WO2024096636A1 - Composition de polyéthylène et film la comprenant - Google Patents

Composition de polyéthylène et film la comprenant Download PDF

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Publication number
WO2024096636A1
WO2024096636A1 PCT/KR2023/017420 KR2023017420W WO2024096636A1 WO 2024096636 A1 WO2024096636 A1 WO 2024096636A1 KR 2023017420 W KR2023017420 W KR 2023017420W WO 2024096636 A1 WO2024096636 A1 WO 2024096636A1
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ethylene
mpa
mol
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PCT/KR2023/017420
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English (en)
Korean (ko)
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최은엽
유영석
김태진
이상화
김인교
박철훈
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주식회사 엘지화학
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Publication of WO2024096636A1 publication Critical patent/WO2024096636A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • the present invention is intended to provide a polyethylene composition suitable for polyethylene films that maintain excellent printability, transparency, productivity, and film processability, and have excellent rigidity with a high initial modulus, and a film containing the same.
  • Thin film products made from linear low density polyethylene (LLDPE) and/or high density polyethylene (HDPE) are widely used in packaging applications such as merchandise bags, grocery bags, food and specialty packaging, and industrial liners. It is being used.
  • shrink film which allows packaging while maintaining the shape of the product, is mainly used to protect the product from touch when displayed.
  • LLDPE is widely used as a PE resin for films because it is flexible and has appropriate impact resistance and processability.
  • LLDPE film is produced through blown method, cast method, and biaxial stretching method and is used as packaging material, shrink film, and agricultural film.
  • biaxially stretched LLDPE films have been developed and applied to improve the mechanical properties of the film and down-gauging.
  • commercialized packaging films are a composite material made of polyethylene (PE) resin and other resins, so they can be recycled by replacing other film layers made of resins such as polyamide (Nylon) and polyethylene terephthalate (PET). Attempts to develop all-PE packaging materials are also underway.
  • LLDPE resin has a relatively low crystallinity and density compared to HDPE resin, and its application is limited due to its insufficient mechanical properties when producing films.
  • it lacks rigidity compared to other film materials such as Nylon and PET, so it cannot effectively replace them, and the development of recycled packaging materials is limited.
  • the present invention is to provide a polyethylene composition capable of producing a polyethylene film with excellent rigidity with excellent mechanical properties while maintaining excellent printability, transparency, productivity and film processability, and showing high tensile strength and initial modulus, and a film containing the same. will be.
  • a polyethylene composition comprising at least one type of ethylene-alphaolefin copolymer, wherein the polyethylene composition has a molecular ratio eluting above 90°C derived from TREF analysis (TREF ⁇ 90°C ) of 55.0%. or more, and the ratio of molecules eluted at a temperature above 35°C and below 90°C derived from TREF analysis (TREF 35-90°C ) is 45% or less.
  • a polyethylene film comprising the polyethylene composition of the above embodiment is provided.
  • (co)polymer includes both homo-polymer and co-polymer.
  • copolymerization may mean block copolymerization, random copolymerization, graft copolymerization, or alternating copolymerization
  • copolymer may mean block copolymer, random copolymer, graft copolymer, or alternating copolymerization. It can mean merging.
  • a polyethylene composition comprising at least one type of ethylene-alphaolefin copolymer, wherein the polyethylene composition has a molecular ratio eluting above 90°C derived from TREF analysis (TREF ⁇ 90°C ) of 55.0%.
  • a polyethylene composition is provided wherein the ratio of molecules eluted at a temperature above 35°C and below 90°C derived from TREF analysis (TREF 35-90°C ) is 45.0% or less.
  • part by weight refers to a relative concept expressed as a ratio of the weight of the remaining material based on the weight of a certain material. For example, in a mixture containing 50 g of substance A, 20 g of substance B, and 30 g of substance C, the amounts of substance B and substance C would each be 40 parts by weight based on 100 parts by weight of substance A. parts by weight and 60 parts by weight.
  • % by weight refers to an absolute concept expressed as a percentage of the weight of a certain material out of the total weight.
  • the contents of material A, material B, and material C out of 100% of the total weight of the mixture are 50% by weight, 20% by weight, and 30% by weight, respectively.
  • the polyethylene composition is composed of a first ethylene-alphaolefin copolymer with excellent mechanical properties and a second ethylene-alphaolefin copolymer with excellent flow properties that can provide stretchability by applying a specific metallocene catalyst to be described later.
  • the content ratio (TREF ⁇ 90°C ) of the highly crystalline fraction eluted at 90°C or higher is 55.0% or more or 55.0% or more of the total weight of all eluted fractions. It may be less than 95%.
  • the content ratio of the highly crystalline fraction is 57% or more, 58% or more, 59% or more, 59.5% or more, 60% or more, 60.5% or more, 61% or more of the total weight of the total eluted fraction, It may be 61.5% or higher, 62% or higher, 62.5% or higher, 63% or higher, 63.5% or higher, 64% or higher, or 66% or higher, and if necessary, 93% or lower, 90% or higher, 88% or lower, 85% or higher, It may be 82% or less, 80% or less, 79.5% or less, 79% or less, or 78.5% or less.
  • the content ratio (TREF 35-90°C ) of the mesocrystalline fraction eluted at a temperature above 35°C and below 90°C is 45.0% or less of the total weight of all eluted fractions. Or it may be 10% or more and 45.0% or less.
  • the content ratio of the medium crystalline fraction (TREF 35-90°C ) is 44.9% or less, 44% or less, 43% or less, 42% or less, 41% or less, 40% or less, 39.5% of the total weight of the total eluted fraction.
  • It may be 39% or less, 38.5% or less, 38% or less, 37% or less, 36% or less, 35% or less, 34% or less, 33.5% or less, 33% or less, 32.5% or less, or 32.1% or less, and 12 % or more, 12.5% or more, 13% or more, 13.5% or more, 15% or more, 15.5% or more, 16% or more, 17% or more, 18% or more, 18.5% or more, 18.8% or more, 19% or more, 20% or more , or may be more than 21%.
  • the soluble fraction (TREF ⁇ 35°C ) eluted at less than 35°C may be 3.0% or less or 0.1% to 3.0% or less of the total weight of the total eluted fraction. there is.
  • the soluble fraction (TREF ⁇ 35°C ) is 2.9% or less, 2.8% or less, 2.7% or less, 2.6% or less, 2.5% or less, 2.4% or less, 2.3% or less, 2.2% or less, It may be 2.1% or less, 2.0% or less, or 1.9% or less, and if necessary, 0.1% or more, 0.15% or more, 0.2% or more, 0.25% or more, 0.3% or more, 0.35% or more, 0.4% or more, 0.45% or more, It may be at least 0.5%, at least 0.55%, at least 0.6%, at least 0.65%, at least 0.7%, at least 0.75%, or at least 0.8%.
  • the polyethylene composition has a content ratio (TREF ⁇ 90°C ) of the highly crystalline fraction eluted at 90°C or higher when analyzed by cross fractionation chromatography (CFC), and a fraction eluted at 35°C or higher and less than 90°C.
  • the content ratio of the crystalline fraction (TREF 35-90°C ) and the amorphous fraction eluted below 35°C, that is, the soluble fraction (TREF ⁇ 35°C ) are the high crystalline fraction and the medium crystalline fraction as described above.
  • Each ratio value is set within a range where the total of the fraction and the amorphous fraction does not exceed 100%.
  • CFC cross fractionation chromatography
  • the polyethylene composition may have a density of 0.925 g/cm 3 or more and 0.945 g/cm 3 or less.
  • the density is at least 0.930 g/cm 3 , at least 0.935 g/cm 3 , or at least 0.937 g/cm 3 and at most 0.944 g/cm 3 , at most 0.943 g/cm 3 , at most 0.942 g/cm 3 , or 0.941 g/cm 3 or less, or 0.940 g/cm 3 or less.
  • density (g/cm 3 ) can be measured using a density gradient pipe according to the American Society for Testing and Materials ASTM D 1505 standard.
  • ASTM D 1505 standard the method for measuring this density (g/cm 3 ) is as described in Test Examples 1 and 2 described later.
  • the polyethylene composition may have a melt index (MI 2.16 , 190°C, 2.16 kg load) of 0.18 g/10min to 1.5 g/10min.
  • the melt index (MI 2.16 , 190°C, 2.16kg load) is 0.2 g/10min or more, 0.3 g/10min or more, 0.4 g/10min or more, 0.5 g/10min or more, or 0.6 g/10min or more.
  • the melt index (MI 2.16 ) can be measured at 190°C and under a load of 2.16 kg according to the American Society for Testing and Materials standard ASTM D 1238 (Condition E, 190°C, 2.16 kg).
  • ASTM D 1238 Condition E, 190°C, 2.16 kg.
  • the method of measuring the melt index (MI 2.16 ) is as described in Test Examples 1 and 2 described later.
  • the polyethylene composition has a number average molecular weight (Mn) of 18500 g/mol or more, 18800 g/mol or more, 19000 g/mol or more, 19500 g/mol or more, 20000 g/mol or more, 25000 g/mol or more. , or 28000 g/mol or more, or 30000 g/mol or more, or 31000 g/mol or less, or 100000 g/mol or less, 70000 g/mol or less, 50000 g/mol or less, 40000 g/mol or less, 35000 g /mol or less, or 34000 g/mol or less.
  • Mn number average molecular weight
  • the weight average molecular weight (Mw) of the polyethylene composition may be 100000 g/mol or more, 105000 g/mol or more, or 110000 g/mol or more, and may be 500000 g/mol or less, 400000 g/mol or less, or 300000 g/mol or less, It may be 200000 g/mol or less, 180000 g/mol or less, 160000 g/mol or less, 140000 g/mol or less, 120000 g/mol or less, 116000 g/mol or less, or 114000 g/mol or less.
  • the molecular weight distribution Mw/Mn of the polyethylene composition may be 1.0 or more and 10.0 or less. More preferably, the molecular weight distribution Mw/Mn of the polyethylene composition may be 1.5 or more, 2.0 or more, 2.5 or more, 2.8 or more, 3.0 or more, or 3.3 or more. Additionally, the molecular weight distribution Mw/Mn may be 9.5 or less, 9.0 or less, 8.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.8 or less, or 3.7 or less.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are converted values for standard polystyrene measured using gel permeation chromatography (GPC, manufactured by Water).
  • GPC gel permeation chromatography
  • the weight average molecular weight is not limited to this and can be measured by other methods known in the technical field to which the present invention pertains.
  • the method of measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) is as described in Test Examples 1 and 2 described later.
  • the polyethylene composition may have a melting point (Tm) of 127 °C or higher to 130 °C or lower, 127.2 °C or higher to 129.8 °C or lower, 127.5 °C or higher to 129.5 °C, or 1285 °C or higher to 128.7 °C or lower, and a crystallization temperature (Tc) It may be 110 °C or more and 115 °C or less, 111 °C or more and 114.8 °C or less, 111.5 °C or more and 114.5 °C or less, or 111.6 °C or more and 113.85 °C or less, and the crystallinity (Xc) is 50% or more and 70% or less, 52 % or more and 69.8% or less, 55% or more and 69.5% or less, 58% or more and 69% or less, or 60% or more and 68.5% or less.
