WO2008143306A1 - エチレン系重合体組成物およびフィルム - Google Patents
エチレン系重合体組成物およびフィルム Download PDFInfo
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- WO2008143306A1 WO2008143306A1 PCT/JP2008/059403 JP2008059403W WO2008143306A1 WO 2008143306 A1 WO2008143306 A1 WO 2008143306A1 JP 2008059403 W JP2008059403 W JP 2008059403W WO 2008143306 A1 WO2008143306 A1 WO 2008143306A1
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- 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
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to an ethylene polymer composition and a film.
- linear low density polyethylene For films and sheets used for packaging foods, pharmaceuticals, daily necessities, etc., many molded products made by extruding an ethylene polymer are used.
- ethylene-based polymers a linear copolymer of ethylene and ⁇ -olefin, so-called linear low density polyethylene, is superior in impact strength compared to a high pressure method low density polyethylene having long chain branches. Therefore, the packaging material made of linear low density polyethylene can be made thinner than the packaging material made of high pressure method low density polyethylene.
- linear low-density polyethylene has a lower melt tension than high-pressure low-density polyethylene, and bubbles are shaken during inflation molding, and the film becomes thicker and the knitted meat of the film becomes larger.
- moldability these are referred to as moldability.
- polymer compositions in which 5 to 30% by weight of high-pressure low-density polyethylene is blended with linear low-density polyethylene have been proposed (for example, (Japanese Patent Publication No. 6 2-3 1 77 7, Japanese Patent Application Laid-Open No. 11-1 8 1 1 7 3).
- the polymer composition sometimes has lower strength than linear low density polyethylene.
- the present invention provides a tylene-based polymer composition and a film formed by extruding the polymer composition.
- the first of the present invention contains the following component (A) and the following component (B), and the content of the component (B) is 0.5 to 20 parts by weight per 100 parts by weight of the component (A) It relates to a polymer composition.
- Component (A) Ethylene polymer that satisfies all of the following requirements (a l) to (a 3)
- Melt melt mouth rate (MFR) is 0.1 to 10 gZ for 10 minutes.
- Flow activation energy (E a) is 50 k JZmo 1 or more.
- Component (B) An ethylene- ⁇ -olefin copolymer that satisfies all of the following requirements (b l) to (b 3)
- the second of the present invention relates to a film formed by extruding the ethylene polymer composition.
- ethylene-based polymer of component (A) examples include ethylene- ⁇ -aged refin copolymer and high-pressure low-density polyethylene. From the viewpoint of increasing impact strength, ethylene- ⁇ -olefin copolymers are preferred.
- ethylene monoolefin copolymer is a copolymer containing a monomer unit based on ethylene and a monomer unit based on ⁇ -olefin.
- the eleven-year-old olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4 —Methyl 1-hexene, etc., may be used alone or in combination of two or more.
- the ⁇ -olefin is preferably an ⁇ -year-old lefin having 3 to 20 carbon atoms, more preferably an ⁇ -year-old lefin having 4 to 8 carbon atoms, and more preferably 1-butene, 1 1-hexene, 1-octene, 4-methyl-1-pentene It is at least one kind of hyolefin selected from.
- the ethylene- ⁇ -age refin copolymer includes, in addition to the above-mentioned monomer units based on ethylene and monomer units based on ⁇ -year-old olefins, in a range that does not impair the effects of the present invention. It may have monomer units based on other monomers.
- Other monomers include, for example, conjugation (eg, butadiene and isoprene), non-conjugation (eg, 1,4-pentagene), acrylic acid, acrylic acid esters (eg, methyl acrylate and ethyl acrylate), methacrylic acid, etc. Examples thereof include acid, methacrylic acid ester (for example, methyl methacrylate and ethyl acetate), and pinyl acetate.
- Examples of the component ( ⁇ ) ethylene- ⁇ -year-old refin copolymer include: ethylene 1-1 butene copolymer, ethylene 1 1 hexene copolymer, ethylene 1 4-methyl-1 1 pentene copolymer, Ethylene 1-octene copolymer, ethylene 1-butene 1-hexene copolymer, ethylene 1-butene 1 4-methyl-1 1-pentene copolymer, ethylene 1-butene 1-octene copolymer, etc. can give.
