymer containing more than 50% by weight of units derived from propylene monomers in polymerized form. This refers to polymers, including propylene homopolymers, random copolymers, polypropylene Polypropylene, impact copolymer, propylene / alpha-olefin interpolymer polymers, and propylene / alpha-olefin copolymers. Polypropylene materials are generally known to those skilled in the art.

[0017] "Multilayer film" means any structure having multiple layers. For example, a multilayer structure The body may have 2, 3, 4, 5, or more layers. Multilayer films are designated by the letter For example, a core layer B and two outer layers A and B may be described as having two outer layers A and B. A three-layer structure having a core and a core C may be designated as A / B / C. A structure with layers B and C and two outer layers A and D is designated as A / B / C / D. Additionally, one skilled in the art will appreciate that additional layers E, F, G, etc. may be incorporated into this structure. You will know that.

[0018] Catalyst Description The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a procatalyst that converts the procatalyst into a catalytically active catalyst. As used herein, "cocatalyst" and "cocatalyst" refer to compounds that chemically react with the catalyst. The terms "activator" and "activator" are interchangeable terms.

[0019] When used to describe certain carbon atom-containing chemical groups, "(C x -C y ) " bracketed expressions of the form " indicate that the unsubstituted form of the chemical group has x carbon atoms, inclusive of x and y. It means that there are y carbon atoms from the atom. For example, (C1-C 50 ) alkyl In its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In the embodiments and general structures, certain chemical groups are R S by one or more substituents such as may be substituted by

[0020] "(C1-C 50 The term "hydrocarbyl" refers to a hydrocarbon group having from 1 to 50 carbon atoms. means hydrocarbon radicals, where each hydrocarbon radical may be aromatic or non-aromatic, saturated or are unsaturated, straight or branched chain, cyclic (having 3 or more carbons, monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and one or more R S to It is either replaced or not replaced by

[0021] In the present disclosure, (C1-C 50 ) hydrocarbyl is unsubstituted or substituted (C-C 50 ) alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 )Cycloalkyl- (C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 ) Ant Rule-(C1-C 20 ) alkylene (such as benzyl (-CH2-C6H5)) .

[0022] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to Unsubstituted or one or more R S each of 1 to 50 carbon atoms substituted by and saturated straight-chain or branched hydrocarbon radicals having 1 to 18 carbon atoms. means a straight-chain or branched hydrocarbon radical. Unsubstituted (C1-C 50 ) Examples of alkyl are: Unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C 5) Alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl , 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-hexyl butyl, 1-nonyl, and 1-decyl. 40 ) Examples of alkyl are: Substitution (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" includes substituents. This means that there are up to 45 carbon atoms in the radical, e.g., (C1 -C5) one R that is alkyl S is replaced by (C 27 -C 40 ) alkyl Each (C1-C5) alkyl is methyl, trifluoromethyl, ethyl, 1-propyl, It can be pyryl, 1-methylethyl, or 1,1-dimethylethyl.

[0023] "(C6-C 50 The term "aryl" refers to unsubstituted aryls having 6 to 40 carbon atoms. or (one or more R S Monocyclic, bicyclic, or tricyclic aromatic hydrocarbons substituted by It means a hydrogen radical, and at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon radicals contain one aromatic ring, while bicyclic aromatic hydrocarbon radicals A tricyclic aromatic hydrocarbon radical has two rings, and a bicyclic or When a tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical One of the rings in the aromatic radical may be aromatic. The other ring or rings in the aromatic radical may be independently fused or non-fused. It can be fused, aromatic or non-aromatic. Unsubstituted (C6-C 50 ) Examples of aryl are , unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 ) aryl, 2-(C1-C 5) Alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indane indenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydroindacenyl Substituted (C6-C 40 ) Aryl Examples of substitutions (C1-C 20) Aryl, substituted (C6-C 18 ) aryl, 2,4 -bis([C 20 ] alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl Examples include fluoren-9-on-1-yl, and fluoren-9-on-1-yl.

[0024] "(C3-C 50 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more substituted aryl groups. R S saturated cyclic hydrocarbon radicals having 3 to 50 carbon atoms, substituted by Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is x~ It has y carbon atoms and is unsubstituted or has one or more R S is replaced by unsubstituted (C3-C 40 ) Cycloal An example of a kill is a non-substituted (C3-C 20 ) cycloalkyl, unsubstituted (C3-C 10 ) Cycloa alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C-C 20 ) cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl. do.

[0025] The term "halogen atom" or "halogen" refers to fluorine atom (F), chlorine atom ( "Halogen" refers to the radical of a halogen atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "fluoride" refers to fluoride (F- ), chloride (Cl - ), bromide (Br - ) or Yo I - ) means the anionic form of a halogen atom.

[0026] Ziegler-Natta catalysts typically include a procatalyst and a cocatalyst. The main components in the Natta Pro catalyst are titanium species, magnesium chloride (MgCl2) support, and and optionally an electron donor. In some embodiments, the titanium precursor and the magnesium precursor The neodymium precursor is chlorinated using a chlorinating agent, optionally in the presence of an electron donor. In some embodiments, magnesium chloride is used to convert the magnesium chloride into a Ziegler-Natta procatalyst. The titanium support is pre-fabricated from a magnesium precursor and subsequently titanium species are introduced, which In some particular embodiments, the chlorination of titanium species can be carried out using a chlorinating agent. The polymerization proceeds in the absence of an electron donor. In some particular embodiments, a salt of the titanium species The oxidation proceeds in the presence of an electron donor. The magnesium chloride carrier is a magnesium compound. In some embodiments, the magnesium chloride support may be prepared via chlorination of The magnesium precursor is prepared by chlorination of a solution of a hydrogen chloride-soluble magnesium precursor. Obtain a MgCl2 slurry in the same hydrocarbon solvent used to make the serum solution. In some embodiments, the magnesium chloride support is added prior to introducing the other procatalyst components. Such magnesium chloride supports may be prepared by preforming magnesium chloride supports, For example, it is also called a preformed MgCl2 slurry.

[0027] In some embodiments, a non-reducing hydrocarbon-soluble amine in the +2 or +3 oxidation state A soluble transition metal compound is combined with a titanium compound to make a Ziegler-Natta catalyst. In some embodiments, the Ziegler-Natta procatalyst is a magnesium Preformed MgC in the same hydrocarbon solvent used to make the precursor solution In some embodiments, the non-reducing transition metal compound is prepared using a 12 slurry. is soluble in the hydrocarbon solvent of the MgCl2 slurry. Without being bound by any theory, Although it is not intended to be used as a catalyst, if MgCl2 is soluble in the hydrocarbon solvent of the slurry, A better dispersion of the transition metal compounds is obtained, and the phase between the transition metal compounds and the MgCl2 surface is In some embodiments, the chlorinating agent also acts as a Ziegler In some embodiments, preformed Natta procatalysts are also used in the synthesis of MgCl2 slurry, titanium compounds, non-reducing hydrocarbons in the +2 or +3 oxidation state Soluble transition metal compounds, and chlorinating agents to prepare Ziegler-Natta procatalysts Titanium compounds, transition metal compounds, and chlorinating agents are added to a MgCl2 slurry. The addition of may be performed simultaneously, together, or in any order (see Table 1 below). (If two or three ingredients are listed together, they are premixed and (They are added together or simultaneously.) [Table 1]

[0028] The present inventors have surprisingly found that non-reducing hydrocarbon-soluble transition metal compounds can be used in the +2 or or +3 oxidation state in the procatalyst to obtain polyethylene copolymers. It was found that the polymer-high density fraction in the polymer solution was significantly reduced. Although not required, the reaction between the transition metal compound and the chlorinating agent may convert the transition metal compound into a hydrocarbon. The MgCl2 is converted to a non-soluble species and deposited on the MgCl2 surface, thus Changes the nature of the interaction between the body and the active titanium species, resulting in a change in the polymer composition Further improvement of polymer properties is also believed to be achieved by including a vanadium compound in the procatalyst. The vanadium compounds were also obtained unexpectedly, along with other procatalyst components. , together, or in any order, may be introduced to the procatalyst.

[0029] In some embodiments, the chlorinating agent is added to the MgCl before the other ingredients. In some embodiments, less than 10% of the non-reducing hydrocarbon soluble transition metal compounds are chlorinated. In another embodiment, the MgCl2 is added to the treated MgCl2 and remains in the solution phase for 30 minutes. Less than 5% of non-reducing hydrocarbon-soluble transition metal compounds were treated with chlorinating agents, such as MgCl2. It remains in the solution phase for 75 minutes after being added to the

[0030] The reaction temperature for adding each procatalyst component to MgCl2 may be the same but different. In some embodiments, the reaction temperature may be from -30°C to 200°C, or from 0°C to The temperature may be selected from 100°C or from 20°C to 50°C.

[0031] The reaction time for adding each procatalyst component to MgCl2 may be different even if the reaction time is the same. In some embodiments, the reaction time is from 1 minute to 10 days, or from 10 minutes to 24 hours. The time can be selected from 30 minutes to 12 hours.

[0032] Embodiments of the present disclosure include heterogeneous procatalysts. The heterogeneous procatalysts include a titanium species, a structure M(OR 1 ) z Hydrocarbon soluble transition metal compounds having the structure A(Cl) x (R 2 )3 -x and a magnesium chloride component.