  • Tm melting point
  • Tc crystallization temperature
  • the melting point may be 128.0°C or higher, 129.0°C or lower, or 128.6°C or lower.
  • the crystallization temperature may be 111.6°C or higher, 114°C or lower, 113°C or lower, or 112.3°C or lower.
  • the crystallinity may be 55% or more, 58% or more, 60% or more, or 60.1% or more, and 69% or less, or 68.4% or less.
  • the melting point Tm, crystallization temperature Tc, and crystallinity Xc can be measured using a Differential Scanning Calorimeter (DSC, device name: DSC Q20, manufacturer: TA instrument).
  • DSC Differential Scanning Calorimeter
  • the method of measuring the melting point Tm, crystallization temperature Tc, and crystallinity Xc is as described in Test Example 2, which will be described later.
  • the polyethylene composition of the present invention shows high yield strength and secant modulus, that is, 1% and 2% initial modulus, and exhibits excellent mechanical properties.
  • the polyethylene composition has a yield strength measured according to the ASTM D 638 standard of 18 MPa or more, 18.2 MPa or more, 18.5 MPa or more, 18.8 MPa or more, 19 MPa or more, 19.5 MPa or more, 20 MPa or more, and 20.5 MPa or more. , or may be 20.8 MPa or more and 100 MPa or less.
  • the yield strength represents the strength of the yield point.
  • the tensile test for the polyethylene composition is performed by compression molding at 180°C and 4500 lbf pressure for 15 minutes to produce a polyethylene composition sheet with a thickness of 1 mm, then preparing a tensile test specimen according to ASTM D 638 standard, and performing a tensile test at room temperature ( It is carried out at 20 °C to 25 °C) and a tensile speed of 500%/min, and measured according to ASTM D 638 standard.
  • the specific measurement method is as shown in Test Example 2 described later.
  • the polyethylene composition has an initial modulus measured according to the ASTM D 638 standard, that is, an initial modulus at 1% and 2% elongation, and a 1% modulus, respectively, in the strength-elongation curve obtained from a tensile test according to the ASTM D 638 standard. (modulus) and 2% modulus are high, and it has excellent rigidity.
  • the polyethylene composition has a 1% modulus of 400 MPa or more, 420 MPa or more, 450 MPa or more, 480 MPa or more, 500 MPa or more, 520 MPa or more, 550 MPa or more, 580 MPa or more, 600 MPa or more.
  • ⁇ 605 MPa or more may be 1100 MPa or less, and have a 2% modulus of 330 MPa or more, 340 MPa or more, 350 MPa or more, 375 MPa or more, 400 MPa or more, 420 MPa or more, 450 MPa or more, 480 MPa It may be 500 MPa or more, or 505 MPa or more, and 1000 MPa or less.
  • 1% modulus and 2% modulus represent the modulus values at the 1% and 2% elongation points, respectively, in the strength-elongation curve obtained from the tensile test as described above.
  • the polyethylene composition has a tensile strength measured according to the ASTM D 638 standard of 32 MPa or more, 32.5 MPa or more, 33 MPa or more, 33.5 MPa or more, 34 MPa or more, 34.5 MPa or more, 35 MPa or more, 35.5 MPa or more, It may be 36 MPa or more, or 36.2 MPa or more, or 36.6 MPa or more, and may be 100 MPa or less.
  • the tensile strength represents the strength at break in the tensile test as described above.
  • the polyethylene composition has an elongation at break of 625% to 785%, or 630% to 780%, or 640% to 775%, or 650% to 770%, as measured according to the ASTM D 638 standard. % or less, 670% or more and 765% or less, 690% or more and 760% or less, 695% or more and 730% or less, or 700% or more and 720% or less.
  • the elongation at break represents the elongation at break in the tensile test as described above.
  • the polyethylene composition according to one embodiment of the present invention has (a) a density of 0.930 g/cm 3 to 0.960 g/cm 3 and a melt index (MI 2.16 , 190° C., 2.16 kg load) of 0.05 g/10 min.
  • MI 2.16 , 190° C., 2.16 kg load 15 g/10 min or less.
  • the polyethylene composition according to one embodiment of the present invention includes 82% by weight or more and less than 97% by weight of the first ethylene-alpha olefin copolymer (a), and the second ethylene-alpha olefin copolymer (a) b) in an amount greater than 0% by weight and not more than 18% by weight.
  • the mechanical properties and properties were obtained through optimized blending of the first ethylene-alphaolefin copolymer, which has excellent mechanical properties, and the second ethylene-alphaolefin copolymer, which has excellent flowability and can provide stretchability, within the above-mentioned range.
  • By adjusting the balance between film processability it is possible to manufacture a polyethylene film with excellent mechanical properties with high tensile strength and initial modulus while maintaining printability, transparency, productivity and film processability equal to or superior to existing ones.
  • the first ethylene-alphaolefin copolymer (a) is 83 wt% or more, 84 wt% or more, or 85 wt% or more, and 99 wt% or less, 97 wt% or less, or 95 wt% or less. may be included.
  • the second ethylene-alpha olefin copolymer (b) may be included in an amount of 1% by weight or more, 3% by weight or more, or 5% by weight or less, and 17% by weight or less, 16% by weight or less, or 15% by weight or less. there is.
  • the first ethylene-alpha olefin copolymer (a) is contained in an amount of 82% by weight or more and 97% by weight or less, and the second ethylene-alpha olefin copolymer (b) is contained in an amount of 3% by weight or more to 18% by weight. It may be included as above.
  • the first ethylene-alpha olefin copolymer (a) is 4 times or more, or 4 times or more to less than 100 times the weight of the second ethylene-alpha olefin copolymer (b).
  • the first ethylene-alpha olefin copolymer (a) is 4.2 times or more, or 4.4 times or more, or 4.5 times or more, or 5 times more than the second ethylene-alpha olefin copolymer (b). or greater than or equal to 5.2 times, or greater than or equal to 5.4 times, or greater than or equal to 5.5 times, or greater than or equal to 5.6 times, but not more than 99 times, or less than or equal to 80 times, or less than or equal to 50 times, or less than or equal to 40 times, or less than or equal to 35 times, or less than or equal to 33 times.
  • the first ethylene-alpha olefin copolymer (a) may be an ethylene/1-hexene copolymer
  • the second ethylene-alpha olefin copolymer (b) may be an ethylene/1-octene copolymer
  • the first ethylene-alpha olefin copolymer (a) has excellent mechanical properties and is suitable for manufacturing a polyethylene film with excellent stretchability and high mechanical properties through an appropriate balance between crystallinity and processability. can be granted.
  • the first ethylene-alpha olefin copolymer (a) has a density of 0.930 g/cm 3 to 0.960 g/cm 3 and a melt index (MI 2.16 , 190° C., 2.16 kg load) of 0.05 g/10 min. or more or 0.05 g/10min to 2.0 g/10min.
  • MI 2.16 , 190° C., 2.16 kg load 0.05 g/10 min. or more or 0.05 g/10min to 2.0 g/10min.
  • the first ethylene-alphaolefin copolymer (a) has a density of 0.933 g/cm 3 or more, 0.935 g/cm 3 or more, 0.938 g/cm 3 or more, or 0.941 g/cm 3 or more, and 0.955 g/cm 3 or more. It may be less than or equal to g/cm 3 , less than or equal to 0.950 g/cm 3 , or less than or equal to 0.948 g/cm 3 .
  • the first ethylene-alpha olefin copolymer (a) has a melt index (MI 2.16 , 190 o C, 2.16 kg load) of 0.05 g/10min or more, 0.1 g/10min or more, or 0.15 g/10min or more, It may be more than 0.17 g/10min, or more than 0.2 g/10min.
  • the melt index (MI 2.16 , 190 o C, 2.16 kg load) of the first ethylene-alphaolefin copolymer (a) is 1.8.
  • It may be less than or equal to g/10min, less than or equal to 1.5 g/10min, less than or equal to 1.2 g/10min, less than or equal to 1.0 g/10min, less than or equal to 0.8 g/10min, or less than or equal to 0.6 g/10min.
  • the first ethylene-alpha olefin copolymer (a) has a number average molecular weight (Mn) of 12,000 g/mol or more and 50,000 g/mol or less, and a weight average molecular weight (Mw) of 80,000 g/mol or more and 250,000 g/mol or less. And the molecular weight distribution (Mw/Mn) may be 3.0 or more and 20.0 or less.
  • the number average molecular weight Mn of the first ethylene-alphaolefin copolymer (a) may be 13000 g/mol or more, 14000 g/mol or more, or 15000 g/mol or more, 40000 g/mol or less, 30000 It may be less than or equal to g/mol, or less than or equal to 28000 g/mol.
  • the weight average molecular weight Mw of the first ethylene-alpha olefin copolymer (a) may be 90,000 g/mol or more, 100,000 g/mol or more, or 114,000 g/mol or more, and 230,000 g/mol or less, 210,000 g/mol. mol or less, or may be 200000 g/mol or less.
  • the molecular weight distribution (Mw/Mn) of the first ethylene-alpha olefin copolymer (a) may be 3.5 or more, 3.8 or more, 4.0 or more, or 4.1 or more, and 17.0 or less, 15.0 or less, 14.0 or less, or 13.1 or less. there is.
  • the first ethylene-alpha olefin copolymer (a) may have at least one of the above-mentioned properties, and may have all of the above-mentioned properties to exhibit excellent mechanical strength.
  • the first ethylene-alphaolefin copolymer (a) includes ethylene and 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, It may contain one or more alpha-olefins selected from the group consisting of 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and mixtures thereof.
  • the first ethylene-alpha olefin copolymer (a) may be an ethylene/1-hexene copolymer.
  • the first ethylene-alpha olefin copolymer (a) is the above-mentioned copolymer, the above-mentioned physical properties can be more easily realized.
  • the type of the first ethylene-alpha olefin copolymer (a) is not limited to the above-mentioned types, and various types known in the art to which the present invention pertains may be provided as long as they can exhibit the above-mentioned physical properties.
  • the first ethylene-alpha olefin copolymer (a) having the above physical properties may be manufactured in the presence of a metallocene catalyst.
  • the first ethylene-alphaolefin copolymer (a) is a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2) in a ratio of 1:1 to 1:8. It can be prepared by copolymerizing ethylene and a comonomer while adding hydrogen gas in the presence of a catalyst composition containing a molar ratio of .