- a copolymer having a monomer unit based on ethylene and a monomer unit based on an ⁇ -year-old lefin having 6 to 8 carbon atoms specifically, Ethylene 1-hexene copolymer, ethylene 1-octene copolymer, ethylene 1-butene 1-hexene copolymer, ethylene 1-butene 1-octene copolymer, etc. .
- the content of monomer units based on ethylene is usually based on the total weight (100% by weight) of the ethylene-one-year-old lefin copolymer. 80 to 98% by weight, and the content of monomer units based on the 1-year-old refin is usually 2 to 20% by weight with respect to the total weight of the ethylene polymer (100% by weight).
- the activation energy (Ea; the unit is kJZmo 1) of the flow of the ethylene polymer of the component ( ⁇ ) is 50 k J / mo 1 or more.
- the E a is preferably 55 kJ / mo 1 or more, more preferably 60 k J / mo 1 or more, from the viewpoint of improving molding processability. From the viewpoint of increasing the impact strength, Ea is preferably 100 kJ / mo 1 or less, more preferably 90 kJZmo 1 or less.
- the activation energy of flow (Ea) depends on the angular frequency (unit: rad / sec) of the melt complex viscosity (unit: Pa ⁇ sec) at 190 ° C, based on the temperature-time superposition principle This is a numerical value calculated by the Arrhenius equation from the shift factor (a T ) at the time of creating a master curve showing the property, and is obtained by the following method.
- melt complex viscosity-angular frequency curve of one ⁇ -olefin copolymer is divided into an ethylene-based copolymer at 190 for each melt complex viscosity angular frequency curve at each temperature ( ⁇ ).
- the shift factor (a T ) at each temperature ( ⁇ ) obtained when superimposed on the melt complex viscosity angular frequency curve of the polymer is obtained, and the shift factor at each temperature (T) and each temperature (T) is obtained.
- Equation (I) the first-order approximation (Equation (I) below) of [I n (a T )] and [lZ (T + 273.16)] is calculated by the method of least squares.
- Ea is obtained from the slope m of the following equation and the following equation (II).
- calculation software examples include Rhio os V.4.4.4 manufactured by Rheometrics.
- the logarithmic curve of the melt complex viscosity angular frequency in) moves the angular frequency a T times and the melt complex viscosity lZa T times.
- the shift factor at four temperatures, including 190, and the first-order approximation formula (I) obtained from the temperature are minimized.
- the correlation coefficient obtained by multiplication is usually 0.99 or more.
- the melt complex viscosity angular frequency curve is measured by using a viscoelasticity measuring device (for example, Rheom) etrics Rheome tries Mechanical Spectrum om eter RMS—800 etc.
- a viscoelasticity measuring device for example, Rheom
- the geometry is: parallel plate, plate diameter: 25mm, plate interval: 1.2 to 2mm, strain: 5%, angular frequency: 0.1 to 100 ra dZ seconds.
- the measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount of an antioxidant (for example, 1000 ppm) is blended in advance with the measurement sample.
- the density of the ethylene polymer of component (A) (unit is kg / m 3 ) is 890 to 9 25 kgZm 3 . From the viewpoint of increasing rigidity, the density is preferably 900 kg / m 3 or more, more preferably 905 kg Zms or more, and further preferably 910 kg Zm 3 or more. From the viewpoint of increasing impact strength, it is preferably 920 kgZm 3 or less.
- the density is measured according to an underwater substitution method defined in JI S K7112-1980 after annealing described in J I S K6760-1995.
- the MFR is preferably 0.3 g / 10 min or more, more preferably 0.5 gZ 10 min or more, from the viewpoint of reducing the extrusion load during molding. Further, from the viewpoint of improving the moldability and impact strength, it is preferably 8 g / 10 min or less, more preferably 5 gZl 0 min or less.
- the melt mouth rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N according to the method defined in JIS K7210-1995.