[0033] Structure of transition metal compounds M(OR 1 ) z In the case of M, the oxidation state is +2 or +3. The transition metal M may be non-reducible and may not contain Ti. The term "transition metal" refers to elements in groups 3-12 of the IUPAC nomenclature, including lanthanides. In one or more embodiments, the transition metal M is a first In some embodiments, the metal is selected from the group consisting of transition metals from the first row (also referred to as fourth row transition metals). M is selected from zinc, copper, cobalt, manganese, iron, or chromium.

[0034] For hydrocarbon-soluble transition metal compounds, M(OR 1 ) z Each R 1 are independently (C1 -C 30 ) hydrocarbyl or -C(O)R 11 wherein R 11 teeth,( C1-C 30 ) hydrocarbyl. M(OR 1 ) z The subscript z is either 2 or 3. The transition metal compound is soluble in a hydrocarbon solvent. In one or more embodiments, each R 1 and R 11 is optionally one or more halogen atoms, or one or more Two or more -Si(RS )3, wherein each R S is (C1-C 30 )Hido In some embodiments, R 1 and R 11 are methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, n -hexyl, n-heptyl, n-octyl, 2-ethylhexyl, tert-octyl, In some embodiments, R may be selected from n-nonyl, n-decyl, or n-decyl. 1 Ga-C (O)R 11 If R 11 3-heptyl and 2-methyloctan-2-yl In one or more embodiments, the hydrocarbon soluble transition metal compound may be selected from naphthenic acid, Naphthenic acids are a mixture of alicyclic carboxylic acids and can be metal salts of the formula C n H2 (n-z) O2, where n is 5 to 30 and z is 0 to 4. In a non-limiting example, when the hydrocarbon-soluble transition metal compound is a metal salt of naphthenic acid: R 1 is -C(O)R 11 and R 11 is (3-ethyl)-2-cyclopentyl-2 Naphthenic acid can be isolated from crude oil.

[0035] In some embodiments, the R of the transition metal compound 1 or R 11 But one or more -Si (R S ) 3 groups, R S is methyl, ethyl, n-propyl, 2-propyl , n-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl n-octyl, 2-ethylhexyl, tert-octyl, n-nonyl, or n In some embodiments, R 1 -C(O)R 11 In this case If, R 11 may be selected from 3-heptyl and 2-methyloctan-2-yl.

[0036] In some embodiments, the transition metal compound is heated to 50° C. or below, preferably 35° C. or below. Most preferably, it is a metal alkoxide or carboxylate having a melting point of 25°C or less. In some embodiments, the transition metal compound M(OR 1 ) z or M(OC(O)R 1 1 ) z is R 1 or R 11 At the second position of the group (C1-C 10 ) containing hydrocarbyl substitution In one or more embodiments, M is zinc, cobalt, copper, manganese, iron, or chromium. In some embodiments, the transition metal compound is selected from zinc(II) 2-ethylhexyl xanoate, zinc(II) neodecanoate, zinc(II) naphthenate, cobalt ( II) 2-ethylhexanoate, cobalt(II) neodecanoate, cobalt(II) ) naphthenate, copper(II) 2-ethylhexanoate, copper(II) neodecanoate, Copper(II) naphthenate, manganese(II) 2-ethylhexanoate, manganese(II ) neodecanoate, manganese(II) naphthenate, iron(III) 2-ethylhexanoate Iron(III) ethoxylate, Iron(III) neodecanoate, Iron(II) naphthenate, Iron(III) ethoxylate Cid, Chromium(III) 2-ethylhexanoate, Chromium(III) neodecanoate or chromium(III) naphthenate.

[0037] Chlorinating Agent Structure A(Cl) x (R 2 ) 3-x So, A is aluminum or boron and R 2 is (C1-C 30 ) hydrocarbyl, where the subscript x is 1, 2, or or 3. In one or more embodiments, the subscript x is 2 and R 2 is methyl, butyl, n-propyl, 2-propyl, n-butyl, tert-butyl, isobutyl, n- Pentyl, n-hexyl, n-heptyl, n-octyl, tert-octyl, n-noni In some embodiments, the subscript x is 3. do.

[0038] In some embodiments, the chlorinating agent is aluminum trichloride, methylaluminum dichloride, or aluminum, dimethylaluminum chloride, ethylaluminum dichloride, diethylaluminum chloride aluminum, ethyl aluminum sesquichloride, isobutyl aluminum dichloride, diisobutyl chloride Aluminum, n-hexylaluminum dichloride, di-n-hexylaluminum chloride, n-Octyl aluminum dichloride, di-n-octylaluminum chloride, boron trichloride, Phenylboron dichloride, dicyclohexylboron chloride, silicon tetrachloride, methyltrichloro Silane, dimethyldichlorosilane, chlorotrimethylsilane, ethyltrichlorosilane, Dichlorodiethylsilane, chlorotriethylsilane, n-propyltrichlorosilane, di Chlorodi(n-propyl)silane, chlorotri(n-propyl)silane, isopropyltri Dichlorosilane, dichlorodiisopropylsilane, chlorotriisopropylsilane, n- Butyltrichlorosilane, Dichlorodi(n-butyl)silane, Chlorotri(n-butyl) Silane, isobutyltrichlorosilane, dichlorodiisobutylsilane, chlorotriisobutyl Trichlorosilane, cyclopentyltrichlorosilane, dichlorodicyclopentylsilane, n- Hexyltrichlorosilane, cyclohexyltrichlorosilane, dichlorodicyclohexyl The hydroxybenzoates may be selected from the group consisting of hydroxybenzoates, ...

[0039] In one or more embodiments, the heterogeneous procatalyst further contains a vanadium component. The vanadium species is VX4, VOX3, or VO(OR 3 )3, wherein each X is independently a halogen atom or (C-C 40 ) heterohydrocarbyl, and R 3 is (C1-C 20 ) hydrocarbyl or -C(O)R 31 and R 31 is (C 1-C 30 ) hydrocarbyl. In one or more embodiments, R 3 and R 31 Is, butyl, ethyl, n-propyl, 2-propyl, n-butyl, tert-butyl, isobutyl n-pentyl, n-hexyl, n-heptyl, n-octyl, tert-octyl, In some embodiments, R may be selected from n-nonyl, n-decyl, or n-decyl. 1 Ga-C (O)R 31 If R 31 is 3-heptyl.

[0040] In some embodiments, the vanadium component is vanadium(IV) chloride, oxytrisalt Vanadium(V) oxide, vanadium(V) oxytrimethoxide, vanadium(V) oxytrimethoxide Triethoxide, Vanadium(V) Oxytripropoxide, Vanadium(V) Oxytripropoxide vanadium(V) oxyisopropoxide, vanadium(V) oxytributoxide, vanadium(V) oxy Triisobutoxide, Vanadyl Acetate, Vanadium(IV) Oxide Stearate, Octa vanadium phosphate, vanadium phosphate, and combinations thereof.

[0041] In embodiments, the polymerization process for the ethylene-based polymer comprises reacting ethylene with a catalyst system and optionally one or more α-olefins, wherein the catalyst system comprises contacting It comprises a heterogeneous procatalyst or two or more heterogeneous procatalysts.

[0042] In an embodiment, the process for producing a heterogeneous procatalyst comprises adding a MgCl slurry This involves forming magnesium chloride (MgCl2) in a hydrocarbon solvent. mixing the chlorinating agent, the transition metal compound, and the titanium species in the MgCl slurry; Therefore, transition metal compounds have the structure M(OR 1 ) z and the chlorinating agent has the structure A(Cl) x (R 2 ) 3-x It has.

[0043] In one or more embodiments of the heterogeneous catalyst, the magnesium chloride component is When measured at 100m 2 In some embodiments, the salt has a surface area of ​​1 / g or more. The magnesium chloride component is 150m 2 / g or more, or 200m 2 / g or more surface area In another embodiment, the magnesium chloride component is 100 ml2 / g~800m 2 / g, or 200m 2 / g~600m 2 / g, or 300m 2 / g~500m 2 / g surface area It has.

[0044] In one or more embodiments, the magnesium chloride is obtained from the chlorination of a magnesium compound. Such magnesium compounds include organomagnesium compounds, such as magnesium nitrate, ... , organic magnesium halides, magnesium alkoxides, magnesium carbonate alkoxides oxide, magnesium carboxylate, and combinations thereof. In the form, magnesium chloride can be obtained from the conversion of magnesium chloride adducts. Suitable magnesium chloride adducts include magnesium chloride adducts with alcohols and In some embodiments, magnesium chloride adducts with ethers are included. The neodymium adduct is a magnesium chloride adduct with ethanol. In this case, the magnesium chloride adduct is a magnesium chloride adduct with tetrahydrofuran. do.

[0045] In one or more embodiments, the magnesium chloride component may be prepared by, for example, combining a chloride source with a hydrocarbon including reaction products with a soluble hydrocarbyl magnesium compound or mixture of compounds Exemplary organomagnesium compounds include di(C1-C 20 ) Alkyl magnesium Or Ji (C1-C 20 ) Aryl magnesium compounds, especially di(n-butyl) magnesium magnesium, di(sec-butyl)magnesium, diisopropylmagnesium, di-n-hexyl Silmagnesium, Isopropyl-n-butyl-magnesium, Ethyl-n-hexylmagnesium magnesium, ethyl-n-butylmagnesium, di-n-octylmagnesium, and Combinations thereof are also included. Exemplary suitable magnesium diaryls include di Examples include phenylmagnesium, dibenzylmagnesium, and ditolylmagnesium. Organomagnesium compounds are used to improve solubility, reduce solution viscosity, or Optionally, an organoaluminum compound may be added to improve solubility and reduce solution viscosity. Stabilizers, including those derived from substituted phenolic compounds, may also be present. Additional suitable organomagnesium compounds include alkyl and aryl magnesium compounds. Included are alkoxides, aryloxides and chlorides, as well as mixtures of the foregoing. The preferred organomagnesium compounds are always halogen-free organomagnesium compounds. be.