  • M 2 is a Group 4 transition metal
  • Cp 1 and Cp 2 are each cyclopentadienyl, which is unsubstituted or substituted with C 1-20 hydrocarbon;
  • R a and R b are the same or different from each other, and are each independently hydrogen, C 1-20 alkyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 6-20 aryloxy, C 2-20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, C 2-20 alkynyl, or selected from the group consisting of N, O and S substituted or unsubstituted C 2-20 heteroaryl containing one or more heteroatoms, provided that at least one of R a and R b is not hydrogen;
  • Z 2 is each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 6-20 aryl, substituted or unsubstituted C 1-20 alkylidene, substituted or unsubstituted amino group, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy;
  • n 1 or 0;
  • M 3 is a group 4 transition metal
  • T 2 is carbon, silicon or germanium
  • X 3 and X 4 are the same or different from each other, and are each independently halogen or C 1-20 alkyl,
  • R 11 to R 14 are the same as or different from each other, and are each independently hydrogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7- 20 arylalkyl, or R 11 to R 14 two or more of which are adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic ring, an aromatic ring, or a heteroaromatic ring containing at least one selected from the group consisting of N, O, and S,
  • Q 3 and Q 4 are the same or different from each other, and are each independently C 1-20 alkyl, C 2-20 alkenyl, C 6-30 aryl, or C 2-20 alkoxy alkyl,
  • R 15 is C 1-20 alkyl, C 2-20 alkenyl, or C 6-30 aryl.
  • Halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • the C 1-20 alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group.
  • the C 1-20 alkyl group is a C 1-15 straight chain alkyl group; C 1-10 straight chain alkyl group; C 1-5 straight chain alkyl group; C 3-20 branched chain or cyclic alkyl group; C 3-15 branched chain or cyclic alkyl group; Or it may be a C 3-10 branched chain or cyclic alkyl group.
  • the alkyl group of C 1-20 is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, It may be a neo-pentyl group or a cyclohexyl group.
  • the C 2-20 alkenyl group may be a straight chain, branched chain, or cyclic alkenyl group.
  • the C 2-20 alkenyl group is C 2-20 straight chain alkenyl group, C 2-10 straight chain alkenyl group, C 2-5 straight chain alkenyl group, C 3-20 branched chain alkenyl group, C 3-15 branched chain alkenyl group. It may be a nyl group, a C 3-10 branched chain alkenyl group, a C 5-20 cyclic alkenyl group, or a C 5-10 cyclic alkenyl group. More specifically, the C 2-20 alkenyl group may be an ethenyl group, propenyl group, butenyl group, pentenyl group, or cyclohexenyl group.
  • C 6-20 Aryl refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon and includes monocyclic or condensed ring aryl.
  • C 6-20 aryl may be a phenyl group, biphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, or fluorenyl group.
  • C 7-40 alkylaryl may refer to a substituent in which one or more hydrogens of aryl are replaced by alkyl.
  • C 7-40 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.
  • C 7-40 Arylalkyl may refer to a substituent in which one or more hydrogens of alkyl are replaced by aryl.
  • C 7-40 arylalkyl may be a benzyl group, phenylpropyl, or phenylhexyl.
  • C 6-20 aryloxy examples include phenoxy, biphenoxy, naphthoxy, etc., but are not limited thereto.
  • the C 1-20 alkoxy group includes methoxy group, ethoxy group, phenyloxy group, cyclohexyloxy group, etc., but is not limited thereto.
  • the C 2-20 alkoxyalkyl group is a functional group in which one or more hydrogens of the alkyl group described above are replaced with an alkoxy group, and specifically, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, and iso-propoxy group.
  • Alkoxyalkyl groups such as ethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group may be included, but are not limited thereto.
  • the C 1-20 alkylsilyl group or C 1-20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH 3 are replaced with 1 to 3 alkyl groups or alkoxy groups as described above, specifically methylsilyl group, die Alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group, or dimethylpropylsilyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups such as methoxydimethylsilyl group, diethoxymethylsilyl group, or dimethoxypropylsilyl group may be included, but are not limited thereto.
  • the C 1-20 silylalkyl group is a functional group in which one or more hydrogens of the alkyl group as described above are replaced with a silyl group, and specific examples include -CH 2 -SiH 3 , methylsilylmethyl group, or dimethylethoxysilylpropyl group. , but is not limited to this.
  • the sulfonate group has the structure of -O-SO 2 -R', where R' may be a C 1-20 alkyl group.
  • R' may be a C 1-20 alkyl group.
  • the C 1-20 sulfonate group may include a methane sulfonate group or a phenyl sulfonate group, but is not limited thereto.
  • the heteroaryl is a C 2-20 heteroaryl containing at least one of N, O, and S as a heteroelement, and includes monocyclic or condensed ring heteroaryl.
  • Specific examples include xanthene, thioxanthen, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, and pyridyl group.
  • Midyl group triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group Ginyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, etc., but is not limited to these.
  • the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherphodium (Rf), and specifically, titanium (Ti), zirconium (Zr), or hafnium (Hf). It may be, and more specifically, it may be zirconium (Zr) or hafnium (Hf), but it is not limited thereto.
  • the Group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and may specifically be boron (B) or aluminum (Al). and is not limited to this.
  • substituents are optionally hydroxy groups within the range of having the same or similar effect as the desired effect; halogen; Alkyl group or alkenyl group, aryl group, alkoxy group; an alkyl group or alkenyl group, an aryl group, or an alkoxy group containing one or more heteroatoms from groups 14 to 16; silyl group; Alkylsilyl group or alkoxysilyl group; Phosphine group; phosphide group; Sulfonate group; and may be substituted with one or more substituents selected from the group consisting of a sulfone group.
  • the fact that two adjacent substituents are connected to each other to form an aliphatic or aromatic ring means that the atom(s) of the two substituents and the atoms (atoms) to which the two substituents are bonded are connected to each other to form a ring.
  • examples in which R 9 and R 10 of -NR 9 R 10 are connected to each other to form an aliphatic ring include a piperidinyl group
  • R 9 and R 10 of -NR 9 R 10 are Examples of groups connected to each other to form aromatic rings include pyrrolyl groups.
  • the first metallocene compound represented by Formula 1 is a non-crosslinked compound containing ligands of Cp 1 and Cp 2 , and is mainly a low molecular weight copolymer with a low SCB (short chain branch) content. It is advantageous for making
  • the ligands of Cp 1 and Cp 2 may be the same or different from each other, are each cyclopentadienyl, and may be substituted with 1 or more or 1 to 3 C 1-10 alkyl.
  • the ligands of Cp 1 and Cp 2 can exhibit high polymerization activity by having a lone pair of electrons that can act as a Lewis base.
  • the ligands of Cp 1 and Cp 2 are cyclopentadienyl groups with relatively little steric hindrance. Therefore, it exhibits high polymerization activity and low hydrogen reactivity, allowing low molecular weight polyethylene to be polymerized with high activity.
  • the ligands of Cp 1 and Cp 2 for example, have properties such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of polyethylene, which is manufactured by controlling the degree of steric hindrance effect depending on the type of substituted functional group. can be easily adjusted.
  • the ligands of Cp 1 and Cp 2 are each substituted with R a and R b , where R a and R b are the same or different from each other, and are each independently hydrogen, C 1-20 alkyl, C It may be 2-20 alkoxyalkyl, C 7-40 arylalkyl, or substituted or unsubstituted C 2-12 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S, and may be more Specifically, C 1-10 alkyl, C 2-10 alkoxyalkyl, C 7-20 arylalkyl, or substituted or unsubstituted C containing one or more heteroatoms selected from the group consisting of N, O and S. 4-12 heteroaryl;
  • M 2 Z 2 3-m exists between the ligands of Cp 1 and Cp 2 , and M 2 Z 2 3-m may affect the storage stability of the metal complex.
  • Z 1 may each independently be halogen or C 1-20 alkyl, and more specifically, may each independently be F, Cl, Br or I.
  • M 2 is Ti, Zr, or Hf; is Zr or Hf; Or it may be Zr.
  • Cp 1 and Cp 2 are each unsubstituted or substituted cyclopentadienyl group, and R a and R b are each independently hydrogen, C 1-10 alkyl, C 2-10 alkoxyalkyl, or C 7-20 arylalkyl, where at least one of R a and R b is alkoxyalkyl such as t-butoxyhexyl group, more specifically, -(CH 2 ) p -OR It may be a compound that is a substituent of c (where R c is a straight or branched chain alkyl group having 1 to 6 carbon atoms, and p is an integer of 2 to 4.).
  • the first metallocene compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • the first metallocene compound represented by Chemical Formula 1 can be synthesized by applying known reactions, and the Examples can be referred to for more detailed synthesis methods.
  • the second metallocene compound represented by Formula 2 includes an aromatic ring compound including cyclopentadienyl or a derivative thereof and a nitrogen atom, and the aromatic ring compound and the nitrogen atom It has a structure in which the atoms are cross-linked by a bridging group, T 2 Q 3 Q 4 .
  • the second metallocene compound having this specific structure can be applied to the polymerization reaction of polyethylene, exhibits high activity and copolymerization, and can provide a high molecular weight olefin copolymer.
  • the second metallocene compound represented by Formula 2 has a well-known CGC (constrained geometry catalyst) structure, so it is excellent in introducing comonomers, and in addition, the comonomer is excellent due to the electronic and steric properties of the ligand.
  • the distribution of monomers is controlled. From these properties, the average ethylene sequence length (ASL) is adjusted to increase the middle to high molecular region in the molecular weight distribution, thereby expanding the tie molecule fraction ratio and increasing the entanglement of the polymer chain, along with excellent pipe internal pressure characteristics. It is easy to manufacture polyethylene resin that exhibits long-term stability and processability.
  • CGC constrained geometry catalyst
  • M 3 of the metallocene compound represented by Formula 2 may be a Group 4 transition metal, preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).
  • T 2 may be silicon
  • X 3 and X 4 may each independently be methyl or chlorine (Cl).
  • R 11 to R 14 are the same or different, and may each independently be methyl or phenyl.
  • R 11 to R 14 adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic ring, an aromatic ring, or any one selected from the group consisting of N, O, and S.
  • a heteroaromatic ring containing the above can be formed.
  • R 11 to R 14 Among them two or more adjacent ones are connected to each other to form an aliphatic ring, aromatic ring, or heteroaromatic ring, and cyclopentadiene is fused to an indenyl group, fluorenyl group, benzothiophene group, or dibenzo It can form thiophene groups (dibenzothiophene), etc.
  • the indenyl group, fluorenyl group, benzothiophene group, and dibenzothiophene group may be substituted with one or more substituents.
  • R 15 to R 16 are the same or different, and may each independently be methyl, ethyl, phenyl, propyl, hexyl, or tert-butoxyhexyl.
  • R 17 may be methyl, ethyl, n-propyl, iso-propyl, n-butyl, or tert-butyl.
  • the metallocene compound of Formula 2 is a group consisting of the following compounds: It may be any one selected from, but the present invention is not limited thereto:
  • the second metallocene compound represented by Formula 2 can be synthesized by applying known reactions. Specifically, it may be manufactured by connecting a nitrogen compound and a cyclopentadiene derivative with a bridge compound to prepare a ligand compound, and then performing metallation by adding a metal precursor compound, but is not limited to this and is described in more detail. For synthetic methods, refer to the examples.
  • the second metallocene compound of Formula 2 has excellent activity and can polymerize high molecular weight polyethylene resin. In particular, it exhibits high polymerization activity even when used while supported on a carrier, making it possible to produce ultra-high molecular weight polyethylene resin.