- the melting point ratio (MFRR) of the ethylene-based polymer of component (A) is preferably 40 or more from the viewpoint of improving moldability. Further, from the viewpoint of increasing impact strength, 200 or less is preferable.
- MFR-H melt flow rate
- the molecular weight distribution (Mw / Mn) of the ethylene polymer of component (A) is preferably 3 or more, more preferably 5 or more, and even more preferably 6 or more, from the viewpoint of improving the moldability. Further, from the viewpoint of increasing the impact strength, it is preferably 25 or less, more preferably 20 or less, and further preferably 15 or less.
- the molecular weight distribution (Mw / Mn) is a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn), and Mw and Mn are gel permeation chromatograph (GPC). ) Measured by the method. As measurement conditions for the GPC method, for example, the following conditions can be given.
- a metallocene complex having a ligand in which two (substituted) indenyl groups are bonded by a crosslinking group such as an alkylene group or a silylene group for example, and a method of copolymerizing ethylene and a one-year-old olefin with a meta-locene catalyst using ethylene bis (1 indenyl) zirconium diphenoxide as a catalyst component.
- a co-catalyst component that activates the meta-orcene complex is used.
- the co-catalyst component include organic aluminum oxy compounds, boron compounds, and organic zinc compounds. These promoter components are preferably used by being supported on a particulate carrier.
- the particulate carrier, porous materials are preferable, S I_ ⁇ 2, A l 2 ⁇ 3, Mg_ ⁇ , Z R_ ⁇ 2, T I_ ⁇ 2, B 2 ⁇ 3, Ca_ ⁇ , ZnO, B A_ ⁇ Inorganic oxides such as T h 0 2 ; clays and clay minerals such as smectite, montmorillonite, hectorite, labnite and saponite; organics such as polyethylene, polypropylene and styrene-dipinylbenzene copolymers A polymer or the like is used.
- the 50% volume average particle diameter of the particulate carrier is usually 10 to 500 m, and the 50% volume average particle diameter is measured by a light scattering laser diffraction method or the like.
- the pore volume of the particulate carrier is usually 0.3 to 10 m 1 Z g, and the pore volume is mainly measured by a gas adsorption method (BET method).
- the specific surface area of the particulate carrier is usually 10 to 1000 m 2 Zg, and the specific surface area is mainly measured by a gas adsorption method (BET method).
- the method for producing the ethylene mono-olefin copolymer of component (A) particularly preferably, the following promoter support (A) and two (substituted) indenyl groups with a crosslinking group such as an alkylene group or a silylene group are used.
- a method of copolymerizing ethylene and ⁇ -talifine in the presence of a polymerization catalyst obtained by contacting a metallocene complex (B) having a ligand to which a group is bonded with an organoaluminum compound (C). can give.
- the co-catalyst carrier ( ⁇ ) consists of component (a) jetyl zinc, component (b) two types of fluorinated phenol, component (c) water, component (d) inorganic particulate carrier and component (e) 1, 1 1,3,3,3 Hexamethyldisilazane (((CH 3 ) 3 S i) 2 NH) is a carrier obtained by contact.
- Component (b) fluorine ⁇ f ⁇ phenol includes pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol, etc. I can give you. From the viewpoint of increasing the activation energy (Ea) of the flow of the ethylene- ⁇ -olefin copolymer of component ( ⁇ ), it is preferable to use two types of fluorinated phenols having different numbers of fluorine.
- pentafluoro Preferred examples include phenol 3,4,5-trifluorophenol, penfluorophenol / 2,4,6-trifluorophenol, pentafluorophenol 3,5-difluorophenol, and the like.
- the molar ratio of the fluorinated phenol having a large number of fluorines and the fluorinated phenol having a small number of fluorines is usually 20-80-8020. From the viewpoint of increasing the flow activation energy (Ea) of the ethylene- ⁇ -olefin copolymer of component (A), the molar ratio is preferably large, and preferably 50/50 or more.
- the inorganic compound particles of component (d) are preferably silica gel.
