Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • 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
  • C08F2420/00—Metallocene catalysts
  • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
• • 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
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/26—Use as polymer for film forming
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a polyethylene powder and a method for producing the same, and a catalyst for olefin polymerization and a method for producing the same.
• Ethylene polymers are used in a wide variety of applications such as films, sheets, microporous membranes, fibers, foams, and pipes. Ethylene polymers are used because they are easy to melt process, and the resulting molded products have high mechanical strength, excellent chemical resistance, rigidity, and the like. Among them, ultra-high molecular weight ethylene polymers have a large molecular weight, so they have higher mechanical strength, excellent sliding properties and abrasion resistance, and excellent chemical stability and long-term reliability. From this point of view, ultra-high molecular weight polyethylene powder is used as a raw material for microporous membranes for secondary battery separators, particularly those typified by lead-acid batteries and lithium ion batteries.
• Patent Document 1 states that when the intrinsic viscosity is within a predetermined range and a specific proportion of the heat of fusion obtained under specific measurement conditions of a differential scanning calorimeter (DSC) is greater than or equal to a specific lower limit value, Ethylene-based polymers have been proposed that can provide molded products (e.g., stretched molded products, microporous membranes) with excellent oxidation resistance and shrinkage resistance.
• DSC differential scanning calorimeter
• Patent Document 2 describes a method for producing a supported metallocene catalyst that can produce a polyolefin polymer with improved apparent density while maintaining the properties of a highly active catalyst, and a method for producing a polyolefin using the same. A method is proposed.
• Patent No. 6383479 Special Publication No. 2017-518423
• the present invention has been made in view of the above circumstances, and aims to provide a polyethylene powder that has excellent heat resistance, film uniformity, dimensional stability, and high heat resistance rate when made into a microporous film, for example. purpose.
• the present inventors have succeeded in improving heat resistance and film uniformity by controlling predetermined physical properties within a specific range in polyethylene powder with a predetermined viscosity average molecular weight. They have discovered that it is possible to provide a microporous membrane with excellent dimensional stability and high heat resistance, and have completed the present invention.
• the viscosity average molecular weight is 100,000 or more and 4,000,000 or less
• a polyethylene powder whose crystal thickness parameter obtained from measurement using a differential scanning calorimeter (DSC) is 5°C or more and 9°C or less.
• DSC differential scanning calorimeter
• the polyethylene according to [1] which has a z-average shrinkage factor gz value of 0.600 or more and 1 or less as measured by a gel permeation chromatography (GPC) measuring device that combines a differential refractometer and a viscosity detector. powder.
• GPC gel permeation chromatography
• the peak top temperature (Tm2 top ) is 135°C or more and 140°C or less.
• ⁇ Measurement conditions> (1) Leave at 50°C for 1 min. (2) Raise the temperature from 50°C to 180°C at 10°C/min (first heating process) (3) Leave at 180°C for 5 min. (4) Cool from 180°C to 50°C at 10°C/min. (5) Leave at 50°C for 5 min. (6) Raise the temperature from 50°C to 180°C at 10°C/min.
• the transition metal compound component [B-1] and/or the transition metal compound component [B-2] and the activator [C] and/or the organometallic compound component [B-2] are added to the particles obtained in the first supporting reaction step.
• D] includes a second supporting reaction step of reacting with The transition metal compound [B-1] is a compound represented by the following (formula 3), and the transition metal compound [B-2] is a compound represented by the following (formula 4), and the transition metal compound [B-2] is a compound represented by the following (formula 4).
• the curing agent [C] is a compound represented by the following (Formula 5) or (Formula 6), and the organometallic compound component [D] is a compound represented by the following (Formula 5) or (Formula 6). It is a compound containing at least one metal selected from the group consisting of Group 13, and the inorganic solid particles [A] are porous polymeric materials or Groups 2 to 4, 13 and 14 of the periodic table. Inorganic solid particles containing at least one element selected from the group consisting of A method for producing an olefin polymerization catalyst that satisfies ⁇ Condition 1> and/or ⁇ Condition 2> below.
• ⁇ Condition 1> In the first supporting reaction step, the transition metal compound [B-1] and/or the transition metal compound component [B-2] are reacted with the activator [C] and/or the organometallic compound component [D].
• the method includes a premixing step and a step of reacting the mixture obtained in the premixing step with the inorganic solid particles [A].
• ⁇ Condition 2> In the first supporting reaction step, the activator [C] and the organometallic compound component [D] are added to the molar amount [B] of the transition metal compound component [B-1] and/or the transition metal compound component [B-2].
• the molar ratio (([C]+[D])/[B]) of the molar amount ([C]+[D]) is 1 or more and 60 or less.
• X 1 is each independently a monovalent anionic ⁇ -bond ligand, a divalent anionic ⁇ -bond ligand that binds to M in a divalent manner, and a monovalent each to L and M.
• each X 2 independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms; j is 1 or 2, provided that when j is 2, the two ligands L are optionally bonded to each other via a divalent group having up to 20 non-hydrogen atoms, and the 2
• the valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and a hydrocarbyleneamino group having 1 to 12 carbon atoms.