  • the second metallocene compound of Formula 2 according to the present invention exhibits low hydrogen reactivity and still has a high molecular weight distribution. Due to its activity, polymerization of ultra-high molecular weight polyethylene resin is possible. Therefore, even when used in combination with a catalyst with other characteristics, a polyethylene resin that satisfies the characteristics of high molecular weight can be produced without a decrease in activity, making it easy to produce a polyethylene resin with a wide molecular weight distribution, including a high molecular weight polyethylene resin. It can be manufactured.
  • the first metallocene compound represented by Formula 1 mainly contributes to making a low molecular weight copolymer with a low SCB content
  • the second metallocene compound represented by Formula 2 The compounds can mainly contribute to making high molecular weight copolymers with high SCB content. More specifically, the catalyst composition exhibits high copolymerization to comonomers in the copolymer in the high molecular weight region due to the second metallocene compound, and also exhibits high copolymerization in the low molecular weight region due to the first metallocene compound. shows low copolymerization of the comonomer. As a result, a polyethylene resin that not only has excellent mechanical properties but also exhibits a bimodal molecular weight distribution and excellent heat resistance can be manufactured.
  • the above-described physical properties can be realized through controlling the content ratio of the first and second metallocene compounds in the catalyst composition in the present invention, and the resulting improvement effect can be further enhanced.
  • the middle molecular region within the molecule is increased to expand the tie molecule fraction ratio and the polymer chain. Entanglement can be increased and the ratio of the high molecule region to the low molecule region can be optimized.
  • the first and second metallocene compounds should be included in a molar ratio of 1:1 to 1:8.
  • the first and second metallocene compounds may be included in a molar ratio of 1:1 to 1:7, 1:1 to 1:6, or 1:1 to 1:5.5.
  • the polyethylene resin manufactured using them adjusts the balance between mechanical properties and extensibility, thereby providing printability, transparency, and productivity that are equivalent to or superior to the existing ones. and film processability, and can secure excellent mechanical properties with high tensile strength and initial modulus.
  • the first and second metallocene compounds have the above-described structural characteristics and can be stably supported on a carrier.
  • the first and second metallocene compounds are used while supported on the carrier.
  • the particle shape and bulk density of the produced polymer are excellent, and can be suitably used in conventional slurry polymerization, bulk polymerization, and gas phase polymerization processes.
  • the carrier include silica, alumina, magnesia, silica-alumina, silica-magnesia, etc., and these are usually oxides such as Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) 2 , may further include carbonate, sulfate, and nitrate components.
  • silica carrier since the transition metal compound is supported by chemically bonding with reactive functional groups such as siloxane groups present on the surface of the silica carrier, there is almost no catalyst released from the surface of the carrier during the propylene polymerization process. As a result, when producing polypropylene through slurry or vapor phase polymerization, fouling that occurs on the reactor wall or between polymer particles can be minimized.
  • the carrier may be surface modified through a calcination or drying process to increase support efficiency and minimize leaching and fouling.
  • a calcination or drying process to increase support efficiency and minimize leaching and fouling.
  • the calcination or drying process for the carrier may be performed in a range from a temperature at which moisture disappears from the surface of the carrier to a temperature below which reactive functional groups, especially hydroxy groups (OH groups) present on the surface are completely eliminated.
  • the temperature may be 150 to 600 °C, or 200 to 500 °C. If the temperature during calcination or drying of the carrier is low below 150°C, the moisture removal efficiency is low, and as a result, there is a risk that the moisture remaining in the carrier may react with the cocatalyst and reduce the supporting efficiency.
  • the drying or calcination temperature is too high, exceeding 600 °C, the specific surface area decreases as the pores existing on the surface of the carrier merge, and many reactive functional groups such as hydroxy groups or silanol groups existing on the surface are lost, and the siloxane There is a risk that only residues will remain and the number of reaction sites with the cocatalyst will decrease.
  • the total amount of the first and second metallocene compounds described above is 40 ⁇ mol or more, or 80 ⁇ mol based on 1 g of silica. It may be supported in a content range of ⁇ mol or more, 240 ⁇ mol or less, or 160 ⁇ mol or less. When supported in the above content range, it exhibits appropriate supported catalyst activity, which can be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.
  • the catalyst composition may additionally include a cocatalyst to improve high activity and process stability.
  • the type and content of the additional cocatalyst are the same as previously described with respect to the first ethylene-alpha olefin copolymer (a), and detailed details are omitted.
  • the cocatalyst may be, more specifically, an alkylaluminoxane-based cocatalyst such as methylaluminoxane.
  • the alkylaluminoxane-based cocatalyst stabilizes the metallocene compounds and acts as a Lewis acid
  • the functional group introduced into the bridge group of the second metallocene compound is a Lewis acid- Catalytic activity can be further improved by including a metal element that can form a bond through base interaction.
  • the amount of the cocatalyst used can be appropriately adjusted depending on the physical properties or effects of the desired catalyst and resin composition.
  • the cocatalyst may be supported in an amount of 8 mmol or more, or 10 mmol or more, and 25 mmol or less, or 20 mmol or less, per weight of the carrier, for example, based on 1 g of silica. there is.
  • the above-described catalyst composition may be used for polymerization as such, or may be used in a prepolymerized state through contact with an ethylene monomer before use in a polymerization reaction.
  • the production method according to one embodiment of the invention may further include the step of pre-polymerizing (or pre-polymerizing) the catalyst composition by contacting it with an ethylene monomer before producing polyethylene through a polymerization reaction.
  • the catalyst composition includes aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, aromatic hydrocarbon solvents such as toluene and benzene, and chlorine such as dichloromethane and chlorobenzene. It can be dissolved or diluted in an atom-substituted hydrocarbon solvent, etc. and then introduced into the polymerization reaction described later.
  • the solvent used here is preferably treated with a small amount of alkyl aluminum to remove a small amount of water or air, which acts as a catalyst poison, and it is also possible to use a cocatalyst.
  • the polymerization process may be performed by contacting ethylene and a comonomer in the presence of the catalyst composition described above.
  • the polymerization reaction may be bimodal, using two or more reactors, or may be performed in a single polymerization reactor.
  • the polymerization temperature may be 25°C to 500°C, preferably 25°C to 200°C, and more preferably 50°C to 150°C.
  • the polymerization pressure may be 1 kgf/cm2 to 100 kgf/cm2, preferably 1 kgf/cm2 to 50 kgf/cm2, and more preferably 5 kgf/cm2 to 30 kgf/cm2.
  • the amount of 1-hexene added may be about 4.0% by weight to about 6.0% by weight based on the total weight of ethylene added. More specifically, the amount of 1-hexene added is about 4.1% by weight or more, or about 4.2% by weight or more, or about 4.3% by weight or more, or about 4.4% by weight or more, or about 4.5% by weight or more, based on the total weight of ethylene input.
  • weight percent may be less than or equal to about 5.9 weight percent, or less than or equal to about 5.8 weight percent, or less than or equal to about 5.6 weight percent, or less than or equal to about 5.4 weight percent, or less than or equal to about 5.2 weight percent, or less than or equal to about 5.0 weight percent.
  • the polyethylene resin according to the present invention can be produced by copolymerizing ethylene and a comonomer by adding hydrogen gas in the presence of the catalyst composition described above.
  • the hydrogen gas has a content of 35 ppm to 250 ppm, or 40 ppm to 200 ppm, or 50 ppm to 190 ppm, or 55 ppm to 180 ppm, or 58 ppm to 170 ppm, or 60 ppm, based on the weight of ethylene.
  • the content may be from ppm to 145 ppm.
  • the first and second transition metal compounds are added to the cocatalyst-supporting carrier, stirred, and then a cocatalyst can be further added to prepare a supported catalyst.
  • the content of the carrier, co-catalyst, co-catalyst supporting carrier, and transition metal compound used can be appropriately adjusted depending on the physical properties or effects of the desired supported catalyst.
  • first transition metal compound first transition metal compound: second transition metal compound
  • first transition metal compound second transition metal compound
  • the amount of the metallocene compound supported on the silica carrier through the above step may be 0.01 to 1 mmol/g based on 1 g of the carrier. That is, it is desirable to control the amount to fall within the above-mentioned range, taking into account the contribution effect of the metallocene compound as a catalyst.
  • reaction solvents include hydrocarbon solvents such as pentane, hexane, and heptane; Alternatively, an aromatic solvent such as benzene, toluene, etc. may be used.
  • the method for producing the supported catalyst is not limited to the content described herein, and the production method may additionally employ steps commonly employed in the technical field to which the present invention pertains, and the steps of the production method ( s) can be changed by conventionally changeable step(s).
  • the polyethylene copolymer as described above can be prepared through a method comprising copolymerizing ethylene and alpha-olefin in the presence of the hybrid supported metallocene catalyst.
  • the above-described hybrid supported catalyst can exhibit excellent supporting performance, catalytic activity, and high copolymerization properties, and can produce a polyethylene copolymer capable of producing a polyethylene film with excellent expandable processing area characteristics and mechanical properties.
  • the method for producing the first ethylene-alpha-olefin copolymer (a) can be performed by slurry polymerization using ethylene and alpha-olefin as raw materials in the presence of the above-described hybrid supported catalyst by applying conventional equipment and contact technology.
  • the method for producing the first ethylene-alpha-olefin copolymer (a) may copolymerize ethylene and alpha-olefin using a continuous slurry polymerization reactor, a loop slurry reactor, etc., but is not limited thereto.
  • the mechanical properties of the polyethylene copolymer are increased due to the interaction of two or more catalysts. In addition to physical properties, both processability and shrinkage can be further improved.
  • the polymerization process with a carrier for supporting the first metallocene compound and the second metallocene compound and an additional cocatalyst is performed prior to the first ethylene-alpha olefin copolymer.
  • (a) is the same as described above, and specific details are omitted.
  • the first ethylene-alpha-olefin copolymer (a) according to the present invention can be produced by copolymerizing ethylene and alpha-olefin using the above-described supported metallocene catalyst.
  • the first ethylene-alphaolefin copolymer (a) having the above-described physical properties can be produced.
  • the polyethylene composition according to one embodiment of the present invention includes the above-described first ethylene-alpha olefin copolymer (a) and the second ethylene-alpha olefin copolymer (b) which has excellent flowability and excellent stretching stability and shrinkage resistance.
  • a first ethylene-alpha olefin copolymer
  • b second ethylene-alpha olefin copolymer
  • the second ethylene-alpha olefin copolymer (b) has a density of 0.870 g/cm 3 to 0.920 g/cm 3 and a melt index (MI 2.16 , 190° C., 2.16 kg load) of 15 g/10 min. It may be less than or equal to 3.0 g/10min to 15 g/10min.
  • the second ethylene-alphaolefin copolymer (b) has a density of 0.880 g/cm 3 or more, 0.890 g/cm 3 or more, 0.895 g/cm 3 or more, or 0.900 g/cm 3 or more, It may be 0.915 g/cm 3 or less, 0.910 g/cm 3 or less, 0.905 g/cm 3 or less, or 0.904 g/cm 3 or less.
  • the second ethylene-alphaolefin copolymer (b) has a melt index (MI 2.16 , 190° C., 2.16 kg load) of 15 g/10min or less, 13.5 g/10min or less, 12 g/10min or less, 10 g /10min or less, 9.0 g/10min or less, 8.0 g/10min or less, or 7.0 g/10min or less.