[0046] Among the chloride sources that may be used in preparing the magnesium chloride component for use herein are These include metal chlorides and non-metal chlorides, including organic chlorides and hydrogen chloride. Suitable metal chlorides that may be used herein are MR y-a Cl a where M is is a metal of Group 13, 14, or 15 of the Periodic Table of Elements, and R is a monovalent organic radical. where y has a value corresponding to the valence of M, and a has a value from 1 to y.

[0047] In one or more embodiments, the metal chloride has the formula AlR 3-a Cl a Alkyl groups having aluminum chloride, wherein each R is independently selected from the group consisting of (C-C 10 ) Hydroca Preferably, a is 1 to 3. Examples of alkylaluminum include ethylaluminum sesquichloride and diethylaluminum chloride. Examples of suitable chlorine-containing compounds include, but are not limited to, aluminum, and ethylaluminum dichloride. Ethyl aluminum chloride is particularly preferred. Alternatively, metal chlorides such as aluminum trichloride are also preferred. or aluminum trichloride and alkylaluminum chloride or trialkylaluminum chloride A combination with a tungsten compound may be preferably used.

[0048] Suitable non-metallic chlorides and organic chlorides have the formula R'Cl r wherein R' is hydrogen, (C1-C 10 ) hydrocarbyl, or Si, P, Ga, or Ge, etc. The subscript r is an integer from 1 to 6. Particularly suitable chloride sources include, for example, For example, hydrogen chloride, as well as t-alkyl chloride, sec-alkyl chloride, aryl chloride, chloride, and benzyl chloride, as well as other active hydrocarbyl chlorides. Included are organic chlorides, wherein hydrocarbyl is as defined hereinbefore. Active organic chlorides are those that are at least as active, i.e., readily convertible to other compounds. Preferably, t-butyl chloride, such as sec-butyl chloride, is used, which is lost in the By hydrocarbyl chloride is meant a hydrocarbyl chloride containing an unstable chloride that is as active as chloride. In addition to the organic monochlorides, organic dichlorides, trichlorides, etc., which are active as defined herein above, It is believed that chlorides, and other polychlorides, may also be suitably used. Examples of preferred chloride sources are: Examples include hydrogen chloride, t-butyl chloride, t-amyl chloride, allyl chloride, and benzene chloride. Most preferred are: Hydrogen chloride, t-butyl chloride, allyl chloride, and benzyl chloride.

[0049] In some embodiments, the chloride compound may be hydrochloride gas. Organomagnesium compounds and chloride compounds are stored at temperatures between -25°C and 100°C, or between 0°C and 50°C. In some embodiments, the reaction temperature may be within ±5°C, e.g., Heat removal is required to control the temperature, for example, to within ±3°C. The amount of source is controlled to achieve the target molar ratio of Cl to Mg in the resulting MgCl. For example, the molar ratio of Cl to Mg is 0.05 for chloride-deficient MgCl2 supports. is 1.8-2.0, and in the case of MgCl2 support containing a large amount of chloride, it is 2.0-2.2. In some embodiments, the organomagnesium compound and the metal or non-metal chloride The slurry of material may be in contact for a period of 1 hour to 12 hours, or for a period of 4 hours to 6 hours. the concentration of organomagnesium compounds in the slurry (i.e., before the chloride compounds are added to the slurry) ) is the amount of chloride compound added to a slurry so that the resulting composition is May contain magnesium concentrations from 0.005 molar (mol / L) to 1.000 mol / L It may be sufficient to do so.

[0050] In some embodiments, the MgCl slurry may be treated with other procatalyst components prior to treatment. These are prepared in advance and are referred to herein as "preformed MgCl slurries." In this embodiment, the MgCl slurry is 0.005 mol / L to 10.00 mol / L , or may have a concentration of MgCl2 of 0.05 mol / L to 1.00 mol / L.

[0051] The magnesium chloride support is preformed from an organomagnesium compound and a chloride source. It can be obtained and stored for later use, or it can be preformed in situ and In this case, the procatalyst may be prepared by reacting, in a suitable solvent or reaction medium, (1) an organomagnesium component and (2) It is preferably prepared by mixing a chloride source followed by the other procatalyst components. It's nice.

[0052] In one or more embodiments, the titanium species can be a catalytically active titanium species. In some embodiments, the titanium species is TiCl 4-c (OR) c or TiCl 3-d (O R) d where R is (C1-C 20 ) hydrocarbyl, and c is 0, 1, 2 , 3, or 4, and d is 0, 1, 2, or 3. For example, in some embodiments In the titanium species, titanium(IV) tetrachloride, titanium(III) trichloride, tris(2,2 ,6,6-tetramethyl-3,5-heptanedionato)titanium(III), trichloro Tris(tetrahydrofuran)titanium(III), di-n-butoxytitanium(IV) dichloride , diethoxytitanium(IV) dichloride, diisopropoxytitanium(IV) dichloride, di Isobutoxytitanium(IV), triisopropoxytitanium(IV) chloride, tri-n- Butoxytitanium(IV), triisobutoxytitanium(IV) chloride, titanium(IV) tetrachloride Isopropoxide (Ti(O i Pr)4), titanium(IV) ethoxide, titanium(IV) n-Butoxide, Titanium(IV) Isobutoxide, Titanium(IV) 2-Ethylhexoxy Dichlorobis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium (IV), tetrachlorobis(tetrahydrofuran)titanium(IV), methyltitanium trichloride (IV), or combinations thereof. In some embodiments, the titanium species is titanium(IV) tetrachloride or titanium(IV) Tetraisopropoxide (Ti(O i Pr) 4). For example, in some embodiments In this embodiment, the titanium species may be a titanium halide, a titanium alkoxide, or a combination thereof. For example, in some embodiments, the titanium species may include titanium tetrachloride (T iCl4), titanium(IV) tetraisopropoxide (Ti(O i Pr)4), other halos Titanium fluoride, titanium alkoxide, or a combination thereof. , but not limited to these.

[0053] In embodiments, the process for making the heterogeneous procatalyst includes a hydrocarbon solvent. The solvent is non-halogenated (C3-C 30 ) alkyl or non-halogenated (C3-C 30 ) Shi In some embodiments, the hydrocarbon solvent may be selected from isopropyl alcohol, methyl alcohol, methyl methyl methacrylate ... Examples of isoparaffinic solvents include those from ExxonMobil ISOPAR™ synthetic paraffinic solvents (e.g., ISOPAR™) available from Paraffinic solvents) and special boiling points (S) according to Shell Chemicals BP) solvents (e.g., SBP 100 / 140 high-purity dearomatized hydrocarbon solvent) Other examples of hydrocarbon solvents include, but are not limited to, isobutane, Pentane, isopentane, cyclopentane, hexane, 2-methylpentane, 3-methyl Pentane, cyclohexane, methylcyclopentane, heptane, 2-methylhexane, 3 -methylhexane, octane, 2,2,4-trimethylpentane, tetradecane, and Combinations of these may be included.

[0054] In one or more embodiments of the heterogeneous catalyst, the transition metal M (in the transition metal compound) and titanium The ratio of the hydroxybenzoates to the hydroxybenzoates is 0.1 to 10 (mol / mol). All individual values ​​and subranges included are herein disclosed as separate embodiments. For example, the range "0.1 to 10 (mol / mol)" can be expressed as subranges of 0.2 to 5, 0. Including 5 to 3 and 0.3 to 2.

[0055] In one or more embodiments of the heterogeneous catalyst, the molar ratio of magnesium chloride to titanium is: 1 to 100 (moles of magnesium chloride per mole of titanium metal) All individual values ​​and subranges encompassed by the above are herein disclosed as separate embodiments. For example, the range "1 to 100" can be expressed as subranges of 8.0 to 80, 15 to 50, and 30-70 inclusive.

[0056] In one or more embodiments of the heterogeneous catalyst, the molar ratio of vanadium to titanium is 0.1 ~10 (moles of vanadium per mole of titanium metal). Included in "0.1~10" All individual values ​​and subranges listed herein are disclosed herein as separate embodiments, and For example, the range "0.1 to 10 (mol / mol)" can be divided into subranges of 0.2 to 5 and 0.5 ~3, and 0.3~4.

[0057] In some embodiments, the method of claim 9,255, which is incorporated herein by reference. Multimetallic procatalysts can be utilized as described in U.S. Pat. No. 6,160. The multimetallic procatalysts used in the production of the compounds are at least trimetallic, but may contain more than three metals. Transition metals may also be included, and therefore, in one embodiment, may be more generally defined as multimetallic. These three or more transition metals are selected prior to catalyst formation. In certain embodiments, The multimetallic catalyst contains titanium as one element.