• k is 0 or 1
• p is 0, 1 or 2
• X 1 is a monovalent anionic ⁇
• p is an integer that is at least 1 smaller than the formal oxidation number of M
• p is an integer that is at least (j+1) smaller than the formal oxidation number of M
• q is 0, 1 or 2).
• M2 represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and whose formal oxidation number is +2, +3, or +4,
• R 5 each independently represents 1 to 20 groups selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof.
• X3 each independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a silyl group having 1 to 18 carbon atoms.
• two substituents X 3 work together to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms
• Y 1 represents -O-, -S-, -NR 6 - or -PR 6 -, provided that R 6 is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms.
• [14] Contains inorganic solid particles [A], transition metal compound component [B-1] and/or transition metal compound component [B-2], and activator [C] and/or organometallic compound component [D] ,
• the transition metal compound [B-1] is a compound represented by the following (formula 3)
• the transition metal compound [B-2] is a compound represented by the following (formula 4)
• the transition metal compound [B-2] is a compound represented by the following (formula 4).
• the curing agent [C] is a compound represented by the following (Formula 5) or (Formula 6)
• the organometallic compound component [D] is a compound represented by the following (Formula 5) or (Formula 6).
• the inorganic solid particles [A] are porous polymeric materials or Groups 2 to 4, 13 and 14 of the periodic table.
• Inorganic solid particles containing at least one element selected from the group consisting of The content (mol) of the central metal M contained in the transition metal compound component [B-1] and/or the transition metal compound component [B-2] is 20 ⁇ mol or more and 1000 ⁇ mol or less, and the content of the central metal M is 20 ⁇ mol or more and 1000 ⁇ mol or less.
• a catalyst for olefin polymerization, wherein the molar ratio (Al/M) between Al content (mol) and Al content (mol) is 1 or more and 30 or less.
• L 1 is each independently selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group
• X 1 is each independently a monovalent anionic ⁇ -bond ligand, a divalent anionic ⁇ -bond ligand that binds to M in a divalent manner, and a monovalent each to L and M.
• each X 2 independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms; j is 1 or 2, provided that when j is 2, the two ligands L are optionally bonded to each other via a divalent group having up to 20 non-hydrogen atoms, and the 2
• the valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and a hydrocarbyleneamino group having 1 to 12 carbon atoms.
• k is 0 or 1
• p is 0, 1 or 2
• X 1 is a monovalent anionic ⁇
• p is an integer that is at least 1 smaller than the formal oxidation number of M
• p is an integer that is at least (j+1) smaller than the formal oxidation number of M
• q is 0, 1 or 2).
• M2 represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and whose formal oxidation number is +2, +3, or +4,
• R 5 each independently represents 1 to 20 groups selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof.
• X3 each independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a silyl group having 1 to 18 carbon atoms.
• two substituents X 3 work together to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms
• Y 1 represents -O-, -S-, -NR 6 - or -PR 6 -, provided that R 6 is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms.
• the polyethylene powder of the present invention it is possible to provide a microporous membrane that is excellent in heat resistance, membrane uniformity, dimensional stability, and high heat resistance rate, for example.
• this embodiment a mode for carrying out the present invention (hereinafter also referred to as “this embodiment”) will be described in detail. Note that the present invention is not limited to this embodiment, and can be implemented with appropriate modifications within the scope of the gist.
• the polyethylene powder of this embodiment has a viscosity average molecular weight of 100,000 or more and 4,000,000 or less,
• the crystal thickness parameter obtained from measurement using a differential scanning calorimeter (DSC) is 5°C or more and 9°C or less.
• DSC differential scanning calorimeter
• the polyethylene powder of the present embodiment can provide a microporous membrane that is excellent in heat resistance, membrane uniformity, dimensional stability, and high heat resistance rate.
• the polyethylene powder of this embodiment has a z -average shrinkage factor (hereinafter referred to as "average shrinkage factor") measured by a gel permeation chromatography (GPC) measuring device that combines a differential refractometer and a viscosity detector.
• GPC gel permeation chromatography
• the polyethylene powder of the present embodiment can provide a microporous membrane that is even more excellent in heat resistance, membrane uniformity, dimensional stability, and high heat resistance rate.
• the above crystal thickness parameter is determined by the temperature at the peak top (Tm2 top ) and the temperature at the peak convergence point (Tm2 end ) in the DSC curve of the second heating process obtained by the measurement shown in ⁇ Measurement conditions> below. (Tm2 end - Tm2 top ) (hereinafter also referred to as "temperature difference (Tm2 end - Tm2 top ) in the DSC curve").
• ⁇ Measurement conditions> (1) Leave at 50°C for 1 min.
• the polyethylene powder of this embodiment has a peak top temperature (Tm2 top ) is 135°C or more and 140°C or less, ⁇ Measurement conditions> (1) Leave at 50°C for 1 min. (2) Raise the temperature from 50°C to 180°C at 10°C/min (first heating process) (3) Leave at 180°C for 5 min. (4) Cool from 180°C to 50°C at 10°C/min. (5) Leave at 50°C for 5 min. (6) Raise the temperature from 50°C to 180°C at 10°C/min. 2nd heating process) It is preferable that the crystal thickness parameter is 6.7°C or more and 9.0°C or less.