  • the melt index (MI 2.16 , 190 o C, 2.16 kg load) of the second ethylene-alphaolefin copolymer (b) is 4.0 g/10 min. or more, 5.0 g/10min or more, 5.5 g/10min or more, 5.8 g/10min or more, or 6.0 g/10min or more.
  • the second ethylene-alpha olefin copolymer (b) has a number average molecular weight (Mn) of 20,000 g/mol or more to 50,000 g/mol or less, and a weight average molecular weight (Mw) of 50,000 g/mol or more to 100,000 g/mol. mol or less, and the molecular weight distribution (Mw/Mn) may be 1.5 or more to 4.0 or less.
  • the number average molecular weight (Mn) of the second ethylene-alphaolefin copolymer (b) is 22000 g/mol or more, 23000 g/mol or more, 24000 g/mol or more, 25000 g/mol or more, or 28000. g/mol or more, and may be less than or equal to 45000 g/mol, less than or equal to 40000 g/mol, less than or equal to 38000 g/mol, less than or equal to 35000 g/mol, less than or equal to 32000 g/mol, or less than or equal to 30000 g/mol.
  • the weight average molecular weight (Mw) of the second ethylene-alpha olefin copolymer (b) is 51000 g/mol or more, 52000 g/mol or more, 55000 g/mol or more, 60000 g/mol or more, or 65000 g/mol or more. mol or more, and may be less than or equal to 90000 g/mol, less than or equal to 85000 g/mol, less than or equal to 80000 g/mol, less than or equal to 75000 g/mol, less than or equal to 70000 g/mol, or less than or equal to 68000 g/mol.
  • the molecular weight distribution (Mw/Mn) of the second ethylene-alphaolefin copolymer (b) is 1.7 or more, 1.9 or more, 2.0 or more, 2.1 or more, or 2.2 or more, and is 3.5 or less, 3.0 or less, 2.8 or less, and 2.5 or more. It may be less than or equal to 2.3.
  • the second ethylene-alpha olefin copolymer (b) may have at least one of the above-described physical properties, and may have all of the above-described physical properties in order to exhibit excellent mechanical strength.
  • the second ethylene-alphaolefin copolymer (b) includes ethylene and 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, It may include one or more alpha-olefins selected from the group consisting of 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and mixtures thereof.
  • the second ethylene-alpha olefin copolymer (b) may be an ethylene 1-octene copolymer.
  • the second ethylene-alpha olefin copolymer (b) is the above-mentioned copolymer, the above-mentioned physical properties can be more easily realized.
  • the type of the second ethylene-alpha olefin copolymer (b) is not limited to the above-mentioned types, and various types known in the art to which the present invention pertains may be provided as long as they can exhibit the above-mentioned physical properties.
  • the second ethylene-alpha olefin copolymer (b) was manufactured in the presence of a metallocene catalyst.
  • the second ethylene-alphaolefin copolymer (b) can be produced by copolymerizing ethylene and a comonomer in the presence of a catalyst composition containing a metallocene compound represented by the following formula (3).
  • M 1 is a Group 4 transition metal
  • Z is -O-, -S-, -NR a -, or -PR a -,
  • R a is hydrogen, any one of a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, and a silylhydrocarbyl group having 1 to 20 carbon atoms;
  • T 1 is C, Si, Ge, Sn or Pb,
  • Q 1 and Q 2 are the same or different from each other, and are each independently hydrogen, a hydrocarbyl group with 1 to 30 carbon atoms, a hydrocarbyloxy group with 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group with 2 to 30 carbon atoms, -SiH 3 , any one of a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR b R c ,
  • R b and R c are each independently hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic or aromatic ring;
  • C 1 is any one of the ligands represented by the following formulas 3a to 3d,
  • Y is O or S
  • R 1 to R 6 are the same as or different from each other, and are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyloxy group having 1 to 30 carbon atoms.
  • Hydrocarbyl group is a monovalent functional group obtained by removing a hydrogen atom from hydrocarbon, and includes alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, aralkenyl group, aralkynyl group, alkylaryl group, alkenylaryl group, and alkyl group. It may include a nylaryl group, etc.
  • the hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 10 carbon atoms.
  • the hydrocarbyl group may be straight chain, branched chain, or cyclic alkyl.
  • the hydrocarbyl group having 1 to 30 carbon atoms is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group.
  • Straight-chain, branched-chain, or cyclic alkyl groups such as actual group, n-heptyl group, and cyclohexyl group; Alternatively, it may be an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl.
  • alkylaryl such as methylphenyl, ethylphenyl, methylbiphenyl, and methylnaphthyl
  • arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, and naphthylmethyl
  • alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, and pentenyl.
  • a hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen.
  • a hydrocarbyloxy group having 1 to 30 carbon atoms may be a hydrocarbyloxy group having 1 to 20 carbon atoms or a hydrocarbyloxy group having 1 to 10 carbon atoms.
  • the hydrocarbyloxy group may be straight chain, branched chain, or cyclic alkyl. More specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms is methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, and n-pentoxy group.
  • straight-chain, branched-chain, or cyclic alkoxy groups such as n-hexoxy group, n-heptoxy group, and cyclohexoxy group; Alternatively, it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.
  • Hydrocarbyloxyhydrocarbyl group is a functional group in which one or more hydrogens of the hydrocarbyl group are replaced with one or more hydrocarbyloxy groups.
  • a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms may be a hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms or a hydrocarbyloxyhydrocarbyl group having 2 to 15 carbon atoms.
  • the hydrocarbyloxyhydrocarbyl group may be straight chain, branched chain, or cyclic alkyl.
  • the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms is methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-part Alkoxyalkyl groups such as toxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group; Or it may be an aryloxyalkyl group such as a phenoxyhexyl group.
  • Hydrocarbyl (oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH 3 are replaced with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups.
  • the hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms may be a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms.
  • the hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms is an alkyl group such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group, or dimethylpropylsilyl group.
  • silyl group Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; It may be an alkoxyalkyl silyl group such as methoxydimethylsilyl group, diethoxymethylsilyl group, or dimethoxypropylsilyl group.
  • a silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which one or more hydrogens of the hydrocarbyl group are replaced with a silyl group.
  • the silyl group may be -SiH 3 or a hydrocarbyl (oxy)silyl group.
  • a silylhydrocarbyl group having 1 to 20 carbon atoms may be a silylhydrocarbyl group having 1 to 15 carbon atoms or a silylhydrocarbyl group having 1 to 10 carbon atoms.
  • the silylhydrocarbyl group having 1 to 20 carbon atoms is a silylalkyl group such as -CH 2 -SiH 3 ; Alkylsilylalkyl groups such as methylsilylmethyl group, methylsilylethyl group, dimethylsilylmethyl group, trimethylsilylmethyl group, dimethylethylsilylmethyl group, diethylmethylsilylmethyl group, or dimethylpropylsilylmethyl group; Or it may be an alkoxysilylalkyl group such as dimethylethoxysilylpropyl group.
  • Halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • the sulfonate group has the structure of -O-SO 2 -R d , where R d may be a hydrocarbyl group having 1 to 30 carbon atoms. Specifically, the sulfonate group having 1 to 30 carbon atoms may be a methane sulfonate group or a phenyl sulfonate group.
  • the sulfone group having 1 to 30 carbon atoms has the structure of -R e' -SO 2 -R e" , where R e' and R e" are the same or different from each other and are each independently any one of the hydrocarbyl groups having 1 to 30 carbon atoms. You can.
  • the sulfone group having 1 to 30 carbon atoms may be a methylsulfonylmethyl group, a methylsulfonylpropyl group, a methylsulfonylbutyl group, or a phenylsulfonylpropyl group.
  • the fact that two adjacent substituents are connected to each other to form an aliphatic or aromatic ring means that the atom(s) of the two substituents and the atoms (atoms) to which the two substituents are bonded are connected to each other to form a ring. do.
  • examples of R b and R c or R b' and R c' of -NR b R c or -NR b' R c' being linked together to form an aliphatic ring include a piperidinyl group , etc.
  • R b and R c or R b' and R c' of -NR b R c or -NR b ' R c' being connected to each other to form an aromatic ring include a pyrrolyl group, etc. It can be exemplified.
  • the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherphodium (Rf), and specifically, titanium (Ti), zirconium (Zr), or hafnium (Hf). It may be, and more specifically, it may be zirconium (Zr) or hafnium (Hf), but it is not limited thereto.
  • the Group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and may specifically be boron (B) or aluminum (Al). and is not limited to this.
  • substituents are optionally hydroxy groups within the range of having the same or similar effect as the desired effect; halogen; hydrocarbyl group; hydrocarbyloxy group; A hydrocarbyl group or hydrocarbyloxy group containing one or more heteroatoms from groups 14 to 16; silyl group; Hydrocarbyl (oxy)silyl group; Phosphine group; phosphide group; Sulfonate group; and may be substituted with one or more substituents selected from the group consisting of a sulfone group.
  • Z is -NR a -
  • R a may be a hydrocarbyl group having 1 to 10 carbon atoms, and specifically, R a is a straight-chain or branched alkyl group having 1 to 6 carbon atoms. It may be, and more specifically, it may be a tert-butyl group.
  • T is and T 1 is carbon (C) or silicon (Si), and Q 1 and Q 2 may each independently be hydrogen, a hydrocarbyl group with 1 to 30 carbon atoms, or a hydrocarbyloxy group with 1 to 30 carbon atoms.
  • Q 1 and Q 2 may each be a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 12 carbon atoms.
  • Q 1 and Q 2 may each be an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy having 1 to 6 carbon atoms.
  • Q 1 and Q 2 may each independently be hydrogen, methyl, ethyl, or tert-butoxy substituted hexyl.
  • T 1 may be silicon (Si), and both Q 1 and Q 2 may be methyl, or one of Q 1 and Q 2 may be methyl and the other may be tert-butoxy substituted hexyl.
  • the metallocene compound represented by Formula 3 may be represented by any one of the following Formulas 3-1 to 3-4.
  • R 1 to R 4 may each be hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms
  • R 5 and R 6 may each be a hydrocarbyl group having 1 to 10 carbon atoms.
  • R 1 to R 4 may each be hydrogen or alkyl having 1 to 10 carbon atoms
  • R 5 and R 6 may each be alkyl having 1 to 10 carbon atoms.
  • R 1 to R 4 may each be hydrogen or methyl
  • R 5 and R 6 may be methyl.
  • M 1 may be titanium (Ti), zirconium (Zr), or hafnium (Hf), and preferably titanium (Ti).
  • the metallocene compound may be represented by one of the following structural formulas.
  • Metallocene compounds represented by the above structural formulas can be synthesized by applying known reactions, and more detailed synthesis methods can be referred to the Examples and Synthesis Examples described later.
  • the transition metal compound represented by Formula 3 used in the present invention controls the degree of introduction of alpha-olefin monomers in the copolymerization process due to the structural characteristics of the catalyst, exhibits the density as described above, and as a result, excellent Flow stone and stretching processability can be secured.