[0058] promoter component The heterogeneous procatalysts according to the present disclosure may be combined with a cocatalyst to form Ziegler-Natta catalysts. Ziegler-Natta catalysts, including heterogeneous procatalysts, are useful in olefin polymerization reactions. Any technique known in the art for activating the Ziegler-Natta type procatalyst for the reaction For example, heterogeneous procatalysts can be made catalytically active by by contacting the procatalyst with an activating cocatalyst or by combining the procatalyst with an activating cocatalyst. Suitable activating cocatalysts for use herein are alumoxanes, including polymeric or oligomeric alumoxanes (also known as aluminoxanes) Combinations of one or more of the foregoing activating cocatalysts are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides. Or monoalkylaluminum dihalide, dialkylaluminum hydride or means a dialkylaluminum halide or a trialkylaluminum. Examples of malealumoxanes or oligomeric alumoxanes include methylalumoxane, thiaminyl ... Examples include triisobutylaluminum-modified methylalumoxane and isobutylalumoxane. In some embodiments, the co-catalyst may be an alkyl of aluminum, an alkyl of aluminum, or an alkyl of aluminum. aluminum haloalkyls, alkylaluminum halides, and mixtures thereof In some embodiments, the co-catalyst may be selected from the group consisting of triethylaluminum, trimethylaluminum, and the like. butylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri- n-Hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride chloride, MAO, MMAO, diethylaluminum ethoxide, and mixtures thereof can be selected from:

[0059] Ethylene-based polymers The catalyst systems described in this disclosure are useful for the polymerization of olefins, primarily ethylene-based polymers. In some embodiments, a single olefin or Only α-olefins are present to form homopolymers. However, additional α-olefins The additional α-olefin comonomer may be incorporated into the polymerization procedure. , and has 20 or less carbon atoms. For example, the α-olefin comonomer has 3 to 10 carbon atoms. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, Examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. 1-pentene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, the one or more α-olefin comonomers may be propylene, 1 from the group consisting of 1-butene, 1-hexene, and 1-octene, or alternatively 1-hexene The alkylene may be selected from the group consisting of 1-octene and 1-octene.

[0060] Ethylene-based polymers, such as homopolymers and / or interpolymers of ethylene a mer (including a copolymer), and optionally one or more comonomers such as an α-olefin. The monomers contain at least 50 mole percent (mol%) ethylene-derived monomer units. All individual values ​​encompassed by "from at least 50 mole percent" and Each and every subrange is disclosed herein as a separate embodiment, and includes, for example, ethylene-based polymers. , ethylene homopolymers and / or interpolymers (including copolymers), and optionally one or more comonomers such as an α-olefin, at least 60 mole percent of ethylene-derived monomer units and at least 70 mole percent of ethylene-derived monomer units mole percent, at least 80 mole percent of monomer units derived from ethylene; or 50 to 100 mole percent of ethylene-derived monomer units, or It may contain 80 to 100 mole percent mer units.

[0061] In some embodiments, the catalyst system comprises at least 90 mole percent ethylene-derived The ethylene-based polymer may comprise at least 90 mole percent of the units. All individual values ​​and subranges are included herein and are treated as separate embodiments disclosed herein. For example, an ethylene-based polymer may contain at least 93 mole percent ethylene-derived units. at least 96 mole percent of units derived from ethylene, and at least 97 mole percent of units derived from ethylene. mole percent, or alternatively, 90 to 100 mole percent of units derived from ethylene; 90 to 99.5 mole percent of ethylene-derived units, or 90 to 99.5 mole percent of ethylene-derived units It may contain 7 to 99.5 mole percent.

[0062] In some embodiments, the catalyst system is less than 50 mole percent (mol%) In other embodiments, the ethylene-based polymer may be formed with an amount of additional α-olefin. The amount of the added α-olefin is at least 0.01 mol % to 25 mol %, and further In the form, the amount of additional α-olefin contains at least 0.1 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene or 1-hexene. It is.

[0063] Producing an ethylene-based polymer in the presence of a catalyst system comprising the heterogeneous procatalyst of the present disclosure Any conventional polymerization process can be used to prepare the polymerizable polymer. For the purpose of the present invention, one or more conventional reactors may be used, such as a loop reactor, an isothermal reactor, a fluidized bed gas phase reactor, Stirred tank reactors, batch reactors, etc., can be used in parallel, series, or any combination thereof. solution polymerization process, gas phase polymerization process, slurry phase polymerization process, and In one embodiment, ethylene The system polymer is prepared by solution polymerization in a dual reactor system, e.g., a dual loop reactor system. wherein ethylene, and optionally one or more α-olefins, are produced by the method of the present invention. The polymerisation is carried out in the presence of a catalyst system as described herein and optionally one or more co-catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, is used in a first reactor or In one embodiment, the ethylene-based polymer may be used in either the first or second reactor. can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system. wherein ethylene, and optionally one or more α-olefins, are The polymerization is carried out in both reactors in the presence of the catalyst system described in

[0064] In another embodiment, the ethylene-based polymer is produced in a single reactor system, e.g., a single loop It can be produced via solution polymerization in a reactor system or a single stirred tank reactor system, where: The ethylene and optionally one or more α-olefins are as described in this disclosure. Such a catalyst system, optionally one or more cocatalysts as described in the previous paragraph, and optionally The copolymer is polymerized in the presence of one or more other catalysts in combination.

[0065] In the embodiments described herein, the ethylene-based polymer is polyethylene polymer 10 100,000 parts by weight of at least three metal residues, Preferably, the at least three metallic residues are zinc, titanium, zirconium, hafnium, vanadium, Aluminum, niobium, tantalum, chromium, molybdenum, tungsten, and combinations thereof and each of the at least three metal residues is 0.2 ppm or more, e.g., For example, it is present in the range of 0.2 to 5 ppm. All individual values ​​from 0.2 ppm and above All ranges and subranges are included herein and disclosed herein. For example, ethylene-based polyolefins The polymers further comprise, per million parts of the polyethylene composition, residual polymers from the multimetallic polymerization catalyst. At least three metal residues may be present in a total of 2 parts by weight or more. The ethylene-based polymer contains at least 0.75 ppm of V (vanadium). All individual values ​​and subranges from V of at least 0.75 ppm are included and are within the scope of the present specification. For example, the lower limit of V in the ethylene-based polymer is 0.75, 1, 1 0.1, 1.2, 1.3, or 1.4 ppm above V in the ethylene-based polymer The limits are 5, 4, 3, 2, 1.9, 1.8, 1.7, 1.6, 1.5, or 1 ppm. It is possible.

[0066] The ethylene-based polymer may further include one or more additives. These include antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, Processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. is about 0 to about 10 percent, based on the weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer may further comprise a filler. The filler may include organic or inorganic fillers. The ethylene-based polymer is not limited to the ethylene-based polymer and all additives. or based on the total weight of the filler, e.g., calcium carbonate, talc, or Mg(OH The ethylene-based polymer may contain from about 0 to about 20 weight percent of a filler such as ethylene-based copolymer (EPO) 2. It may be further compounded with one or more polymers to form a blend. In embodiments, the additives, fillers, one or more polymers, or compounding agents may be added to the overall ethylene The density of the system polymer may be increased or decreased.

[0067] The ethylene-based polymers are prepared according to ASTM D792, which is incorporated herein by reference in its entirety. The density may be 0.850 g / cc to 0.970 g / cc due to the addition of Ethylene polymers: 0.904-0.925g / cc, 0.904-0.920g / cc, 0.910~0.920g / cc, 0.916~0.920, 0.915~0.9 25, 0.917-0.923, or 0.912-0.918 g / cc Further, the ethylene-based polymer may include LLDPE. c, 0.931~0.965g / cc, 0.932~0.950, 0.930~0.94 L with a density of 0, 0.950-0.970, or 0.933-0.940 g / cc Further, the ethylene-based polymer may include LDPE. , 0.916~0.929g / cc, 0.917~0.928, or 0.918~0. It may include LLDPE having a density of 927 g / cc.

[0068] In another embodiment, the ethylene-based polymer (e.g., LLDPE) is heated to 190°C and 2.16 kg load according to ASTM D1238 (incorporated herein by reference in its entirety). When measured according to procedure D, the melt index, I2, between 0.1 and 7.0 For blown film applications, ethylene polymers have a viscosity of 0.5 to 2.5 g / 10 min, or 0.5 to 2.0 g / 10 min, or 1 g / 10 min or less melt index For cast film applications, ethylene The polymer is 2.0 to 7.0 g / 10 min, or 2.0 to 4.0 g / 10 min, or 2 It may be an LLDPE having a melt index (I2) of 0.5 to 3.5 g / 10 min.

[0069] Further, the ethylene-based polymer may have a viscosity of 5 to 9, or 5 to 7.7, or 6.5 to 7.7. , or 6.5 to 7.6, or 6.5 to 7.5 melt flow ratio (I 10 / I2) It can be LLDPE, I 10 meets ASTM D12 at 190°C and 10 kg load. 38 (Procedure D).

[0070] In other embodiments, the LLDPE is soluble in water by conventional gel permeation chromatography (GPC). When measured by the method, the molecular weight distribution (MWD) may be 2.5 to 3.6, and the MWD is M w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the LLDPE has an MWD of 2.8 to 3.8. In a further embodiment, the LLDPE has an MWD of 3.0 to 3.6. The PE has an MWD of 3.1 to 3.5. In a further embodiment, the LLDPE has an MWD of 3. It has an MWD of 2 to 3.4.

[0071] Furthermore, LLDPE is characterized by an improved comonomer content distribution (iCCD) curve. In one embodiment, the LLDPE comprises 0.5 to 8.0% of short chain branching. The high density fraction may have a high density fraction determined by CCD, the high density fraction being 95% of the total eluted mass. It is defined as the proportion of the mass that is eluted at temperatures above 9 °C. In some cases, the temperature range is In a further embodiment, the LLDPE may be 0.5 to 8.0%, 0 It may have a high density fraction of 0.5 to 7.5%, or 3.0% to 8.0%.