• the polyethylene powder of the present embodiment can provide a microporous membrane that is even more excellent in heat resistance, membrane uniformity, dimensional stability, and high heat resistance rate.
• the DSC curve of the second heating process obtained by the measurement shown in ⁇ Measurement conditions> above using a differential scanning calorimeter (DSC) shows the characteristics of crystals generated in the recrystallization process of polyethylene powder. .
• the characteristics of such crystals correspond to, for example, the characteristics of crystals generated in the cooling process after melt-kneading polyethylene powder in the actual process of manufacturing a microporous membrane, and the characteristics of crystals generated here. It is thought that the characteristics of the crystals affect the physical properties of the microporous membrane.
• the fact that the temperature difference (Tm2 end - Tm2 top ) in the DSC curve is within the above range indicates that it contains a polyethylene component with a high melting point, that is, the presence of thickly grown crystal parts. It is thought that there are.
• the process by which the crystal part grows thickly is that during the cooling process, a low-mobility region with one end restrained, such as a long chain branch, starts to crystallize first, and then crystallization occurs using this low-mobility region as a nucleus. It is estimated that the thickness of the crystal part locally increases as the crystallization progresses further.
• the generation of such crystal parts during the recrystallization process is one of the reasons why it is possible to provide a microporous film with excellent heat resistance, film uniformity, dimensional stability, and high heat resistance rate. It is presumed that this is the cause.
• the polyethylene powder of this embodiment preferably has a viscosity average molecular weight of 200,000 or more and 4,000,000 or less, more preferably 250,000 or more and 3,000,000 or less, and 300,000 or more and 2,000,000 or less. ,500,000 or less.
• the polyethylene powder of this embodiment tends to have sufficient mechanical strength when formed into a microporous membrane when the viscosity average molecular weight is equal to or higher than the lower limit.
• the viscosity average molecular weight of the polyethylene powder of this embodiment when the viscosity average molecular weight of the polyethylene powder of this embodiment is below the above upper limit, it has excellent moldability, and when formed into a microporous membrane, thickness unevenness and the occurrence of unmelted substances are suppressed (uniformity ), the residual stress in the microporous membrane is suppressed (low shrinkage rate), and it also tends to be easily mixed with other polyethylene resins, making it difficult to segregate in the microporous membrane during blending.
• the viscosity average molecular weight of the polyethylene powder can be measured by the method described in Examples below.
• the polyethylene powder of this embodiment has a temperature difference (Tm2 end - Tm2 top ) in the DSC curve of 5°C or more and 9°C or less, preferably 6°C or more and 8.5°C or less, and preferably 6.7°C or more and 8.5°C or less. More preferably, the temperature is 8°C or lower.
• the temperature difference (Tm2 end ⁇ Tm2 top ) in the DSC curve is 6.7°C.
• the temperature is preferably 9.0°C or higher, more preferably 6.7°C or higher and 8.5°C or lower, even more preferably 6.7°C or higher and 8°C or lower.
• Tm2 end - Tm2 top when the temperature difference (Tm2 end - Tm2 top ) in the DSC curve is equal to or higher than the lower limit value, heat resistance is improved when formed into a microporous film due to the high melting point component, and By blending it with other polyethylene resins, it is possible to improve the heat resistance when forming a microporous membrane.
• the polyethylene powder of this embodiment is used as a microporous membrane for a secondary battery separator, if the temperature difference (Tm2 end - Tm2 top ) in the DSC curve is below the above-mentioned upper limit, there will be a slight difference in temperature during abnormal heat generation of the battery.
• the pores of the porous membrane tend to close more easily, and the stretching process tends to be more uniform.
• the method for obtaining polyethylene powder having a temperature difference (Tm2 end - Tm2 top ) in the above range in the DSC curve is not particularly limited, but for example, a trace amount of long chain Included are methods of manufacturing polymers to include branching. Specifically, there is a method in which the main chain and the side chain are controlled separately and the proportion of the side chain is suppressed to a very small amount. Methods for separately controlling the main chain and side chains are not particularly limited, but for example, a catalyst containing two types of active species ((A) for macromonomer incorporation and (B) for macromonomer synthesis) may be used.
• Another method is to form a multilayer structure on the surface of the carrier by changing the type of co-catalyst for each active species, pre-mixing the co-catalyst and the active species, and supporting them in two or more stages.
• the method of suppressing the proportion of side chains to a very small amount is not particularly limited, but for example, the proportion of the above two types of active species ((A) for macromonomer incorporation/(B) for macromonomer synthesis) may be in the range of 1 to 1000.
• the ratio of the co-catalyst (C) and the active species for macromonomer uptake (A) ((C)/(A)) was controlled within the range of 0.5 to 1.5, and the co-catalyst (D) and the active species for macromonomer synthesis (B) ((D)/(B)) may be controlled in the range of 1 to 60.
• the temperature difference (Tm2 end - Tm2 top ) in the DSC curve of the polyethylene powder can be measured by the method described in Examples below.