- X in the above formula is preferably a number from 0.01 to 1.99, more preferably a number from 0.110-1.80, and even more preferably a number from 0.20 to 1.50. Most preferred is a number between 0.30 and 1.00.
- the amount of the component (a) component (d) inorganic fine particle carrier used for the jetty zinc is obtained by contacting the component (a) jetyl zinc with the component (d) inorganic fine particle carrier.
- Component (a) contained in the particles It is preferable that the zinc atom derived from jetyl zinc is in an amount of 0.5 lmmo 1 or more in terms of the number of moles of zinc atoms contained in the obtained particle lg. The amount is more preferably 20 mmo 1.
- Component (d) Component used for inorganic fine particle carrier (e) The amount of trimethyldisilazane is as follows: Component (d) Inorganic fine particle carrier 1 gram component (e) Trimethyldisilazane 0.
- lmmo 1 or more The amount is preferably 0.5 to 2 Ommo 1, and more preferably.
- Preferred examples of the meta-octene complex (B) having a ligand in which two (substituted) indenyl groups are bonded by a bridging group such as an alkylene group or a silylene group include ethylene bis (1 indenyl) zirconium diphenoxide. Can do.
- the organoaluminum compound (C) is preferably triisoptyl aluminum or trinormaroctyl aluminum.
- the amount of use of the meta-octacene complex (B) is preferably 5 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 4 mo 1 to the promoter support (A) lg.
- the amount of the organoaluminum compound (C) used is preferably the ratio of the number of moles of aluminum atoms in the organoaluminum compound (C) to the number of moles of metal atoms in the metamouth complex (B) (A1 / M) It is 1 to 2000.
- the promoter support (A) and the metallocene are optionally mixed.
- a polymerization catalyst may be obtained by bringing the electron-donating compound (D) into contact with the copper complex (B) and the organoaluminum compound (C).
- Preferred examples of the electron donating compound (D) include triethylamine and trinormaloctylamine.
- the electron donating compound (D) used is as follows. Further, it is more preferably 0.1 I mo 1% or more, and even more preferably lmo 1% or more, relative to the number of moles of aluminum atoms in the organoaluminum compound (C).
- the amount used is preferably 1 O m o 1% or less, more preferably 5 m o 1% or less, from the viewpoint of increasing the polymerization activity.
- a small amount of olefin is polymerized using a solid catalyst component in which a catalyst component is supported on a particulate carrier (hereinafter referred to as prepolymerization).
- prepolymerization a solid catalyst component in which a catalyst component is supported on a particulate carrier
- prepolymerization Obtained by polymerizing a small amount of olefins using a prepolymerized solid component obtained by, for example, a promoter carrier, a metallocene complex, and other promoter components (alkylene agents such as organoaluminum compounds).
- a method in which ethylene and olefin are copolymerized using the obtained prepolymerized solid component as a catalyst component or a catalyst is preferred.
- olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-11-pentene, cyclopentene, and cyclohexene. These can be used alone or in combination of two or more. Further, the content of the prepolymerized polymer in the prepolymerized solid component is usually 0.1 to 500 g, preferably 1 to 200 g, per gram of the solid catalyst component.
- the prepolymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a patch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method.
- a method of introducing each catalyst component such as a promoter support, a meta-orthocene complex, and other promoter components (such as an alkylating agent such as an organoaluminum compound) into a polymerization reaction tank for performing prepolymerization A method in which nitrogen, argon, or other inert gas, hydrogen, ethylene, or the like is used, is used in the absence of moisture, or a method in which each component is dissolved or diluted in a solvent and then introduced in a solution or slurry state is used.
- the polymerization temperature in the prepolymerization is usually lower than the melting point of the prepolymerized polymer. The temperature is preferably 0 to 100 ° C, more preferably 10 to 70 °
- examples of the solvent include hydrocarbons having 20 or less carbon atoms.
- hydrocarbons having 20 or less carbon atoms For example, saturated aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane, octane, decane, etc .; aromatic hydrocarbons such as benzene, toluene, xylene, etc. These may be used alone or in combination of two or more.