[0072] Furthermore, LLDPE has a solubility determined by iCCD of 0.5% to 12.0%. or a purge fraction, and the soluble fraction is eluted at a temperature of 35°C or less relative to the total eluted mass. In some cases, the temperature range can be 23-35°C. In a further embodiment, the soluble fraction is less than 5%. Additionally, the soluble fraction is less than 0. 5%~5.0%, 0.5%~4.0%, 0.5%~3.0%, 0.5%~2.0%, 0. 5%~1.0%, 1.0%~5.0%, 1.0%~4.0%, 1.0%~3.0%, 1. 0%~2.0%, 2.0%~5.0%, 2.0%~4.0%, 2.0%~3.0%, 3. 0%~5.0%, 3.0%~4.0%, 4.0%~5.0%.

[0073] Additionally, the LLDPE may have a copolymer fraction of greater than 85%, the copolymer fraction being , above 35°C relative to the total eluted mass as measured using the iCCD curve of eluted mass versus temperature It is defined as the proportion of mass that is eluted at a temperature of less than 95°C. The copolymer fraction is greater than 90%. In a further embodiment, the copolymer fraction is greater than 85%. and less than 92%. In a further embodiment, the ratio of soluble fraction to high density fraction is , 0.4 to 0.65. Without being limited by theory, the improvements discussed below The improved properties are due, in part, to this larger copolymer fraction and the smaller solubility and high This is due to density fractionation.

[0074] Furthermore, the maximum elution peak height for LLDPE can occur at temperatures above 80°C. In this embodiment, the maximum elution peak height of the LLDPE may occur at a temperature of less than 90°C. In other words, the maximum elution peak height of LLDPE is between 80 and 95°C or between 80 and 9 It can occur at temperatures of 0°C.

[0075] Blown Film The above ethylene polymers (e.g., LLDPE) can be used for blown film. Various thicknesses of the blown film are contemplated. In terms of form, blown film is available in thicknesses of 0.3 mil to 10.0 mil, 0.3 mil to 9. 0 mil, 0.3 mil to 8.0 mil, 0.3 mil to 7.0 mil, 0.3 mil to 6.0 mil, 0.3mil to 5.0mil, 0.3mil to 4.0mil, 0.3mil to 3.0mil, 0.3mil mil to 2.0 mil, 0.3 mil to 1.0 mil, 1.0 mil to 10.0 mil, 1.0 mil to 9 0.0 mil, 1.0 mil to 8.0 mil, 1.0 mil to 7.0 mil, 1.0 mil to 6.0 mil , 1.0mil to 5.0mil, 1.0mil to 4.0mil, 1.0mil to 3.0mil, 1.0 The thickness may range from 1.0 mil to 2.0 mil, or any combination of these ranges.

[0076] Without being bound by theory, the above LLDPE is determined by the above iCCD parameters, i.e. The short-chain branching distribution is defined by the soluble fraction, copolymer fraction, and high-density fraction. Improved optical properties (e.g., haze) and abuse resistance (e.g., dirt) Provides a service.

[0077] In one embodiment, the blown film has a thickness of 2.0 mils and a melting point of 4.5% to 10 0.5% total haze (%), 5.4% to 10.2% at 2.0 mil thickness, or 2.0 mil The film may have a total haze of 7.0% to 10.0% at a thickness of 1000 mm. The film is at least 2.0 mils thick and has a resin density of less than 0.918 g / cc. Both have a dirt value of 900g, and / or a thickness of 2.0 mils, and 1.1g / 10min A melt index of less than 0.920 g / cc and a resin density of at least 600 g May have dirt value.

[0078] Various film configurations are contemplated for blown film. The insulation film may be a multi-layer film or a mono-layer film. The number of layers of the inflation film depends, for example, on the desired properties of the film, the desired thickness of the film, thickness, the content of other layers in the film, the end use of the film, the equipment available for producing the film, The thickness of the multilayer blown film may depend on several factors, including: In various embodiments, the membrane may include up to 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 layers. It can be done.

[0079] The ethylene-based polymers described above may, in some embodiments, be used in one or more layers of the film. Within the monolayer film, the layers may, in various embodiments, be any of the above-mentioned epoxy groups. Styrene polymers, LLDPE, VLDPE (very low density polyethylene), MDPE, LD PE, HDPE, HMWHDPE (high molecular weight HDPE), propylene polymers, polio Refinplastomer (POP), Polyolefin elastomer (POE), Olefin Block copolymer (OBC), ethylene vinyl acetate, ethylene acrylic acid, ethylene methacrylate Acrylic acid, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene butyl acrylate, isobutylene, maleic anhydride grafted polyolefin, any of the foregoing a polymer and component selected from any of the ionomers, or a combination thereof; Within a monolayer film, each layer may, in various embodiments, include a The above ethylene polymers, LLDPE, VLDPE (very low density polyethylene), MDPE , LDPE, HDPE, HMWHDPE (high molecular weight HDPE), propylene polymers, Polyolefin plastomer (POP), polyolefin elastomer (POE), olefin OBC, ethylene vinyl acetate, ethylene acrylic acid, ethylene Ethylene methacrylic acid, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene butyl acrylate, isobutylene, maleic anhydride grafted polyolefin, Polymers and components selected from any ionomer, or combinations thereof In some embodiments, the multilayer film of the present disclosure can include a blend comprising: It may include one or more tie layers known to those skilled in the art.

[0080] In one embodiment, the LLDPE is blended with LDPE. The blown film, which can be a monolayer or multilayer film, contains 50 to 95% by weight of LLDPE, or 60-90% by weight of LLDPE, or 70-85% by weight of LLDP Conversely, the blend may contain 5 to 50 wt. % LDPE, or It may contain 10 to 40% by weight of LDPE, or 15 to 30% by weight of LDPE.

[0081] Cast film The above ethylene-based polymers (e.g., LLDPE) can also be incorporated into cast films. Various thicknesses of the cast film are contemplated. The thickness of the film is 0.3 mil to 10.0 mil, 0.3 mil to 9.0 mil, 0.3 mil to 8.0 mil. 0.0 mil, 0.3 mil to 7.0 mil, 0.3 mil to 6.0 mil, 0.3 mil to 5.0 mil , 0.3mil to 4.0mil, 0.3mil to 3.0mil, 0.3mil to 2.0mil, 0.3 mil to 1.0 mil, 0.3 mil to 0.8 mil, 0.2 mil to 0.6 mil, 0.3 mil to 0 0.4 mil, 1.0 mil to 10.0 mil, 1.0 mil to 9.0 mil, 1.0 mil to 8.0 mil 1.0 mil to 7.0 mil, 1.0 mil to 6.0 mil, 1.0 mil to 5.0 mil, 1. 0 mil to 4.0 mil, 1.0 mil to 3.0 mil, 1.0 mil to 2.0 mil, or any of these The thickness may be any combination of the ranges.

[0082] Without being bound by theory, the above LLDPE is determined by the above iCCD parameters, i.e. The short-chain branching distribution is defined by the soluble fraction, copolymer fraction, and high-density fraction. In one or more embodiments, the cap provides an improved balance of stretching and puncture. The film is 20 inches wide and 0.5 mil thick with at least 50 lbf High Furthermore, the cast film has a stretch strength of at least about 1 4 lbf pallet puncture resistance and at least approximately 370% Hi at 0.5 mil thickness It may have a bright extreme extension.

[0083] In another embodiment, the cast film has a pallet puncture resistance of at least 11 lbf. Highlight ultimate elongation of at least 340% at 0.7 mil thickness Additionally, the cast film must be at least 5 mm thick with a width of 20 inches and a thickness of 0.7 mils. It may have a Highlight (200%) stretch force of 9 lbf.

[0084] Like blown film, cast film is available in a variety of film configurations. For example, the cast film can be a multilayer film or a monolayer film. Additionally, the cast film may contain additional components such as ethylene-based polymers. The ethylene-based polymer may, in some embodiments, be used in more than one layer of the film. Other layers within the multilayer film of the present invention may, in various embodiments, be the ethylene copolymers described above. Polymers, LLDPE, VLDPE (very low density polyethylene), MDPE, LDPE, HDPE, HMWHDPE (high molecular weight HDPE), propylene polymers, polyolefins Polyolefin elastomer (POP), polyolefin elastomer (POE), olefin block OBC copolymer, ethylene vinyl acetate, ethylene acrylic acid, ethylene methacrylic acid Acid, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene butyl acrylate acrylate, isobutylene, maleic anhydride grafted polyolefin, any of the foregoing The polymer may include a polymer selected from the group consisting of hydroxyapatite, ... In some embodiments, the multilayer films of the present disclosure may include one or more tie layers known to those skilled in the art. Some additional components or layers commonly used in the art may include: adhesion ("adhesion") to other LLDPE, amorphous hydrocarbons and / or pallets Other LLDPE blended with other materials known in the art to enhance , polypropylene homopolymer, and polypropylene copolymer with polyethylene These may include (but are not limited to):

[0085] In one embodiment, the LLDPE is blended with LDPE. The cast film, which can be a monolayer or multilayer film, is made of 5 to 95% by weight of LLDPE. , 5 to 50 wt% LLDPE, 5 to 25 wt% LLDPE, 5 to 10 wt% LLD PE, 10-95 wt% LLDPE, 10-50 wt% LLDPE, 10-25 wt% % LLDPE, 50-95% by weight LLDPE, 60-90% by weight LLDPE, or Conversely, blends may include blends having 5 to 85 wt.% LLDPE. 50% by weight LDPE, 10-40% by weight LDPE, or 15-30% by weight LDP It may contain E.