• the average shrinkage factor gz of the polyethylene powder of this embodiment is preferably 0.600 or more and 1 or less, more preferably 0.65 or more and 0.985 or less, and 0.7 or more and 0.97 or less. It is even more preferable that there be.
• the average shrinkage factor gz of the polyethylene powder of this embodiment is equal to or higher than the lower limit value, when it is made into a microporous film, the stress remaining in the microporous film is suppressed (low shrinkage rate), and branching The occurrence of entanglement due to chains is suppressed below a certain level, and crystallization tends to be promoted.
• the average shrinkage factor gz of the polyethylene powder of this embodiment is below the upper limit value, high melting point crystals are likely to be generated and the strength when melted is increased, so when formed into a microporous film, heat resistance
• the stability during film formation is further improved, leading to the suppression of film unevenness, and by blending it with other polyethylene resins, it is possible to further improve the heat resistance and stretchability of microporous films. It tends to be possible.
• the method for obtaining polyethylene powder having an average shrinkage factor gz within the above range is not particularly limited, but for example, the polymer may be modified to contain a trace amount of long chain branching using a catalyst obtained by a special production method described below.
• a manufacturing method is mentioned. Specifically, there is a method in which the main chain and the side chain are controlled separately and the proportion of the side chain is suppressed to a very small amount.
• Methods for separately controlling the main chain and side chains are not particularly limited, but for example, a catalyst containing two types of active species ((A) for macromonomer incorporation and (B) for macromonomer synthesis) may be used.
• Examples of methods include changing the type of co-catalyst for each active species, pre-mixing the co-catalyst and the active species, and supporting them in two or more stages to form a multilayer structure on the surface of the carrier.
• the method of suppressing the proportion of side chains to a very small amount is not particularly limited, but for example, the proportion of the above two types of active species ((A) for macromonomer incorporation/(B) for macromonomer synthesis) is in the range of 1 to 1000.
• the ratio of the co-catalyst (C) and the active species for macromonomer uptake (A) ((C)/(A)) is controlled in the range of 0.5 to 1.5, and the co-catalyst (D) and the active species for macromonomer synthesis (B) ((D)/(B)) may be controlled in the range of 1 to 60.
• the average shrinkage factor gz of the polyethylene powder can be measured by the method described in Examples below.
• the polyethylene powder of this embodiment can be stretched under the following conditions. (Stretching conditions) A 100 mm x 100 mm x 1 mm thick gel sheet made of 30 mass % polyethylene powder and 70 mass % liquid paraffin is stretched 7x7 times at 115°C.
• the polyethylene powder of this embodiment can be stretched under the above conditions, unevenness in film thickness when formed into a microporous film tends to be suppressed. Moreover, there is a tendency that microporous membranes can be manufactured with high productivity.
• the method for obtaining polyethylene powder that can be stretched under the above conditions is not particularly limited, but for example, by appropriately adjusting the catalyst composition and polymerization conditions, the proportion of ultra-high molecular weight components (molecular weight > 10 7 or more) can be kept below a certain level. There are ways to reduce this.
• the stretchability under the above conditions can be specifically evaluated by the method described in Examples below.
• the polyethylene powder of this embodiment preferably has an absorption coefficient of 1.0 or more and 4.0 or less at 400 cm -1 to 450 cm -1 in terahertz measurement, and preferably 1.9 or more and 3.5 or less. More preferably, it is 2.1 or more and 3.5 or less.
• the terahertz wave is absorbed as vibrational energy of polymer chains, and the absorption peak of the terahertz wave at 500 cm -1 to 550 cm -1 is due to the absorption peak of polyethylene. Since it corresponds to the vibration of the amorphous part, it is estimated that the absorption peak at 400 cm -1 to 450 cm -1 corresponds to the vibration derived from the long chain branched structure present in the amorphous part.
• the method for obtaining polyethylene powder whose absorption coefficient at 400 cm -1 to 450 cm -1 is within the above range is not particularly limited, but for example, the types of active species and co-catalysts and the combination thereof may be adjusted as appropriate. In this way, one method is to uniformly incorporate the macromonomer.
• the absorption coefficient at 400 cm -1 to 450 cm -1 can be evaluated by the method described in Examples below.
• the polyethylene powder of this embodiment has no peak in the region shown below in 1 H-NMR measurement.
• Both (1) and (2) are regions where signals corresponding to terminal double bonds are detected, and the absence of a peak in this region means that no macromonomer remains in the polyethylene powder.
• the polyethylene powder of this embodiment does not have a peak in the region shown above in 1 H-NMR measurement, it can be stretched uniformly when formed into a microporous film, which tends to suppress film thickness unevenness.
• residual stress in the microporous membrane is further suppressed (low shrinkage rate), and when blended with other polyethylene resins, a uniform microporous membrane tends to be obtained.
• 1 H-NMR measurement there are no particular limitations on how to obtain a polyethylene powder that does not have a peak in the region shown above, but examples include supporting an active species that can incorporate macromonomers on the outermost surface of the catalyst, and An example of this method is to appropriately adjust the raw material composition and amount of comonomer to prevent terminal double bonds from remaining.
• the 1 H-NMR peak of the polyethylene powder can be measured by the method described in Examples below.