- Component (A) ethylene 1! -Year-old refin copolymer can be produced by using ethylene
- a continuous polymerization method involving formation of particles of an olefin copolymer is preferable, for example, a continuous gas phase polymerization method, a continuous slurry polymerization method, or a continuous bulk polymerization method, and preferably a continuous gas phase polymerization method.
- the gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion.
- a stirring blade may be installed in the reaction tank.
- an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is usually used.
- a method of supplying in the absence of moisture, or a method of supplying each component in a solution or slurry after dissolving or diluting each component in a solvent is used.
- the high-pressure low-density polyethylene component (A) generally uses a tank reactor or a tubular reactor, and a free radical generator such as an organic oxide or oxygen is used as a polymerization initiator. It is produced by polymerizing ethylene under the conditions of 0 to 30 OMPa and a polymerization temperature of 1300 to 300 ° C. MFR can be adjusted by using hydrocarbons such as hydrogen, methane, and ethane as molecular weight regulators.
- the component (B), ethylene- ⁇ -agen refin copolymer, is a copolymer comprising a monomer unit based on ethylene and a monomer unit based on ⁇ -age refine.
- the ⁇ -year-old olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-Methylone 1) Hexene and the like are listed, and these may be used alone or in combination of two or more.
- the ⁇ -year-old refin is preferably an ⁇ -olefin having 3 to 20 carbon atoms, more preferably an ⁇ -year-old refin having 4 to 8 carbon atoms. 08059403
- 11 is preferably at least one ⁇ -olefin selected from 1-butene, 1-hexene, and 4-methyl-1-pentene.
- ethylene- ⁇ -olefin copolymer of component ( ⁇ ) in addition to the above-mentioned monomer units based on ethylene and monomer units based on ⁇ -year-old olefins, in the range not impairing the effects of the present invention, You may have a monomer unit based on another monomer.
- Other monomers include, for example, conjugation (eg, butadiene and isoprene), non-conjugation (eg, 1,4-pentene), acrylic acid, acrylic acid esters (eg, methyl acrylate and ethyl acrylate). Methacrylic acid, methacrylic acid ester (for example, methacrylic acid methyl methacrylate), vinyl acetate and the like.
- Examples of the component ( ⁇ ) ethylene- ⁇ -agen refin copolymer include ethylene 1-1 butene copolymer, ethylene 1-hexene copolymer, ethylene 4-methyl-1 1-pentene copolymer. , Ethylene 1-octene copolymer, Ethylene 1-butene 1 1-hexene copolymer, Ethylene 1-butene 4-methyl-1 pentene copolymer, Ethylene 1-butene 1-octene copolymer For example, coalescence.
- the content of monomer units based on ethylene is usually based on the total weight (100% by weight) of ethylene- ⁇ -year-old lefin copolymer. 50 to 99.5% by weight, preferably 80 to 99% by weight. Further, the content of the monomer unit based on ⁇ -olefin is usually 0.5 to 50% by weight with respect to the total weight (100% by weight) of the ethylene polymer, preferably 1 to 20% by weight.
- the density (unit: kg gm 3 ) of the ethylene-a-year-old refin copolymer of component (ii) is 890 to 925 kg gm 3 .
- the density is preferably 890 kgZms or more, more preferably 900 kgZms or more, from the viewpoint of increasing rigidity. Further, from the viewpoint of increasing the heel strength, it is preferably 920 kgZm 3 or less, more preferably 915 kg / ms or less.
- the density is measured according to the underwater substitution method specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. Determined.
- Unit is dLZg. ) Is 4-15 gZl 0 min. [] Is preferably 5 dLZg or more, more preferably 6 dLZg or more, from the viewpoint of increasing impact strength. Further, from the viewpoint of reducing the extrusion load during molding, it is preferably 13 dLZ g or less, and more preferably 11 dL / g or less.
- BHT 2,6-di-t-peptile p-cresol
- a solution (hereinafter referred to as a sample solution) dissolved in a blank solution so that is 1 mg / ml is prepared, and then the falling time of the blank solution and the sample solution at 135 ° C is measured using an Ubbelohde viscometer. Is calculated from the descent time according to the following formula.