[0086] Test Method density Samples for density measurements were prepared according to ASTM D 4703-10. Pressed at 74°F (190°C) for 5 minutes at 10,000 psi (68 MPa). The temperature was maintained at 374°F (190°C) for the above 5 minutes, and then the pressure was increased to 30,000 psi (2 This was followed by a 30,000 bar increase to 70°F (21°C) and 30,000 bar. The pressure was held at 0 psi (207 MPa) for 1 minute. Density measurements were performed according to ASTM D792-08, Method B was used and was performed within 1 hour of sample compression.

[0087] Melt index (I2 and I 10 ) Melt Index (MI) or I2 is determined according to ASTM D1238-13, Condition 19 0°C / 2.16 kg, measured according to procedure D (multiple weighing procedure), dissolved per 10 minutes The values ​​were reported in grams per 10 min (g / 10 min). I10 was calculated using the same procedure but with a 10 kg load. and was also reported as grams dissolved per 10 minutes (g / 10 min).

[0088] Gel Permeation Chromatography (GPC) For gel permeation chromatography (GPC), the chromatographic system is PolymerChar GPC-IR (Valencia, Spain) equipped with an IR5 detector ain) High temperature GPC chromatograph. Autosampler oven compartment The temperature of the inlet was set to 160 degrees Celsius and the column compartment was set to 150 degrees Celsius. The columns used were three Agilent "Mixed B" 30cm 10 micron linear The chromatography solvents used were: 1,2,4-trichlorobenzene and 200 ppm butylated hydroxytoluene ( The solvent source was sparged with nitrogen. The injection volume used was 200 The volume was measured in microliters and the flow rate was 1.0 milliliters / minute.

[0089] Calibration of the GPC column set was performed using six columns with at least one order of magnitude between individual molecular weights. in the range of 580 to 8,400,000 g / mol, arranged in two "cocktail" mixtures. The analysis was carried out using 21 narrow molecular weight distribution polystyrene standards with molecular weights of 1.001 to 1.001. , purchased from Agilent Technologies. Polystyrene standards were 1, 0.025 g in 50 ml of solvent for molecular weights above 100,000 g / mol and 50 ml of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were prepared at 0.05 grams in a medium at 80°C with gentle agitation. The polystyrene standard peak molecular weight was calculated using Equation 1 for polyethylene terephthalate. The molecular weight was converted to a molecular weight (Williams and Ward, J. Sci., Polym. Lett., 6, 621 (1968)). M ポリエチレン =A×(M ポリスチレン ) B (EQ1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0090] A fifth order polynomial was used to fit each polyethylene equivalent calibration point. The column digestion was performed to obtain the standard NBS1475 with a molecular weight of 52,000 g / mol (Mw). A small adjustment to A (approximately 0.415) was made to correct for the effect of band broadening. ~0.44).

[0091] The total plate count of the GPC column set was calculated using (50 ml trichlorobenzene (0.04 g in TCB and dissolved for 20 minutes with gentle stirring) Plate count (Equation 2) and symmetry (Equation 3) were calculated according to the following equations: Measurements were taken with a 0.00 microliter injection.

number

number

[0092] The samples were analyzed using PolymerChar's "Instrument Control" software. The samples were prepared in a semi-automated fashion using Poly Septa caps pre-sparged with nitrogen were placed through a MerChar high-temperature autosampler. A solvent (containing 200 ppm BHT) was added to the vial. The sample was shaken slowly. The mixture was melted at 160 degrees Celsius for 2 hours.

[0093] Mn, Mw, and Mz calculations were performed using PolymerChar GPC-IR chromatography. Using the graph's internal IR5 detector (measurement channel), Polymer Char GPCOne™ software, each equally spaced data collection point (i) The baseline-subtracted IR chromatogram at and the narrow standard at point (i) from Eq. Based on GPC results using polyethylene equivalent molecular weights obtained from a calibration curve.

number

number

number

[0094] To monitor deviations over time, a PolymerChar GPC-IR system was used. A flow rate marker (decane) was introduced into each sample via a controlled micropump. Quantity markers match each decane peak in the sample to a decane peak within a narrow standard calibration. This was used to linearly calibrate the flow rate of each sample by Any change in the time of the marker peak will affect both the flow rate and the chromatographic gradient. The highest accuracy of RV measurement of flow marker peaks is expected. To facilitate accuracy, a least-squares fitting routine was used to fit the flow marker concentration curves. Fit the peaks in the chromatogram to a quadratic equation. Then use the first derivative of the quadratic equation. After calibrating the system based on the flow marker peak, The effective flow rate (as a measure of the calibration slope) is calculated as in Equation 7: Flow Marker Peak Processing was performed with PolymerChar GPCOne™ software. .

number

[0095] An improved method for comonomer content distribution (iCCD) analysis An improved comonomer content distribution (iCCD) analysis method was developed using an IR-5 detector (Pol ymerChar, Spain), and a two-angle light scattering detector model 2040 (Preci sion Detectors, now Agilent Technologies) Crystallization, Elution, and Fractionation The experiment was carried out using a detector (CEF) (PolymerChar, Spain). Just before the IR-5 detector in the oven, a 10 cm (length) x 1 / 4 inch (ID) (0.6 35cm ID) stainless steel, 20-27 micron glass (MoSCi Cor A guard column packed with orthodichloromethane (O-dichloromethane, POration, USA) was installed. Benzene (ODCB, 99% anhydrous grade or technical grade) was used. Silica gel 40 (particle size 0.2-0.5 mm, catalog) from D Chemicals (Product number 10181-3) was obtained (used to fill a column for further purification of ODCB). (The packed column is attached after the outlet of the Agilent pump.) The EF instrument is equipped with an autosampler with N2 purging capability. Sparge with dry nitrogen (N2) for 1 hour. Sample preparation is performed at 160°C without shaking for 1 hour. The autosampler was used at 4 mg / mL (unless otherwise specified). The temperature profile for the iCCD was 105°C to 30°C at 3°C / min. Crystallization at 200°C, thermal equilibration at 30°C for 2 min (including soluble fraction elution time set as 2 min) The flow rate during crystallization was 0.0°C. The flow rate during elution is 0.50 ml / min. The data are shown as one data point. / sec.

[0096] The iCCD column contains gold-coated nickel particles (Bright 7GN M8-NiS (Nippon Chemical Industry) 15cm (length) x 1 / 4 inch (ID) (0.635 The column was packed in a stainless steel tube (2.5 cm). The column was packed and conditioned by References (Cong, R; Parrott, A.; Hollis, C.; Cheatha M, M. U.S. Patent Application Publication No. 2018 / 0172648A1) using a slurry method. The final pressure of the TCB slurry packing was 150 bar.

[0097] Column temperature calibration was performed using a standard linear homopolymer polyethylene (comonomer content The melt index (I2) is 1.0, and the polydispersity Mw / Mn is the same as that of conventional gel permeation copolymers. chromatographically, approximately 2.6, 1.0 mg / mL) and eicosapentaenoic acid in ODCB The iCCD temperature calibration was performed using a mixture of 2 mg / mL of ethanol. (1) Subtract 30.00°C from the measured peak elution temperature of eicosane. (2) calculating the delay volume, defined as the temperature offset between the elution temperature The temperature offset is subtracted from the iCCD raw temperature data, where It should be noted that the elution rate is a function of experimental conditions such as elution temperature and elution flow rate. The homopolymer polyethylene standard has a peak temperature at 101.0°C, while eicosane has a peak temperature of 30. Elution temperatures ranging from 30.00°C to 140.00°C with a peak temperature of 0°C (4) To create a linear calibration line for converting the soluble fraction measured isothermally at 30°C. For minutes, an elution temperature of less than 30.0°C was determined based on the reference (US2018 / 0172648A 1) Linearly extrapolate by using an elution heating rate of 3°C / min.

[0098] iCCD comonomer content versus elution temperature was measured using 12 standards (single-site metallo Ethylene homopolymer and ethylene-octene random copolymer prepared with Sen catalyst -, having an ethylene equivalent average molecular weight in the range of 35,000 to 128,000 g / mol All of these standards were constructed using the previously specified 4 mg / mL standard. The reported values ​​as a function of octene mole % using linear regression were analyzed in the same way as By modeling the elution peak temperature, R 2 Equation 8 (EQ8) is obtained, where is 0.978. The elution peak is the temperature at which the eluted weight fraction is the highest. (Elution temperature in degrees Celsius) = -6.3515 x (octene mole %) + 101.000 EQ 8

[0099] For all resins, the elution temperature range is 23.0°C to 115°C (temperature calibration is specified above). The integration window is set to integrate all weight fractions in the The weight percent of (HDF) is defined by the following equation 9 (EQ9), and the soluble fraction of the resin (SF ) is defined by the following Equation 10 (EQ10), and the copolymer fraction (CF) is defined by the following Equation 11 (EQ1 1) is defined as follows.

number

number

[0100] extreme stretching Extreme stretching was performed using Highlight Industries The test was performed according to the following procedure: Place a film roll (20 inches wide, thickness specified below) into the unwind section of the machine. The second roller maintains a constant rotational speed (corresponding to a film speed of 180 ft / min). The rotation speed of the first roller is continuously reduced while the film is passed through a set of rollers. The film is therefore subjected to increasing strain and increasing force, The test was continued until the film reached the limit of stretching (the strain at which the film breaks between the stretching rollers). The amount of force applied is measured by a load cell to determine the amount of stretch present in the film. The ratio of the roller rotation speeds was used to calculate the average. During each test, the load required to stretch the film was measured. The stretching force recorded at 200% stretch for each test is also listed below. is averaged.