• the aluminum content of the polyethylene powder of the present embodiment is preferably 0 ppm or more and 50 ppm or less, more preferably 0 ppm or more and 30 ppm or less, and even more preferably 0 ppm or more and 15 ppm or less.
• the aluminum content of the polyethylene powder of this embodiment is within the above range, high melting point crystals tend to be easily generated, and when formed into a microporous film, it tends to be of high quality. Furthermore, clogging of the filter during the molding process can be suppressed, leading to improved productivity.
• the aluminum content in the polyethylene powder can be measured by the method described in Examples below.
• the silicon content of the polyethylene powder of this embodiment is preferably 0 ppm or more and 30 ppm or less, more preferably 0 ppm or more and 10 ppm or less, and even more preferably 0 ppm or more and 2 ppm or less.
• silicon content of the polyethylene powder of this embodiment is within the above range, high melting point crystals tend to be easily generated, and when formed into a microporous film, it tends to be of high quality. Furthermore, clogging of the filter during the molding process can be suppressed, leading to improved productivity.
• the silicon content in the polyethylene powder can be measured by the method described in Examples below.
• the polyethylene powder of this embodiment has a peak top temperature (hereinafter also referred to as "Tm2 top ”) of 130°C or more and 140°C or less in the DSC curve during the second heating process.
• Tm2 top peak top temperature
• the temperature is preferably 133°C or higher and 140°C or lower, and even more preferably 135°C or higher and 140°C or lower.
• Tm2 top is preferably 135°C or more and 140°C or less, and 136°C
• the temperature is more preferably 140°C or higher, and even more preferably 137°C or higher and 140°C or lower.
• a method for obtaining a polyethylene powder having Tm2 top within the above range is not particularly limited, but includes, for example, a method of adjusting the catalyst raw material composition and the amount of comonomer.
• Tm2 top can be measured by the method described in Examples below.
• the polyethylene powder of this embodiment preferably has a density of 920 kg/m 3 or more and 960 kg/m 3 or less, more preferably 930 kg/m 3 or more and 955 kg/m 3 or less, and 935 kg/m 3 or more and 950 kg/m 3 or less. It is more preferable that it is m3 or less.
• the density of polyethylene powder can be measured by the method described in Examples below.
• the method for producing an olefin polymerization catalyst of the present embodiment includes adding a transition metal compound [B-1] and/or a transition metal compound component [B-2] to an inorganic solid particle [A], an activator [C], and a transition metal compound component [B-2]. / or a first supporting reaction step of reacting with the organometallic compound component [D]; The transition metal compound component [B-1] and/or the transition metal compound component [B-2] and the activator [C] and/or the organometallic compound component [B-2] are added to the particles obtained in the first supporting reaction step.
• the transition metal compound [B-1] is a compound represented by the following (formula 3)
• the transition metal compound [B-2] is a compound represented by the following (formula 4)
• the transition metal compound [B-2] is a compound represented by the following (formula 4).
• the curing agent [C] is a compound represented by the following (Formula 5) or (Formula 6)
• the organometallic compound component [D] is a compound represented by the following (Formula 5) or (Formula 6). It is a compound containing at least one metal selected from the group consisting of Group 13, and the inorganic solid particles [A] are porous polymeric materials or Groups 2 to 4, 13 and 14 of the periodic table.
• ⁇ Condition 1> In the first supporting reaction step, the transition metal compound [B-1] and/or the transition metal compound component [B-2] are reacted with the activator [C] and/or the organometallic compound component [D].
• the method includes a premixing step and a step of reacting the mixture obtained in the premixing step with the inorganic solid particles [A].
• the activator [C] and the organometallic compound component [D] are added to the molar amount [B] of the transition metal compound component [B-1] and/or the transition metal compound component [B-2].
• the molar ratio (([C]+[D])/[B]) of the molar amount ([C]+[D]) is 1 or more and 60 or less.
• X 1 is each independently a monovalent anionic ⁇ -bond ligand, a divalent anionic ⁇ -bond ligand that binds to M in a divalent manner, and a monovalent each to L and M.
• each X 2 independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms; j is 1 or 2, provided that when j is 2, the two ligands L are optionally bonded to each other via a divalent group having up to 20 non-hydrogen atoms, and the 2
• the valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and a hydrocarbyleneamino group having 1 to 12 carbon atoms.
• k is 0 or 1
• p is 0, 1 or 2
• X 1 is a monovalent anionic ⁇
• p is an integer that is at least 1 smaller than the formal oxidation number of M
• p is an integer that is at least (j+1) smaller than the formal oxidation number of M
• q is 0, 1 or 2).
• M2 represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and whose formal oxidation number is +2, +3, or +4,
• R 5 each independently represents 1 to 20 groups selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof.
• X3 each independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a silyl group having 1 to 18 carbon atoms.
• two substituents X 3 work together to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms
• Y 1 represents -O-, -S-, -NR 6 - or -PR 6 -, provided that R 6 is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms.
• r is an integer of 1 to 7
• s is an integer of 2 to 14
• C-2) -(M 4 R 7 t-2 -O) u -...