- V rel sample solution fall time / blank solution fall time
- the flow activation energy (Ea; unit is k J / mo 1) of the ethylene- ⁇ -olefin copolymer of component (B) is less than 50 k J / mo 1.
- the Ea is preferably 40 kJ / mo 1 or less, more preferably 35 kJ / mo 1 or less, from the viewpoint of increasing impact strength.
- the E a is measured by the method described above.
- Component (B) ethylene-one-year-old refin copolymer is a Ziegler-based catalyst, a meta-octane-based catalyst (preferably a (substituted) cyclopentaenyl group and a (substituted) fluorenyl group are alkylene groups, silylene groups, etc. Etc.) using a known olefin polymerization catalyst, such as a liquid phase polymerization method, a slurry polymerization method, a gas phase polymerization method, and the like. It is produced by copolymerizing ethylene with olefin by a known polymerization method such as high-pressure ion polymerization. These polymerization methods may be either batch polymerization methods or continuous polymerization methods. Commercially available products may also be used.
- the ethylene-based polymer composition of the present invention contains a component (A) and a component (B).
- the content of component (B) is 0.5 to 20 parts by weight per 100 parts by weight of component (A).
- the content of component (B) is preferably 1 part by weight or more per 100 parts by weight of component (A) from the viewpoint of increasing impact strength.
- the content of component (B) reduces the extrusion load during molding. In view of the above, it is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of component (A).
- the ethylene-based polymer composition of the present invention may contain known additives as necessary.
- additives include antioxidants, weathering agents, lubricants, anti-blocking agents, antistatic agents, antifogging agents, drip-free agents, pigments, and fillers.
- the method for producing the ethylene polymer composition of the present invention includes a method in which the component (A) and the component (B) are respectively produced and then mixed, and a composition of the component (A) and the component (B) by a polymerization reaction. Examples of the manufacturing method.
- Component (A) and component (B) can be mixed and then mixed as follows: (1) Elongated flow kneading die (for example, US Pat. No. 5, 4 5 1, 1 06 developed by U tracki et al. (2) Extruder with different direction biaxial screw having a gear pump (preferably, there is a staying part between the screw part and the die). The melt-kneading method using an extruder, and the solvent such as ortho-dichlorobenzene benzene xylene is heated to a temperature at which the resin dissolves, mixed with the solution, and then precipitated with a poor solvent such as ethanol for precipitation. The method etc. which collect a thing are mention
- a method for producing a composition of component (A) and component (B) by polymerization a method of polymerizing using two kinds of olefin polymerization catalysts, for example, And a method of polymerizing by using two kinds of meta-orthocene complexes.
- a method of producing component (B) by pre-stage polymerization and producing component (A) by post-stage polymerization can be given by the multistage polymerization method.
- the ethylene polymer composition of the present invention is obtained by a known molding method, for example, an extrusion molding method such as an inflation film molding method or a T-die film molding method, a hollow molding method, an injection molding method, a compression molding method, etc. Molded into films, sheets, bottles, trays, etc.
- an extrusion molding method particularly inflation molding method
- a hollow molding method are preferably used.
- the ethylene polymer composition of the present invention is preferably used after being formed into a film or a bottle.
- the ethylene-based polymer composition of the present invention is excellent in impact strength, and a molded product obtained by molding the ethylene-based polymer composition is used for various applications such as food packaging and surface protection.
- the present invention will be described with reference to Examples and Comparative Examples.
- J I S K7112 The density was measured according to the underwater displacement method specified in 1980. The sample was annealed as described in JIS K6760-1995.
- melt flow rate was measured by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.
- melt flow rate (hereinafter referred to as MFR-H (unit: g / 10 min)) was measured under the conditions of a load of 211.82 mm and a temperature of 190 ° C. .
- MFRR was calculated from MFR and MFR-H by the following formula.
- a tetralin solution (hereinafter referred to as a blank solution) in which 2, 6-G t-Pitreux p-cresol (BHT) was dissolved at a concentration of 0.5 g / L, and the polymer at a concentration of lmg / ml.