  • the polymerization reaction can be performed by continuously polymerizing ethylene and alpha-olefin monomers by continuously introducing hydrogen in the presence of a catalyst composition containing one or more transition metal compounds represented by Formula 3, and specific This may be performed while introducing hydrogen at 5 to 100 cc/min.
  • the hydrogen gas suppresses the rapid reaction of the transition metal compound at the beginning of polymerization and serves to terminate the polymerization reaction. Accordingly, an ethylene/alpha-olefin copolymer with a narrow molecular weight distribution can be effectively produced by controlling the use and amount of hydrogen gas.
  • the hydrogen may be introduced at 5 cc/min or more, or 7 cc/min or more, or 10 cc/min or more, or 15 cc/min or more, or 19 cc/min or more, and 100 cc/min or less, Alternatively, it may be administered at 50 cc/min or less, or 45 cc/min or less, or 35 cc/min or less, or 29 cc/min or less.
  • the produced ethylene/alpha-olefin copolymer can implement the physical properties of the present invention.
  • the completion of the polymerization reaction may not occur uniformly, making it difficult to manufacture an ethylene/alpha-olefin copolymer with desired physical properties, and if the amount of hydrogen gas is added at a content exceeding 100 cc/min, the polymerization reaction may not be completed uniformly. In this case, there is a risk that the termination reaction may occur too quickly, resulting in the production of an ethylene/alpha-olefin copolymer with a very low molecular weight.
  • the polymerization reaction can be performed at 100°C to 200°C, and by controlling the polymerization temperature along with the hydrogen input amount, the crystallinity distribution and molecular weight distribution in the ethylene/alpha-olefin copolymer can be more easily controlled.
  • the polymerization reaction may be performed at 100°C to 200°C, 120°C to 180°C, 130°C to 170°C, and 140°C to 160°C, but is not limited thereto.
  • a cocatalyst may be additionally used in the catalyst composition to activate the transition metal compound of Formula 3.
  • the cocatalyst is an organometallic compound containing a Group 13 metal, and may specifically include one or more selected from the following Chemical Formulas 4 to 4.
  • R 7 , R 8 and R 9 are each independently hydrogen, halogen, C 1-20 hydrocarbyl group, or C 1-20 hydrocarbyl group substituted with halogen,
  • n is an integer greater than or equal to 2
  • D is aluminum or boron
  • R 10 is each independently halogen, C 1-20 hydrocarbyl group, C 1-20 hydrocarbyloxy group, or C 1-20 hydrocarbyl group substituted with halogen,
  • L is a neutral or cationic Lewis base
  • H is a hydrogen atom
  • W is a group 13 element
  • A is each independently a C 1-20 hydrocarbyl group; C 1-20 hydrocarbyloxy group; and substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents selected from halogen, C 1-20 hydrocarbyloxy group, and C 1-20 hydrocarbyl (oxy)silyl group.
  • [LH] + is Bronsted acid.
  • [LH] + is trimethylammonium; triethylammonium; tripropylammonium; Tributylammonium; diethylammonium; trimethylphosphonium; or triphenylphosphonium, where [L] + is N,N-diethylanilinium; Or triphenylcarbonium.
  • W may be B 3+ or Al 3+ .
  • the compound represented by Formula 4 may serve as an alkylating agent and an activator
  • the compound represented by Formula 5 may serve as an alkylating agent
  • the compound represented by Formula 6 may serve as an activator. there is.
  • the compound of Formula 4 may be an alkylaluminoxane-based compound in which repeating units are bonded in a linear, circular, or network form, and specific examples include methylaluminoxane (MAO), ethyl aluminoxane, and isobutyl aluminoxane. Or tert-butyl aluminoxane, etc. can be mentioned.
  • Non-limiting examples of the compound represented by Formula 4 above include methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, or tert-butyl aluminoxane.
  • Non-limiting examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloroaluminum, triisopropyl aluminum, tri-sec-butyl aluminum, Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide or dimethyl aluminum. Toxide, etc. can be mentioned.
  • non-limiting examples of the compound represented by Formula 6 include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis( Pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium Benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium Tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3 ,5,6-tetrafluorophenyl)
  • the cocatalyst may be, more specifically, an alkylaluminoxane-based cocatalyst such as methylaluminoxane.
  • the amount of the cocatalyst used can be appropriately adjusted depending on the physical properties or effects of the desired hybrid supported metallocene catalyst.
  • the cocatalyst may be used in an appropriate amount to ensure sufficient activation of the transition metal compound of Formula 3.
  • the amount of the cocatalyst used can be appropriately adjusted depending on the physical properties or effects of the desired hybrid supported metallocene catalyst.
  • the transition metal compound of Formula 3 may be used in the form supported on a carrier.
  • the weight ratio of the transition metal compound and the carrier may be 1:10 to 1:1000, more specifically 1:10 to 1:500.
  • a carrier and a transition metal compound are included in a neutral ratio within the above-mentioned range, an optimal shape can be obtained.
  • the weight ratio of co-catalyst to carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50.
  • the cocatalyst and carrier are included in the above weight ratio, the catalytic activity can be improved and the microstructure of the produced polymer can be optimized.
  • the carrier may be silica, alumina, magnesia, or a mixture thereof, or these materials may be dried at high temperature to remove moisture from the surface, thereby forming a state containing highly reactive hydroxy groups or siloxane groups on the surface. It may also be used.
  • the high-temperature dried carriers may further contain oxides, carbonates, sulfates, or nitrates such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 .
  • the drying temperature of the carrier is preferably 200°C to 800°C, more preferably 300°C to 600°C, and most preferably 300°C to 400°C. If the drying temperature of the carrier is less than 200 °C, there is too much moisture, so the moisture on the surface reacts with the cocatalyst. If it is more than 800 °C, the pores on the surface of the carrier merge, the surface area decreases, and many hydroxyl groups on the surface disappear. This is undesirable because only siloxane residues remain and the number of reaction sites with the cocatalyst decreases.
  • the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 mmol/g to 10 mmol/g, and more preferably 0.5 mmol/g to 5 mmol/g.
  • the amount of hydroxy groups on the surface of the carrier can be adjusted by the preparation method and conditions of the carrier or drying conditions such as temperature, time, vacuum or spray drying.
  • an organoaluminum compound is further added to remove moisture in the reactor, and the polymerization reaction can proceed in its presence.
  • organic aluminum compounds include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, or alkyl aluminum sesqui halide, and more specific examples thereof include Al(C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 H, Al(C 3 H 7 ) 3 , Al(C 3 H 7 ) 2 H, Al(iC 4 H 9 ) 2 H, Al(C 8 H 17 ) 3 , Al(C 12 H 25 ) 3 , Al(C 2 H 5 )(C 12 H 25 ) 2 , Al(iC 4 H 9 )(C 12 H 25 ) 2 , Al(iC 4 H 9 ) 2 H, Al(iC 4 H 9 ) 3 , (C 2 H 5 ) 2 AlCl, (iC 3 H 9 )
  • the polymerization pressure is about 1 Kgf/cm 2 to about 100 Kgf/cm 2 , preferably about 1 Kgf/cm 2 to about 50 Kgf/cm 2 , and more preferably about 5 Kgf/cm 2 to about 30 Kgf. It can be / cm2 .
  • the transition metal compound when used in the form supported on a carrier, the transition metal compound may be used in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, toluene, and benzene. It can be dissolved in an aromatic hydrocarbon solvent such as dichloromethane, a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene, or added after dilution.
  • the solvent used here is preferably treated with a small amount of alkyl aluminum to remove a small amount of water or air, which acts as a catalyst poison, and it is also possible to use an additional cocatalyst.
  • the second ethylene-alpha-olefin copolymer (b) can be produced by copolymerizing ethylene and alpha-olefin using the metallocene catalyst described above.
  • the second ethylene-alphaolefin copolymer (b) having the above-described physical properties can be produced.
  • the polyethylene composition of the present invention includes the first ethylene-alpha olefin copolymer and the second ethylene-alpha olefin copolymer with optimized density and melt index as described above, respectively, in a predetermined content ratio, and has a high crystalline molecular content ( ⁇ As the 90 °C elution ratio TREF ⁇ 90 °C increases, the medium crystalline molecule content (35-90 °C elution ratio TREF 35-90 °C ) and soluble fraction ( ⁇ 35 °C elution ratio TREF ⁇ 35 °C ) appear low, It has high yield strength and secant modulus, i.e. 1% and 2% initial modulus. As a result, the polyethylene composition maintains excellent printability, transparency, productivity, and film processability during film processing, while exhibiting high tensile strength and initial modulus, showing excellent mechanical properties and securing excellent mechanical properties such as film rigidity.
  • the polyethylene composition having the above-described composition and physical properties maintains excellent mechanical properties, productivity, and film processability, and can stably form a polyethylene film with excellent mechanical properties, printability, and transparency with high tensile strength and initial modulus.
  • the polyethylene film can be manufactured by a conventional film manufacturing method except for using the polyethylene composition described above.
  • the polyethylene film according to the present invention can stably form a blown film using the above-described polyethylene composition by a melt blown method or the like.
  • the polyethylene film can be manufactured by inflation molding the polyethylene composition to a predetermined thickness, specifically 15 micrometers ( ⁇ m) to 200 micrometers ( ⁇ m), using an extruder during blown film processing.
  • the film thickness may be 18 ⁇ m to 150 ⁇ m, or 20 ⁇ m to 100 ⁇ m, or 25 ⁇ m to 75 ⁇ m.
  • the extrusion temperature of the extruder may be 120 o C to 200 o C, or 125 o C to 190 o C, or 130 o C to 180 o C.
  • the blow up ratio (BUR) may be 3.4 or less or 0.5 to 3.4, specifically 2.8 or less or 1.0 to 2.8, or 2.5 or less or 1.5 to 2.5.
  • the die gap may be 1 mm to 3 mm, specifically 1 mm, 1.75 mm, or 3 mm.
  • the polyethylene film according to the present invention may further include additives well known in the field in addition to the polyethylene copolymer described above.
  • additives include solvents, heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal deactivators, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, optical bleaching agents, flame retardants, antistatic agents, foaming agents, etc.
  • the type of the additive is not particularly limited, and general additives known in the art can be used.
  • the polyethylene film according to one embodiment of the present invention manufactured by the above method can improve performance with excellent expandable processing area characteristics and mechanical properties.
  • the polyethylene film has a blow up ratio (BUR) of 2.2 to 2.5 on the X-axis, which is the food/industrial film processing area, and a take-off speed of 4 m/min to 16 m/min on the Y-axis.
  • BUR blow up ratio
  • the area of the area showing bubble stability according to the blow up ratio (BUR) of 2.2 to 2.5 and the take-off speed of 4 m/min to 16 m/min is the total area of the graph. It may be 80% or more, or 90% or more, or 95% or more, or 98% or more, or 100%.
  • the bubble stability can be measured at a film thickness of 15 ⁇ m to 200 ⁇ m under 180 o C conditions.
  • film forming of each polyethylene composition can be performed using a single screw extruder.
  • Inflation molding can be done by setting the take-off speed from 5 m/min to 20 m/min to achieve a thickness of ⁇ m.
  • the die gap is set to 1.0, 1.75, 3.0 mm, and the blow-up ratio is set to 2.5.