• R 7 is each independently a hydrocarbon group or substituted hydrocarbon group having 1 to 12 carbon atoms
• t is a metal M is the valence of 4
• u is an integer of 2 or more.
• the transition metal compound used in the first supporting reaction step is preferably [B-1]
• the transition metal compound used in the second supporting reaction step is preferably [B-2].
• the activator [C] and the organometallic compound component [B] with respect to the molar amount [B] of the transition metal compound component [B-1] and/or the transition metal compound component [B-2] The molar ratio (([C]+[D])/[B]) of the molar amount ([C]+[D]) of D] is preferably 0.5 or more and 1.5 or less, and 0. More preferably, it is 9 or more and 1.1 or less.
• the molar ratio ([B 2 ]/[B 2 ]) of the transition metal compound component ([B 2 ]) used in the second support reaction step to the transition metal compound component ([B 1 ]) used in the first support reaction step 1 ]) is preferably 1 or more and 1000 or less, more preferably 5 or more and 100 or less.
• the amount of long chain branching in the production of olefin polymers can be increased. It is possible to suppress the amount to a very small amount.
• the method for producing an olefin polymerization catalyst of the present embodiment satisfies the following ⁇ Condition 1> and/or ⁇ Condition 2>. ⁇ Condition 1> In the first supporting reaction step, the transition metal compound [B-1] and/or the transition metal compound component [B-2] are reacted with the activator [C] and/or the organometallic compound component [D].
• the method includes a premixing step and a step of reacting the mixture obtained in the premixing step with the inorganic solid particles [A].
• ⁇ Condition 1> it is likely that a layer in which the transition metal compound and the activator are uniformly mixed can be formed on the surface of the inorganic solid particles [A].
• the macromonomer is incorporated uniformly, making it possible to synthesize an olefin polymer with less segregation of long chain branches.
• the activator [C] and the organometallic compound component [D] are added to the molar amount [B] of the transition metal compound component [B-1] and/or the transition metal compound component [B-2].
• the molar ratio (([C]+[D])/[B]) of the molar amount ([C]+[D]) is 1 or more and 60 or less, and preferably 1 or more and 30 or less.
• Inorganic solid particles [A] used in the method for producing an olefin polymerization catalyst it is preferable to use magnesium chloride particles as the inorganic solid particles [A].
• magnesium chloride particles when magnesium chloride particles are used as the inorganic solid particles [A], the catalyst particles tend to break easily during polymerization, and an olefin polymer with less metal residue can be produced. .
• the olefin polymerization catalyst of this embodiment comprises inorganic solid particles [A], transition metal compound component [B-1] and/or transition metal compound component [B-2], activator [C] and/or organic Contains a metal compound component [D],
• the transition metal compound [B-1] is a compound represented by the above (formula 3)
• the transition metal compound [B-2] is a compound represented by the above (formula 4)
• the transition metal compound [B-2] is a compound represented by the above (formula 4).
• the curing agent [C] is a compound represented by the above (Formula 5) or (Formula 6), and the organometallic compound component [D] is a compound represented by the above (Formula 5) or (Formula 6). It is a compound containing at least one metal selected from the group consisting of Group 13, and the inorganic solid particles [A] are porous polymeric materials or Groups 2 to 4, 13 and 14 of the periodic table.
• the content (mol) of the central metal M contained in the transition metal compound component [B-1] and/or the transition metal compound component [B-2] is 20 ⁇ mol or more and 1000 ⁇ mol or less, and the content of the central metal M is 20 ⁇ mol or more and 1000 ⁇ mol or less.
• (mol) and the content (mol) of Al (Al/M) is 1 or more and 30 or less.
• the content (mol) of the central metal M is preferably 20 ⁇ mol or more and 250 ⁇ mol or less, and the molar ratio (Al/M) is preferably 1 or more and 10 or less.
• the olefin polymerization catalyst of the present embodiment includes the above-mentioned components, and the content (mol) of the central metal M and the molar ratio (Al/M) of the central metal M content (mol) and the Al content (mol). ) is within the above range, it is easy to control the amount and length of long chain branches in the olefin polymer obtained by polymerization, and it is also possible to suppress the amount of long chain branches in the olefin polymer to a very small amount.
• the content (mol) of the central metal M in the catalyst component and the molar ratio (Al/M) between the content (mol) of the central metal M and the content (mol) of Al will be described later. It can be measured by the method described in Examples.
• the inorganic solid particles [A] are preferably magnesium chloride particles.
• the catalyst particles tend to break easily during polymerization, and an olefin polymer with less metal residue can be produced.
• the inorganic solid particles [A], the transition metal compound [B-1], the transition metal compound component [B-2], the activator [C], and the organometallic compound component [ D] is an inorganic solid particle [A], a transition metal compound [B-1], a transition metal compound component [B-2], an activator [C], and an organic
• the contents of the metal compound component [D] can be applied as appropriate.
• the contents of each condition described in the below-mentioned [Method for producing polyethylene powder] can be applied as appropriate to each condition in the method for producing an olefin polymerization catalyst of the present embodiment.
• the method for producing an olefin polymer of the present embodiment includes a step of polymerizing an olefin using the above-described catalyst for olefin polymerization.