[0101] Puncture on the pallet Punctures on the pallets were determined using Lantech stretch wrappers. The 20 inch wide film was wrapped onto a stretch wrapper set at 250% stretch. Wrap the film around a square pallet (approximately 35 x 44 inches) at 10 rpm, moving the film up and down. Instead, it was wrapped around a certain part of the test pallet. The test was performed using the dance bar "F2" setting ( (representing the tension maintained in the film between the pallet and the final stretching roller) Well, it can be adjusted in 0.5lbf increments from 7lbf to 18lbf. When the pre-stretch reaches 250%, the pallet is pulled from one corner of the pallet (rectangle 2" x 2" rectangular prism steel projection extending 6" (parallel to the short side of the The cross section of the protrusion is beveled with a radius of curvature of approximately 4 mm. Smooth the edges to remove any sharp edges and ensure that the radius of curvature of the edges is approximately 2 mm. The row consists of three complete rotations of the pallet, wrapping it around the probe three times, and The test involves assessing whether the probe penetrates the film. If the film breaks within this time, it is considered a failure at that force vs. load setting. Depending on the film's performance at the setting (i.e., pass or fail), the force Adjust the load up or down and repeat the test at the new load setting. The reported load is 0% is the maximum load to pass (3 successes out of a maximum of 6 attempts). Three runs are performed and the average is reported as the pallet puncture value.

[0102] Table 2 below shows the equipment and settings used in this method. [Table 2]

[0103] Total Haze Total haze was measured according to ASTM D1003.

[0104] dirt The Film Dart Drop Test tests plastics under specific conditions of impact with a free-falling dart. The energy required to break the film is measured. The test results are reported for 50% of the specimens tested. The energy, expressed as the weight of a projectile dropped from a certain height, that will result in % damage. It's a guinea pig.

[0105] Dart Impact Strength (Dart) per ASTM D1709, Method A, 26 in. ±0.4 in. (66 cm ±1 cm) drop height and 38.10 ±0.13 mm diameter Measurements are taken using a polished aluminum hemispherical head. [Example]

[0106] The following examples are provided to illustrate the embodiments described in this disclosure and are not intended to be limiting of the scope of the present disclosure. It is not intended to limit the scope of the appended claims.

[0107] Catalyst preparation procedure The catalyst preparation procedures for Comparative Examples A to C and Inventive Examples 1 to 9 are listed below.

[0108] Ziegler-Natta Catalyst (Zinc-Free) - Comparative Examples A-C Approximately 220 lb of 0.20M MgCl2 slurry contains 12.86 lb of (C2H5)A lCl2(EADC) solution (15 wt % in heptane) was added, followed by stirring for 8 h. Next, 6.64 lb of a TiCl4 / VOCl3 mixture (1.10 wt% Ti in heptane and and 2.36 wt% V) was added, followed by Zr(TMHD)4 (zirconium tetrakis(III)). (2,2,6,6-tetramethyl-3,5-heptanedionate) solution (5.19 lb 1.34 wt% Zr solution in heptane) was added. These two additions were made 1 hour after each other. The resulting catalyst premix was stirred for an additional 8 hours before use. It was allowed to mature while doing so.

[0109] Ziegler-Natta Catalyst (Containing Zinc) - Inventive Examples 1-3 and 9 Approximately 210 lb of 0.20M MgCl2 slurry is mixed with 12.52 lb of (C2H5)A. lCl2(EADC) solution (15 wt % in heptane) was added, followed by stirring for 4 h. Zn(EHA)2 (zinc 2-ethylhexanoate) solution (3.81 lb of Isopa 5.0 wt% Zn in rE was added, followed by stirring for 4 hours. Next, 6.34 lb of T iCl4 / VOCl3 mixture (1.10 wt% Ti and 2.36 wt% V in heptane) The resulting catalyst premix was aged with stirring for an additional 8 hours before use. Ta.

[0110] Ziegler-Natta Catalyst (Containing Zinc) - Inventive Examples 4-7 Approximately 220 lb of 0.20M MgCl2 slurry is mixed with 13.12 lb of (C2H5)A. lCl2(EADC) solution (15 wt % in heptane) was added, followed by stirring for 4 h. Zn(EHA)2 (zinc 2-ethylhexanoate) solution (3.99 lb of Isopa 5.0 wt% Zn in rE was added, followed by stirring for 4 hours. Next, 6.64 lb of T iCl4 / VOCl3 mixture (1.10 wt% Ti and 2.36 wt% V in heptane) The resulting catalyst premix was aged with stirring for an additional 8 hours before use. Ta.

[0111] Ziegler-Natta Catalyst (Containing Zinc) - Inventive Example 8 Approximately 215 lb of 0.20M MgCl2 slurry contains 12.82 lb of (C2H5)A lCl2(EADC) solution (15 wt % in heptane) was added, followed by stirring for 4 h. Zn(EHA)2 (zinc 2-ethylhexanoate) solution (3.90 lb of Isopa 5.0 wt% Zn in rE was added, followed by stirring for 4 hours. Next, 6.49 lb of T iCl4 / VOCl3 mixture (1.10 wt% Ti and 2.36 wt% V in heptane) The resulting catalyst premix was aged with stirring for an additional 8 hours before use. Ta.

[0112] Preparation of Comparative Examples A-C and Inventive Examples 1-9 Comparative Examples A-C and Inventive Examples 1-9 were solution polymerized according to the following exemplary process: All raw materials (monomers) and process The solvent (high-purity isoparaffin solvent with a narrow boiling point range, Isopar-E) was filtered through molecular sieves. Hydrogen is supplied in pressurized cylinders as a high purity grade and is not further purified. The reactor monomer feed stream was compressed above the reaction pressure via a mechanical compressor. The solvent feed was pressurized via a pump to a pressure higher than the reaction pressure. The catalyst components are manually diluted in batches with purified solvents to specific component concentrations, and the reaction pressure is All reactor feed streams were measured by mass flow meters and controlled by computer-controlled automatic valves. The control system controlled them independently.

[0113] A continuous solution polymerization reactor is a liquid-filled reactor similar to a continuous stirred tank reactor (CSTR) with heat removal. The reactor was a non-adiabatic isothermal circulation loop reactor. All unused solvent, monomer, hydrogen and Independent control of the total fresh feed stream (solvent) to the reactor was possible. The feed streams (catalyst, monomer, and hydrogen) are temperature controlled by passing them through a heat exchanger. The catalyst components were injected into the polymerization reactor through specially designed injection needles. The primary catalyst component feed was combined into one mixed catalyst / cocatalyst feed stream before being introduced into the primary catalyst component feed. The cocatalyst was computer controlled to maintain the reactor monomer concentration at a specified target. Each injection point was freshly fed to the primary catalyst components based on the specific molar ratios calculated. (either feed or catalyst) immediately after the feed stream is circulated into the polymerization reactor contents. The reactor contents were mixed using static mixing elements, which served to remove most of the heat of reaction. The coolant side temperature is used to maintain an isothermal reaction environment at a specific temperature through a heat exchanger. The circulation around the reactor loop was achieved by a positive displacement pump.

[0114] The final reactor effluent is inactivated by the addition and reaction of water to the zone At this same reactor exit location, other additives were added (e.g., acid scavengers and The stream then passes through a static mixer to separate the post-reactor additive components. Dispersed.

[0115] Following catalyst deactivation and additive addition, the reactor effluent is purified by separating the polymer from the non-polymer phase. The isolated polymer melt was pelletized and then passed into a devolatilization system where it was removed from the stream. The non-polymer stream was used to separate the majority of the ethylene removed from the system. The solvent and most of the unreacted monomers were removed through a purification system. After this, the solvent and monomer were recycled back to the reactor. I did.

[0116] Tables 3A and 3B show the synthesis weights of Comparative Examples A to C and Inventive Examples 1 to 9, respectively. The polymerization conditions are summarized in Table 1. The additive used in these polymerizations was 1000 ppm I RGAFOS™ 168 (which is tris(2,4-di-tert-butylphenyl) phosphatase) 250 ppm IRGANOX™ 1076 (which is an octadecane Sil-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate )), and 200 ppm IRGANOX™ 1010 (tetrakis(methyl) Benzene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane IRGAFOS™ 168 and IRGANOX™ 1076 were Commercially available from ASF. IRGANOX™ 1010 is available from BASF All of these examples were carried out in a single reactor using 1-hexene as the comonomer. generated. [Table 3] [Table 4]

[0117] Example of inflation film Table 4 contains the properties of the resins used in the following blown film examples. As shown, Table 4 summarizes the properties of the resin examples in Tables 3A and 3B, as well as the properties listed below. The properties of other conventional resins (Comparative Examples D-G) are also included, all of which are manufactured by Dow Inc. ., Midland, MI. [Table 5-1] [Table 5-2]

[0118] The monolayer blown film containing 100% by weight of LLDPE is " and polyethylene "Davis Standard Barrier II Screw" The mixture was prepared using a single screw extruder. By adjusting the nip roller speed, the film thickness was reduced to 2 mm. The film is controlled to within ±10% by the film control system. The bubble lay flat is 31 inches wide. The film is wound into a roll. The film parameters are shown in Table 5A. The temperature was measured at the pellet hopper (barrel 1). and increasing in temperature as the polymer is extruded through the die.