  • each physical property is measured by thickness with the film obtained according to die gap and TUR.
  • the polyethylene film has a haze of 28% or less, or 9% to 28%, as measured under the condition of a film thickness of 25 ⁇ m using the ASTM D 1003 method.
  • the film has a haze measured by the ASTM D 1003 method of 9% (25 ⁇ m, die gap 1.0 mm) to 28% (25 ⁇ m, die gap 3.0 mm) at 25 ⁇ m, die gap 1.0 mm. Or, it may be 27% or less or 15% to 27%, or it may be 26% or less or 19% to 26%.
  • the polyethylene film may have a gloss (gloss 45 o ) of 80 GU or more, or 80 GU to 100 GU, as measured according to the ASTM 2457 standard, and preferably 85 GU or more, or 88 GU or more, or 90 GU. It may be greater than or equal to 94 GU.
  • the polyethylene film of the present invention exhibits high tensile strength and secant modulus, that is, 1% and 2% initial modulus, showing excellent mechanical properties.
  • the polyethylene film was manufactured as a blown film by inflation molding under the following equipment and conditions, then a tensile test specimen was prepared according to the ASTM D 882 standard, and the MD direction was measured according to the ASTM D 882 standard. Tensile tests are performed in (Machine Direction) and TD directions (Transverse Direction) to measure tensile strength, 1% and 2% initial modulus, and elongation at break.
  • the MD and TD directions of the film may be the longitudinal and transverse directions of the film, respectively.
  • the polyethylene film has a tensile strength in the MD direction (Machine Direction) and TD direction (Transverse Direction) measured according to the ASTM D 882 standard of 40 MPa or more, 42 MPa or more, 44 MPa or more, and 46 MPa or more, It may be at least 48 MPa, at least 49.5 MPa, at least 50 MPa, at least 52 MPa, or at least 54 MPa, and at least 100 MPa.
  • the tensile strength of the polyethylene film in the MD direction is 40 MPa or more, 42 MPa or more, 44 MPa or more, 46 MPa or more, 48 MPa or more, or 49.5 MPa or more, and in the TD direction (Transverse Direction)
  • the tensile strength may be at least 50 MPa, at least 52 MPa, or at least 54 MPa.
  • the polyethylene film has an MD/TD average tensile strength measured according to the ASTM D 882 standard of 45 MPa or more, 46.5 MPa or more, 48 MPa or more, 49.5 MPa or more, or 50 MPa or more, or 52 MPa or more, and 100 MPa or more. It may be less than MPa.
  • the polyethylene film has an initial modulus in the MD direction (Machine Direction) and TD direction (Transverse Direction) measured according to the ASTM D 882 standard, that is, the MD direction (Machine Direction) and the TD direction (Transverse Direction) according to the ASTM D 882 standard ( Transverse Direction)
  • the initial modulus, 1% modulus, and 2% modulus at 1% and 2% elongation, respectively are high, showing excellent rigidity.
  • the polyethylene film has a 1% modulus in the MD direction (Machine Direction) and the TD direction (Transverse Direction) of 400 MPa or more, or 410 MPa or more, or 450 MPa or more, 480 MPa or more, or 500 MPa or more. It may be MPa or more, or 540 MPa or more, and 1100 MPa or less.
  • the polyethylene film has a 2% modulus in the MD direction (Machine Direction) and TD direction (Transverse Direction) of 300 MPa or more, 305 MPa or more, 330 MPa or more, 340 MPa or more, 350 MPa or more, and 375 MPa or more. It may be MPa or more, or 400 MPa or more, and 1000 MPa or less.
  • the 1% modulus of the MD direction (Machine Direction) of the polyethylene film may be 410 MPa or more, and the 2% modulus may be 305 MPa or more.
  • the 1% modulus of the TD direction (transverse direction) of the polyethylene film may be 500 MPa or more, or 540 MPa or more, and the 2% modulus may be 400 MPa or more, or 405 MPa or more.
  • 1% modulus and 2% modulus represent the modulus values at the 1% and 2% elongation points, respectively, in the strength-elongation curve obtained from the tensile test as described above.
  • the polyethylene film has an average MD/TD 1% modulus measured according to the ASTM D 882 standard of 450 MPa or more, 460 MPa or more, 470 MPa or more, 475 MPa or more, 480 MPa or more, 485 MPa or more, It may be at least 490 MPa, at least 500 MPa, at least 520 MPa, at least 540 MPa, at least 550 MPa, at least 560 MPa, or at least 570 MPa, and at least 1100 MPa.
  • the polyethylene film has an average MD/TD 2% modulus measured according to the ASTM D 882 standard of 350 MPa or more, 355 MPa or more, 358 MPa or more, 360 MPa or more, 365 MPa or more, 370 MPa or more, It may be at least 375 MPa, at least 390 MPa, at least 400 MPa, or at least 430 MPa, and at most 1000 MPa.
  • the polyethylene film has an elongation at break in the MD direction (Machine Direction) and TD direction (Transverse Direction) measured according to the ASTM D 882 standard of 630% to 998%, 650% to 997%, or It may be 680% or more and 995% or less, or 685% or more and 993% or less.
  • the elongation at break in the MD direction (Machine Direction) of the polyethylene film is 630% or more and 750% or less, 650% or more and 745% or less, 680% or more and 740% or less, or 685% or more and 735%.
  • the elongation at break in the TD direction may be 750% or more and 998% or less, 765% or more and 997% or less, 780% or more and 995% or less, or 800% or more and 993% or less.
  • the elongation at break represents the elongation at break in the tensile test as described above.
  • the polyethylene film has an MD/TD average elongation at break measured according to the ASTM D 882 standard of 630% to 995%, or 735% to 815%, or 740% to 812%, or 742%. It may be from % to 810%, or from 743% to 800%.
  • the polyethylene film has a tear strength in the MD direction measured according to the ASTM 1922 standard of 1.2 N/mm to 4.0 N/mm, or 1.3 N/mm to 3.5 N/mm, or 1.35 N/mm to 3.0 N. /mm, or 1.4 N/mm to 2.8 N/mm, and the tear strength in the TD direction is 8 N/mm to 25 N/mm, or 9 N/mm to 20 N/mm, or 10 N/mm. to 18 N/mm, or 10.2 N/mm to 17.9 N/mm.
  • the polyethylene film has an MD/TD average tear strength measured according to the ASTM 1922 standard of 2 N/mm to 20 N/mm, or 3.5 N/mm to 18 N/mm, or 5 N/mm to 15 N/mm. N/mm, or 5.5 N/mm to 14 N/mm, or 5.8 N/mm to 13.5 N/mm.
  • the physical properties of the polyethylene film can be evaluated according to the above-mentioned standards, and the specific method is as described in Test Example 3, which will be described later.
  • the mechanical properties are improved through blending of the first ethylene-alphaolefin copolymer, which has excellent flowability and can provide film processability, and the second ethylene-alphaolefin copolymer, which has excellent mechanical properties.
  • the polyethylene composition according to the present invention maintains excellent printability, transparency, productivity, and film processability, and has the excellent effect of producing a polyethylene film with excellent mechanical properties with a high initial modulus.
  • t-butyl-O-(CH 2 ) 6 -Cl was prepared using 6-chlorohexanol by the method described in Tetrahedron Lett. 2951 (1988), and Na(C 5 H 5 ) [NaCp ] was reacted to obtain t-butyl-O-(CH 2 ) 6 -C 5 H 5 (yield 60%, bp 80 o C/0.1 mmHg).
  • t-butyl-O-(CH 2 ) 6 -C 5 H 5 was dissolved in tetrahydrofuran (THF) at -78 o C, n-butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature. Afterwards, it was reacted for 8 hours.
  • the synthesized lithium salt solution was slowly added to the suspension solution of ZrCl 4 (THF) 2 (170 g, 4.50 mmol) / THF (30 mL) at -78 o C and reacted at room temperature for another 6 hours. I ordered it. All volatile substances were removed by vacuum drying, and hexane was added to the obtained oily liquid material and filtered.
  • the obtained liquid was confirmed to be the desired methyl(6-t-butoxy hexyl)dichlorosilane ⁇ Methyl(6-t-butoxy hexyl)dichlorosilane ⁇ compound through 1 H-NMR.
  • n-BuLi 480 mL was added to the reactor at a rate of 5 mL/min using a feeding pump. After adding n-BuLi, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, an equivalent amount of methyl(6-t-butoxy hexyl)dichlorosilane (326 g, 350 mL) was quickly added to the reactor. The reactor temperature was slowly raised to room temperature and stirred for 12 hours, then the reactor temperature was cooled to 0° C.
  • TiCl 3 (THF) 3 (10 mmol) was synthesized from n-BuLi and the ligand dimethyl(tetramethylCpH)t-Butylaminosilane in a THF solution at -78°C. ) was applied quickly.
  • the reaction solution was stirred for 12 hours while slowly raising the temperature from -78°C to room temperature.
  • an equivalent amount of PbCl 2 (10 mmol) was added to the reaction solution at room temperature and stirred for 12 hours. After stirring for 12 hours, a dark black solution with a blue tinge was obtained.
  • THF was removed from the resulting reaction solution, hexane was added and the product was filtered.
  • a 1-benzothiophene solution was prepared by dissolving 4.0 g (30 mmol) of 1-benzothiophene in THF. Then, 14 mL (36 mmol, 2.5 M in hexane) of n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution. Then, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80°C, and the resulting solution was stirred at room temperature for about 10 hours.
  • a solution was prepared by dissolving the alcohol intermediate in toluene. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution and refluxed for about 10 minutes. The obtained reaction mixture was separated by column chromatography, showing an orange-brown color, and 1.8 g (9.0 mmol, 98%) of liquid 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (Ligand A). % yield) was obtained.
  • Ligand A 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (Ligand A) was added to a 250mL schlenk flask, and 30 mL of THF was added to prepare a Ligand A solution. After cooling the Ligand A solution to -78°C, 3.6 mL (9.1 mmol, 2.5 M in hexane) of n-BuLi solution was added to the Ligand A solution and stirred at room temperature overnight to form a purple-brown solution. got it Solution A was prepared by replacing the solvent of the purple-brown solution with toluene, and adding 39 mg (0.43 mmol) of CuCN dispersed in 2 mL of THF to this solution.
  • solution B prepared by injecting 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilanamine (ligand B) and toluene into a 250 mL schlenk flask. was cooled to -78°C.
  • Solution A prepared previously was slowly injected into the cooled solution B. Then, the mixture of solutions A and B was stirred at room temperature overnight. Then, the produced solid is removed by filtration to produce 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl), a brown-colored and viscous liquid.
  • the cross-linked products of the ligands A and B were lithiated at room temperature, and then H-NMR spectra were obtained using a sample dissolved in a small amount of pyridine-D5 and CDCl 3 .
  • toluene solution was added to a 20 L capacity stainless steel (SUS) high pressure reactor, and the reactor temperature was maintained at 40°C.