• the polyethylene powder of this embodiment can be produced, for example, by polymerizing ethylene or ethylene and other comonomers using a predetermined catalyst component.
• the catalyst components used in the production of the ethylene polymer constituting the polyethylene powder of this embodiment are not particularly limited, but include, for example, inorganic solid particles [A], transition metal compound component [B-1], and transition metal It is preferably composed of a compound component [B-2] and an activator [C] and/or an organometallic compound component [D].
• the inorganic solid particles [A] include, but are not particularly limited to, porous polymeric materials (however, the matrix may be polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethylene-vinyl ester, etc.).
• Polyolefins such as polymers, partial or completely saponified products of styrene-divinylbenzene copolymers and ethylene-vinyl ester copolymers, and their modified products, thermoplastic resins such as polyamides, polycarbonates, and polyesters, phenolic resins, epoxy resins, and urea. resin, thermosetting resin such as melamine resin, etc.), inorganic solid particles (e.g.
• Composite oxides containing silica are not particularly limited, but examples include silica and oxides of elements selected from Group 2 or Group 13 of the periodic table, such as silica-magnesia and silica-alumina. Examples include composite oxides.
• the inorganic solid particles [A] may be selected from silica, alumina, and a composite oxide of silica and an oxide of an element selected from elements belonging to Group 2 or Group 13 of the periodic table. preferable.
• the shape of the silica product used as the inorganic solid particles [A] there is no particular restriction on the shape of the silica product used as the inorganic solid particles [A], and the shape of the silica may be any shape such as granules, spheres, aggregates, and fumes.
• Preferred examples of commercially available silica products include, but are not limited to, SD3216.30, SP-9-10046, Davison Syloid TM 245, Davison 948, or Davison 952 [all of the above, manufactured by Grace Davison ( Manufactured by W.R.
• magnesium chloride used as the inorganic solid particles [A].
• an organomagnesium compound (A-1) which is soluble in an inert hydrocarbon solvent represented by the following (Formula 1) and a chlorinated compound represented by the following (Formula 2) A method of reacting with agent (A-2) can be mentioned.
• M 1 is a metal atom selected from the group consisting of Group 12, Group 13, and Group 14 of the periodic table, and R 1 , R 2 and R 3 each have 2 carbon atoms.
• R 1 , R 2 and R 3 each have 2 carbon atoms.
• the above is a hydrocarbon group of 20 or less, and ⁇ , ⁇ , e, f, and g are real numbers that satisfy the following relationship.
• the organomagnesium compound (A-1) is shown as a complex compound of organomagnesium that is soluble in an inert hydrocarbon solvent, and includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds. It is inclusive.
• the hydrocarbon groups represented by R 1 and R 2 are not particularly limited, but for example, each independently is an alkyl group, a cycloalkyl group, or an aryl group, and more specifically, Examples thereof include, but are not limited to, methyl, ethyl, propyl, butyl, propyl, hexyl, octyl, decyl, cyclohexyl, and phenyl groups. Among these, it is preferable that R 1 and R 2 are each an alkyl group.
• the metal atom M1 a metal atom belonging to any one of the group consisting of Group 12, Group 13, and Group 14 of the periodic table can be used, and more specifically, it is not particularly limited. Examples include zinc, boron, aluminum, and the like. Particularly preferred are aluminum and zinc.
• the ratio ⁇ / ⁇ of magnesium to metal atom M 1 is not particularly limited, but is preferably 0.1 or more and 30 or less, more preferably 0.5 or more and 10 or less.
• At least one of R 1 and R 2 is a hydrocarbon group having 6 or more carbon atoms.
• it is an alkyl group in which the total number of carbon atoms contained in R 1 and R 2 is 12 or more.
• the secondary or tertiary alkyl group having 4 to 6 carbon atoms in group (1) is not particularly limited, but includes, for example, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2- Examples include methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, and 2-methyl-2-ethylpropyl groups. In particular, 1-methylpropyl group is preferred.
• alkyl group having 2 or 3 carbon atoms in group (2) is not particularly limited, and examples thereof include ethyl, 1-methylethyl, propyl, and the like. Particularly preferred is ethyl group.
• the alkyl group having 4 or more carbon atoms is not particularly limited, and examples thereof include butyl, pentyl, hexyl, heptyl, octyl, and the like. Particularly preferred are butyl and hexyl groups.
• the hydrocarbon group having 6 or more carbon atoms in group (3) is not particularly limited, but examples thereof include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl groups, and the like.
• the hydrocarbon groups alkyl groups are preferred, and among the alkyl groups, hexyl and octyl groups are more preferred.
• Form 1 As the number of carbon atoms contained in an alkyl group increases, it tends to become more soluble in an inert hydrocarbon solvent, and the viscosity of the solution tends to increase. Therefore, in the above (Formula 1), it is preferable to use appropriately long-chain alkyl groups as the hydrocarbon groups R 1 and R 2 in terms of handling.
• the above organomagnesium compound (A-1) is used as an inert hydrocarbon solution, but the solution may contain or remain in trace amounts of Lewis basic compounds such as ethers, esters, and amines. can be used without any problem.