- a solution (hereinafter referred to as a sample solution) dissolved in a blank solution was prepared. The falling time of the blank solution and the sample solution at 135 ° C was measured with an Ubbelohde viscometer. The intrinsic viscosity was determined from the fall time by the following formula.
- the baseline on the chromatogram consists of a stable horizontal region with a sufficiently short retention time than the appearance of the sample elution peak and a stable horizontal region with a sufficiently long retention time than the solvent elution peak was observed. A straight line formed by connecting the points of the region.
- the penetrating tip's penetrating part shape is a 15 ⁇ hemisphere
- the effective test piece area is 5 ⁇ circle
- the film impact hole at 23 ° C Opening strength was measured.
- the temperature in the reactor was set to 30 ° C until 0.5 hours from the start of the prepolymerization. Thereafter, the temperature in the reactor was raised to 50 over 30 minutes, and then 50 ° C. From the start of prepolymerization to 0.5 hours, ethylene was supplied at 0.7 kgZ hours, and hydrogen was supplied at a normal temperature and normal pressure at a rate of 1.1 liters Z hours. From 0.5 hours after the start of prepolymerization, ethylene was supplied at a rate of 3.5 kgZ hours and hydrogen at room temperature and normal pressure at a rate of 10.2 liters Z hours. A total of 4 hours of prepolymerization was carried out.
- the pressure inside the reactor was purged to 0.5 MPaG, the slurry-like prepolymerization catalyst component was transferred to a dryer, and nitrogen flow drying was performed to obtain a prepolymerization catalyst component. .
- the prepolymerized amount of the ethylene polymer in the prepolymerized catalyst component was 18.2 g per 1 g of the promoter support.
- the prepolymerized catalyst component, triisobutylaluminum and triethylamine (3% molar ratio to triisobutylaluminum) were continuously supplied.
- the resulting ethylene 1-butene 1-hexene copolymer powder was fed using an extruder (LCM50, Kobe Steel, Ltd.), feed rate 50 kgZhr, screw rotation speed 450 rpm, gate opening 50%
- an ethylene-1-butene_1hexene copolymer (hereinafter referred to as A 1) was obtained. .
- the physical properties of the polymer A 1 are shown in Table 1.
- a 200-liter reactor equipped with a nitrogen-substituted stirrer and baffle plate was charged with 80 L of hexane, 20.6 kg of tetraethoxysilane and 2.2 kg of tetrabutoxytitanium, and stirred.
- 50 L of a dibutyl ether solution (concentration: 2.1 mol ZL) of butyl magnesium chloride was added dropwise to the stirred mixture over 4 hours while keeping the temperature of the reactor at 5.
- the mixture was stirred at 5 ° C for 1 hour and further at 20 ° C for 1 hour, and filtered to obtain a solid component.
- the obtained solid component was washed with 70 L of toluene three times, and 63 L of toluene was added to the solid component to form a slurry.
- a 21-OL reactor equipped with a stirrer was replaced with nitrogen, and a solid component toluene slurry was charged into the reactor.
- Tetrachlorosilane 14. k, diphthalic acid phthalate (2-ethylhexyl) 9.5 kg was added and stirred at 105 for 2 hours. Subsequently, solid-liquid separation was performed, and the obtained solid was washed three times with 90 L of toluene at 95 ° C. Add 63 L of toluene to the solid. The temperature was raised to C, 13.0 kg of TiC was added, and the mixture was stirred at 105 ° C for 2 hours.
- An ethylene-based polymer composition is blended with an antioxidant (Sumitomo Chemical Co., Ltd., Sumitizer GP) 1 000 p pm and calcium stearate 800 p pm, and then the ethylene-based polymer composition is blown into an inflation film molding machine.
- an antioxidant Suditomo Chemical Co., Ltd., Sumitizer GP
- Processing temperature 200 ° C
- extrusion amount 170 g /
- An inflation film having a thickness of 20 m was formed under the processing conditions of hr, frost line height 20 mm, blow ratio 2.0, film take-off speed 2.