[0119] The blown films listed in Tables 5B and 5C below are the same The parameters presented in the table were used. [Table 6] [Table 7] [Table 8]

[0120] Referring to Tables 5A and 5B above, the inventive blown film IBF2 is a comparative blown film CBF with similar density and melt index It shows much better (higher) dirt and improved (lower) haze than 1. Without being bound by theory, this improved balance of dirt and total haze performance is due to i Short-chain branching defined by the soluble fraction, copolymer fraction, and high-density fraction of CCD This is thought to be partly due to the fabric.

[0121] Improvements in dirt and haze are greater than conventional inflation films CBF4 to CBF7. For example, both have similar densities and melt indexes. The inventive film IBF4 and the comparative inflatable film Compared to CBF7, IBF4 showed better total haze and dirt performance. Similarly, IBF5 and CBF4, both of which have similar densities and melt indices, were compared. In comparison, IBF5 showed better haze and dirt performance, both at the same density. When comparing IBF7 and CBF6, which have different degrees of haze, IBF7 has better total haze and It demonstrated dirt performance.

[0122] Cast film Table 6 below lists the additives incorporated into or used in cast films. As shown in Table 6, the resins and resin properties for the resins suitable for the comparative examples are presented. H(CH) is The Dow Chemical Company, Midland, DOWLEX™ GM 8480F available from MI. Comparative Example I (CI) ELITE 5230G, also from The Dow Chemical Company The cast film of the present invention is available from NY, Midland, MI. However, inventive example resin 9 (IE9) , another resin suitable for use in cast film. The polymerization conditions for IE8 and IE9 are Presented in Table 3B. [Table 9]

[0123] Preparation of stretched cast film A five layer (A / B / C / D / E) filter was fabricated using the resins listed in Table 6 above. The film was fabricated on a 5-layer Egan-Davis standard cast extrusion line as follows: The gap was 20 mil, the melt curtain used was 3.5 inches, and the cast roll was 70 The die was maintained at 550°F, the die was maintained at 550°F, and the line speed was increased until the target film thickness was reached. One extruder (A) was operated to produce ATTANE 4404. The remaining extruder produces IE8, CH, or CI. The cast films of the present invention (ICF1 and ICF2) were made using IE8, and the comparative cast films were made using IE8. The films CCF1 and CCF2 used CH resin, and CCF3 used CI. TTANE 4404G is commercially available from The Dow Chemical Company. A commercially available polyethylene resin with an I² of 4.0 g / 10 min and a density of 0.904 g / cc The target layer structure was as follows (wt%): 10 / 23 / 30 / 26 / 1 1. Layer A (adhesive layer) faced the core of the roll during the winding process. Table 7 below shows the The target film thickness, throughput, extruder temperature, and line speed are shown. [Table 10]

[0124] After the cast films of Table 7 are produced, the cast films are subjected to ultimate stretching, Highlig These tests were evaluated based on the force required for stretching to 200% and the puncture on the pallet. The results are shown in Table 8. [Table 11]

[0125] As shown above, the cast films ICF1 and ICF2 of the present invention have a high Light extreme stretching, Highlight 200% stretching force, and maximum puncture on the pallet A comparison of ICF1 and CCF1, both of which have the same thickness of 0.5 mils, shows a good combination. When compared, ICF1 exhibits excellent ultimate extension, high extension force, and puncture on the pallet. It is clear that the thickness of the ICF1 and CCF3 is the same. Therefore, the puncture and ultimate stretching may be comparable. However, ICF1 Highlight has significantly better stretching force performance. Similarly, the I of 0.7 mil film When comparing CF2 and CCF2, ICF2 has improved puncture and highlighting. t extension force, and the combination of equal ultimate extension. These improvements were observed in the soluble fraction, copolymer fraction, high density fraction, and soluble fraction in Table 6. This is believed to be due to a change in polymer structure described by the ratio of the high-density fraction to the high-density fraction.

[0126] Higher ultimate elongation allows wrapping pallets under a wider range of conditions, This is beneficial as it minimizes film breakage during the stretching process. Higher loads (measured in the Highlight 200% stretch test) indicate stiffer films. This correlates with better resistance to puncture during pallet transport. Higher pallet puncture values This is beneficial and indicates a higher overall film abuse resistance.

Claims

1. A linear low density polyethylene (LLDPE) polymer comprising: The LLDPE is a mixture of ethylene monomer and C ３ -C １２ Polymerization reaction with ethylene comonomer It is a reaction product, The LLDPE has a density of 0.904 to 0.925 g / cc, a viscosity of 2.5 at a temperature of 190°C, and a melting point of 1.5 at a temperature of 190°C. 0.5-1.5 g / 10 min when measured according to ASTM 1238 under a load of 16 kg The melt index (I ２ ) 、 I １０ ASTM 1 at 190°C under a load of 10 kg A melt flow ratio (I) of 6.5 to 7.6 as measured in accordance with 238 １０ / I ２ ), and Ge The molecular weight distribution (MWD) of the copolymer is 2.5 to 3.6 as measured by gel permeation chromatography. Mw / Mn), The LLDPE is Copolymer fractions greater than 85% and improved comonomer elution mass vs. temperature >35°C to 9°C for total eluted mass as measured using content distribution (iCCD) curve a copolymer fraction, defined as the proportion of the mass eluted at a temperature below 5°C; 0.5-8.0% of the high density fraction relative to the total mass, eluted at a temperature of 95°C or higher a high density fraction, defined as the ratio of the mass of 1.0% to 12.0% of the soluble fraction of the total mass at a temperature of 35°C or less the soluble fraction, defined as the proportion of the mass eluted, and the short chain branching fraction, defined by LLDPE polymers, including fabrics.

2. A blown film comprising the LLDPE of claim 1.

3. The blown film has a thickness of at least 900 when it is 2.0 mils thick.

3. The composition of claim 2 having a dirt value of 0.01 g and a resin density of less than 0.918 g / cc. Inflation film.

4. The blown film has a total thickness of 4.5% to 10.5% at a thickness of 2.0 mils.

4. The blown film of claim 2, having a size (%).

5. I ２ The inflation method according to any one of claims 2 to 4, wherein the Nfilm.

6. 6. The method of claim 2, wherein the blown film has a thickness of 0.5 to 6 mils. The inflation film according to any one of claims 1 to 14.

7. The inflation method according to any one of claims 2 to 6, wherein the soluble fraction is less than 5%. tion film.

8. Inflator according to any one of claims 2 to 7, wherein the copolymer fraction is greater than 90%. ration film.

9. The inflation film of any one of claims 2 to 8, further comprising LDPE. Room.

10. The blown film comprises 50 to 95 wt % of the LLDPE, and 5 to 95 wt % of the LLDPE.

10. The blown film of claim 9 comprising 50% by weight of the LDPE.

11. 11. The inflation film according to claim 2, wherein the inflation film is a multilayer film. Item 1. The inflation film according to item 1.

12. A linear low density polyethylene (LLDPE) polymer, wherein the LLDPE is Styrene monomer and C ３ -C １２ a polymerization reaction product with ethylene comonomer, The LLDPE has a density of about 0.910 to 0.920 g / cc, a viscosity of 2 at a temperature of 190°C, 2.0-7.0 g / 10 when measured according to ASTM 1238 under a load of 16 kg Melt index (I ２ ), and I １０ A at a temperature of 190°C under a load of 10 kg Melt flow ratio (I) of 6.5 to 7.6 as measured according to STM 1238 １０ / I ２ )of Has, The LLDPE is 0.5-6.0% high density fraction using the iCCD curve of elution mass vs. temperature The ratio of the mass eluted within a temperature range of 95°C or higher to the total eluted mass when measured at a high density fraction, defined as A soluble fraction of 1.0 to 3.0% of the total dissolved mass, in a temperature range of 35°C or less the soluble fraction, defined as the proportion of the mass eluted within the range a ratio of the soluble fraction to the high density fraction of 0.40 to 0.65; 、 The maximum elution peak height occurs at a temperature greater than 80°C. LLDPE polymer containing a short chain branching distribution.

13. 13. The LLDPE of claim 12, wherein the high density fraction is from 3.0% to 6.0%.

14. 14. The LLD according to claim 12 or 13, wherein the soluble fraction is 2.0% to 3.0%. P.E.

15. The LLDPE has a copolymer fraction of greater than 85%, and the copolymer fraction is The temperature at 35°C to 95°C for the total mass as measured using the iCCD curve of mass vs. temperature The method according to any one of claims 12 to 14, wherein the ratio of the mass dissolved at a temperature is defined as LLDPE.

16. 16. Any of claims 12 to 15, wherein the maximum elution peak height occurs at a temperature below 90°C.

3. The LLDPE according to claim 1.

17. A cast film comprising the LLDPE of any one of claims 12 to 16.

18. 20. The cast film of claim 17 further comprising LDPE.

19. The cast film comprises 50 to 95 wt. % of the LLDPE and 5 to 50 wt. % of the LLDPE. % of said LDPE.

20. The cast film according to any one of claims 17 to 19, wherein the cast film is a multilayer film. Cast film shown.

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