  • SUS 20 L capacity stainless steel
  • the toluene slurry was transferred to a filter dryer and filtered. 3.0 kg of toluene was added and stirred for 10 minutes, then stirring was stopped and filtered. 3.0 kg of hexane was added to the reactor and stirred for 10 minutes, then stirring was stopped and filtered. A 500 g-SiO 2 supported catalyst was prepared by drying under reduced pressure at 50° C. for 4 hours.
  • Ethylene/1-hexene copolymer (PE-a) was slurry polymerized in the presence of Hybrid Supported Catalyst 1 prepared in Preparation Example 1.
  • the polymerization reactor was a continuous polymerization reactor using an isobutane (i-C4) slurry loop process, the reactor volume was 140 L, and the reaction flow rate was operated at about 7 m/s.
  • the gases required for polymerization ethylene, hydrogen
  • the comonomer 1-hexene were constantly and continuously introduced, and the individual flow rates were adjusted to suit the target product.
  • the ethylene supply amount was adjusted to 31.1 kg/hr
  • the 1-hexene input amount was adjusted to 2.5 wt% compared to ethylene
  • the hydrogen input amount was adjusted to 56 ppm compared to ethylene.
  • Ethylene/1-hexene copolymer was prepared through a monomodal polymerization process.
  • the mixed supported metallocene catalyst 2 prepared in Preparation Example 2 was prepared under the conditions of ethylene supply amount of 10.0 kg/hr, comonomer 1-hexene input amount of 6.3 ml/min, and hydrogen input amount of 1.73 g/hr.
  • ethylene/1-hexene copolymer (PE-b) using a hexane slurry stirred tank process polymerization reaction in one loop-type reactor (polymerization temperature 93 °C, polymerization pressure 7.7 kgf/cm 2 ) was manufactured.
  • the activity of the catalyst calculated as the weight ratio of the produced polymer to the weight of the catalyst used was 9.9 kgPE/gCat.hr.
  • a 1.5 L continuous process reactor was preheated at 120°C while adding 5 kg/h of hexane solvent and 0.31 kg/h of 1-octene.
  • Triisobutylaluminum (Tibal, Triisobutylaluminum, 0.045 mmol/min), the transition metal compound obtained in Synthesis Example 3, and dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (2.6 ⁇ mol/min) were simultaneously added to the reactor. It was put in.
  • ethylene (0.87 kg/h) and hydrogen gas (10 cc/min) were introduced into the reactor and the copolymerization reaction was carried out by maintaining the temperature at 160.0°C for more than 60 minutes in a continuous process at a pressure of 89 bar to produce ethylene/1-octene.
  • a copolymer (PE-c) was obtained.
  • a 1.5 L continuous process reactor was preheated at 120°C while adding 0.28 kg/h of hexane solvent and 0.31 kg/h of 1-octene.
  • Triisobutylaluminum (Tibal, Triisobutylaluminum, 0.045 mmol/min), the transition metal compound obtained in Synthesis Example 3, and dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (2.6 ⁇ mol/min) were simultaneously added to the reactor. It was put in.
  • ethylene (0.87 kg/h) and hydrogen gas (18 cc/min) were introduced into the reactor and the copolymerization reaction was carried out by maintaining the temperature at 160.0°C for more than 60 minutes in a continuous process at a pressure of 89 bar to produce ethylene/1-octene.
  • a copolymer (PE-e) was obtained.
  • Density (g/cm 3 ) was measured using a density gradient tube according to the ASTM D 1505 standard of the American Society for Testing and Materials.
  • melt index MI 2.16
  • weight g
  • a gel permeation chromatography (GPC) device a Waters PL-GPC220 device was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min.
  • GPC gel permeation chromatography
  • the values of Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen.
  • the weight average molecular weight of polystyrene standard specimens is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g.
  • Nine types of /mol were used.
  • polyethylene compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared, respectively, with the compositions shown in Tables 2 and 3 below.
  • a polyethylene composition was manufactured by extrusion and granulation under the conditions of hopper 18 rpm, screw 350 rpm, and 220 °C (extruder: SMPLATEK TEK30MHS, L/D ratio: 40, die diameter: 4 mm). did.
  • Example 4 The same method as Example 1, except that HP1018TM (manufactured by LG Chemical), a commercially available ethylene/1-hexene copolymer polyethylene product prepared using a Ziegler-Natta catalyst, was used as the sole component (PE-f, 100%)
  • HP1018TM manufactured by LG Chemical
  • ethylene/1-hexene copolymer polyethylene product prepared using a Ziegler-Natta catalyst was used as the sole component (PE-f, 100%)
  • the polyethylene composition of Comparative Example 4 was prepared.
  • the ethylene/1-hexene copolymer (PE-f) has a density of 0.918 g/cm 3 and a melt index (MI 2.16 , 190° C., 2.16 kg load) of 1.0 g/10 min.
  • melt index (MI 2.16 ), density, weight average molecular weight (Mw, g/mol), number average molecular weight (Mn, g/mol), and molecular weight distribution (Mw/Mn, PDI) for the polyethylene composition are It was measured in the same way as Test Example 1 previously.
  • the polyethylene composition was heated to 180°C at 10°C/min by raising the temperature (Cycle 1), isothermalized at 180°C for 5 minutes, cooled to 0°C at 10°C/min, and then isothermalized at 30°C for 5 minutes. Then, it was heated again at 10°C/min to 180°C (Cycle 2).
  • the temperature of the maximum point of the endothermic peak was measured as the melting temperature (Tm, °C)
  • the temperature of the maximum point of the exothermic peak was measured as the crystallization temperature (Tc, °C).
  • Tm melting temperature
  • Tc crystallization temperature
  • Cross-fraction chromatography (CFC) analysis was performed on the polyethylene compositions prepared in Examples and Comparative Examples by the method below, and the content ratio of the highly crystalline fraction eluted at 90 °C or higher (TREF ⁇ 90 °C ) , the content ratio of the low-to-medium crystalline fraction eluted above 35 °C but below 90 °C (TREF 35-90 °C ) and the soluble fraction eluted below 35 °C (TREF ⁇ 35 °C ) were measured.
  • CFC Cross-fraction chromatography
  • CFC Cross-fraction chromatography
  • a polyethylene composition sheet with a thickness of 1 mm was manufactured by compression molding at 180 °C and 4500 lbf pressure for 15 minutes, and then a tensile test specimen was prepared according to ASTM D 638 standard, and the tensile speed was measured at room temperature (25 °C). Tensile tests were performed and measured under 500%/min conditions.
  • the tensile strength and elongation at break represent the strength and elongation at break, respectively
  • the yield strength represents the strength at the yield point
  • the 1% modulus and 2% modulus are obtained from the tensile test as described above.
  • the obtained strength-elongation curve shows the initial modulus at elongation of 1% and 2%, respectively.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Furtherance PE-a(85wt%) +PE-c(15wt%) PE-a(90wt%) +PE-c(10wt%) PE-a(95wt%) +PE-c(5wt%) PE-b(85wt%) +PE-c(15wt%) PE-a(85wt%) +PE-e(15wt%) Density (g/cm 3 ) 0.937 0.938 0.940 0.942 0.938 MI 2.16kg (g/10min) 0.8 0.7 0.6 0.2 0.9 Mn (g/mol) 31000 33000 34000 19000 30000 Mw (g/mol) 114000 110000 112000 179000 114000 Mw/Mn 3.7 3.3 3.3 9.4 3.8 Tm (°C) 128.0 128.4 128.6 128.7 128.2 Tc (°C) 111.6 112.3 112.2 113.8 111.7 Xc (%) 60.1 65.9 68.4 68.2 61.9
  • Example 1 comprising the first ethylene-alphaolefin copolymer and the second ethylene-alphaolefin copolymer having different densities and melt indices according to the present invention at a predetermined content ratio, respectively, and
  • the polyethylene composition of 5 has an increased high crystalline molecule content ( ⁇ 90 °C elution rate TREF ⁇ 90 °C ), medium crystalline molecule content (35-90 °C elution rate TREF 35-90 °C ), and soluble fraction ( ⁇ 35 °C).
  • Blown film was manufactured by inflation molding under the following equipment and conditions.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Haze (%) 25.2 28.5 32.7 45.2 26.1 Tensile strength (MPa) M.D. 54.6 53.1 55.0 50.8 53.5 TD 49.5 48.0 42.2 40.5 46.1 MD, TD average 52.05 50.55 48.6 45.65 49.8 1% Modulus (MPa) M.D. 411.1 457.2 488.9 525.6 423.3 TD 542.9 600.3 656.1 704.1 556.7 MD, TD average 477 528.75 572.5 614.85 490 2% Modulus (MPa) M.D.
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Haze (%) 22.6 20.7 28.0 18.3 Tensile strength (MPa) M.D. 50.6 44.4 48.4 45.0 TD 46.3 44.1 49.5 43.5 MD, TD average 48.45 44.25 48.95 44.25 1% Modulus (MPa) M.D. 310.2 272.4 357.9 153.0 TD 384.5 336.6 466.7 162.6 MD, TD average 347.35 304.5 412.3 157.8 2% Modulus (MPa) M.D. 234.5 192.1 285.0 122.4 TD 291.9 245.9 372.4 130.7 MD, TD average 263.2 219 328.7 126.55 Elongation at break (%) M.D.

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Abstract

La présente invention concerne une composition de polyéthylène et un film la comprenant, cette composition de polyéthylène étant appropriée pour un film de polyéthylène qui conserve d'excellentes propriétés en termes d'aptitude à l'impression, de transparence, de productivité et d'aptitude au façonnage de film et est avantageusement rigide en raison d'un module initial élevé.
PCT/KR2023/017420 2022-11-02 2023-11-02 Composition de polyéthylène et film la comprenant WO2024096636A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990008436A (ko) * 1995-05-09 1999-01-25 그레이스스티븐에스 실질적으로 선형인 폴리에틸렌을 포함하는 중간 모듈러스 성형물질 및 그의 제조 방법
KR100288182B1 (ko) * 1993-05-10 2001-09-17 유현식 전선피복용흑색폴리에틸렌계수지조성물
KR20110020126A (ko) * 2009-08-21 2011-03-02 에스케이이노베이션 주식회사 전력케이블 절연층용 가교 폴리에틸렌 조성물
KR20190073266A (ko) * 2017-12-18 2019-06-26 주식회사 엘지화학 폴리에틸렌 수지 필름
WO2022219467A1 (fr) * 2021-04-14 2022-10-20 Nova Chemicals (International) S.A. Film à orientation biaxiale

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100288182B1 (ko) * 1993-05-10 2001-09-17 유현식 전선피복용흑색폴리에틸렌계수지조성물
KR19990008436A (ko) * 1995-05-09 1999-01-25 그레이스스티븐에스 실질적으로 선형인 폴리에틸렌을 포함하는 중간 모듈러스 성형물질 및 그의 제조 방법
KR20110020126A (ko) * 2009-08-21 2011-03-02 에스케이이노베이션 주식회사 전력케이블 절연층용 가교 폴리에틸렌 조성물
KR20190073266A (ko) * 2017-12-18 2019-06-26 주식회사 엘지화학 폴리에틸렌 수지 필름
WO2022219467A1 (fr) * 2021-04-14 2022-10-20 Nova Chemicals (International) S.A. Film à orientation biaxiale

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