- OmZmin. Table 2 shows the evaluation results of the stability of the bubbles during film forming and the physical properties of the obtained film.
- Example 2 21.3 mg of the solid catalyst component obtained in Example 1 (11-2) was added to initiate polymerization.
- hydrogen 0.667 mo 1%)
- butane, 1-butene, ethylene, and hydrogen were purged to obtain 184 g of an ethylene- 11-butene copolymer (hereinafter referred to as (B2)).
- B2 ethylene- 11-butene copolymer
- An ethylene-based polymer composition is blended with an antioxidant (Sumitomo Chemical Co., Ltd., Sumitizer GP) 1 000 p pm and calcium stearate 800 p pm, and then the ethylene-based polymer composition is blown into an inflation film molding machine.
- an antioxidant Suditomo Chemical Co., Ltd., Sumitizer GP
- the ethylene-based polymer composition is blown into an inflation film molding machine.
- Single screw extruder diameter 0.5 inch, die (die diameter 0.625 inch ⁇ , lip gap 0.03 inch)
- processing temperature 200 ° C
- extrusion amount 170 gZhr frost Inflation film with a thickness of 20 ⁇ m was molded under the processing conditions of line height 20 mm, professional ratio 2.0, film take-off speed 2.
- Om / min The evaluation results of the physical properties of the film are shown in Table 2.
- Comparative Example 1 Polymer A 1 was blended with antioxidant (Sumitomo Chemical Co., Ltd., Sumitizer GP) 1000 p pm and calcium stearate 800 p pm. Molded into an inflation film. Table 2 shows the results of the evaluation of the stability of the bubbles during film formation and the physical properties of the resulting film.
- antioxidant Suditomo Chemical Co., Ltd., Sumitizer GP
- An ethylene-based polymer composition is blended with an antioxidant (Sumitomo Chemical Co., Ltd., Sumitizer GP) 1 000 p pm and calcium stearate 800 p pm, and then the ethylene-based polymer composition is blown into an inflation film molding machine.
- an antioxidant Suditomo Chemical Co., Ltd., Sumitizer GP
- Processing temperature 200 extrusion amount 1708 111 ", Frost line height 20 mm, professional ratio 2.0, film take-up speed 2.
- Table 2 The evaluation results of the physical properties of the films are shown in Table 2. ⁇ table 1 ⁇
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
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DE112008001303T DE112008001303T5 (de) | 2007-05-18 | 2008-05-15 | Polymerzusammensetzung auf Ethylenbasis und Folie |
CN200880024817.5A CN101743277B (zh) | 2007-05-18 | 2008-05-15 | 乙烯类聚合物组合物及薄膜 |
US12/599,069 US8426525B2 (en) | 2007-05-18 | 2008-05-15 | Ethylene based polymer composition and film |
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US (1) | US8426525B2 (ja) |
JP (1) | JP2009001780A (ja) |
CN (1) | CN101743277B (ja) |
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DE112010004477T5 (de) * | 2009-11-17 | 2012-10-31 | Sumitomo Chemical Company, Limited | Harzfolie auf Polyethylenbasis |
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US10995166B2 (en) | 2017-11-07 | 2021-05-04 | Nova Chemicals (International) S.A. | Ethylene interpolymer products and films |
US10882987B2 (en) | 2019-01-09 | 2021-01-05 | Nova Chemicals (International) S.A. | Ethylene interpolymer products having intermediate branching |
US11046843B2 (en) | 2019-07-29 | 2021-06-29 | Nova Chemicals (International) S.A. | Ethylene copolymers and films with excellent sealing properties |
CN117343226B (zh) * | 2023-12-04 | 2024-04-09 | 万华化学集团股份有限公司 | 一种乙烯/α-烯烃共聚物及其应用 |
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CN101743277A (zh) | 2010-06-16 |
DE112008001303T5 (de) | 2010-04-29 |
US8426525B2 (en) | 2013-04-23 |
CN101743277B (zh) | 2013-04-17 |
JP2009001780A (ja) | 2009-01-08 |
US20100216947A1 (en) | 2010-08-26 |
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