• the hydrocarbon group represented by R 3 is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, more preferably an alkyl group or aryl group having 3 to 10 carbon atoms.
• R 3 examples include, but are not limited to, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, Examples include 2-ethylpentyl, 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, and naphthyl groups. Particularly preferred are butyl, 1-methylpropyl, 2-methylpentyl, and 2-ethylhexyl groups.
• the method for synthesizing the organomagnesium compound (A-1) is not particularly limited, but for example, the formula: R 1 MgX 1 and the formula: R 1 2 Mg (R 1 is as described above, and X 1 is a halogen atom).
• any organomagnesium compound belonging to the group consisting of the formula: M 1 R 2 k and the formula: M 1 R 2 (k-1) H (M 1 , R 2 and k are as described above).
• Any organometallic compound belonging to the group consisting of is reacted in an inert hydrocarbon solvent at a temperature of 25° C. to 150° C., if necessary, followed by R 2 (R 2 is as described above).
• R 2 is as described above
• an alkoxymagnesium compound and/or alkoxyaluminum compound having a hydrocarbon group represented by R2 that is soluble in an inert hydrocarbon solvent is a method of synthesis.
• reaction ratio between the organomagnesium compound soluble in an inert hydrocarbon solvent and alcohol is not particularly limited, the molar composition ratio of alkoxy groups to all metal atoms in the alkoxy group-containing organomagnesium compound obtained as a result of the reaction: g/( ⁇ + ⁇ ) satisfies 0 ⁇ g/( ⁇ + ⁇ ) ⁇ 2, and preferably 0 ⁇ g/( ⁇ + ⁇ ) ⁇ 1.
• the chlorinating agent (A-2) is a silicon chloride compound represented by (Formula 2) and having at least one Si—H bond.
• R 4 is a hydrocarbon group having 1 to 12 carbon atoms, and h and i are real numbers that satisfy the following relationship: 0 ⁇ h, 0 ⁇ i, 0 ⁇ h+i ⁇ 4)
• the hydrocarbon group represented by R 4 is not particularly limited, but includes, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples include methyl, ethyl, propyl, 1-methylethyl, butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, and phenyl groups.
• alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and 1-methylethyl groups are more preferred.
• h and i are numbers larger than 0 that satisfy the relationship h+i ⁇ 4, and i is preferably 2 or more and 3 or less.
• chlorinating agent (A-2) a silicon chloride compound consisting of these compounds or a mixture of two or more selected from these compounds is used.
• HSiCl 3 , HSiCl 2 CH 3 , HSiCl(CH 3 ) 2 and HSiCl 2 (C 3 H 7 ) are preferred, and HSiCl 3 and HSiCl 2 CH 3 are more preferred.
• the chlorinating agent (A-2) is mixed in advance with an inert hydrocarbon solvent, a chlorinated hydrocarbon such as 1,2-dichloroethane, o-dichlorobenzene, or dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, It is preferable to use it after diluting it with a mixed solvent or a mixed solvent thereof. Among these, it is more preferable to use an inert hydrocarbon solvent in view of the performance of the catalyst.
• an inert hydrocarbon solvent in view of the performance of the catalyst.
• the reaction ratio between the organomagnesium compound (A-1) and the chlorinating agent (A-2) is not particularly limited; ) is preferably 0.01 mol or more and 100 mol or less, more preferably 0.1 mol or more and 10 mol or less.
• the reaction method of the organomagnesium compound (A-1) and the chlorinating agent (A-2), and the organomagnesium compound (A-1) and the chlorinating agent (A-2) can be reacted simultaneously in a reactor.
• a simultaneous addition method in which the chlorinating agent (A-2) is introduced into the reactor while reacting a method in which the organomagnesium compound (A-1) is introduced into the reactor after the chlorinating agent (A-2) is introduced into the reactor, or an organomagnesium compound (A-1) is introduced into the reactor.
• Any method can be used in which the chlorinating agent (A-2) is introduced into the reactor after chlorinating agent (A-1) is charged into the reactor in advance.
• Particularly preferred is a method in which the chlorinating agent (A-2) is charged into the reactor in advance and then the organomagnesium compound (A-1) is introduced into the reactor.
• the reaction temperature between the organomagnesium compound (A-1) and the chlorinating agent (A-2) is not particularly limited, but is preferably 25°C or higher and 150°C or lower, and preferably 30°C or higher and 120°C or lower.
• the temperature is more preferably 40°C or higher and even more preferably 100°C or lower.
• the temperature of the reactor is adjusted to a predetermined temperature in advance, and the simultaneous addition is performed. It is preferable to adjust the temperature inside the reactor to a predetermined temperature while performing the reaction.
• the chlorinating agent (A-2) is charged into the reactor. It is preferable to adjust the temperature to a predetermined temperature and adjust the temperature inside the reactor to a predetermined temperature while introducing the organomagnesium compound (A-1) into the reactor.
• the temperature of the reactor containing the organomagnesium compound (A-1) It is preferable to adjust the temperature inside the reactor to a predetermined temperature while introducing the chlorinating agent (A-2) into the reactor.
• the magnesium chloride obtained by the above reaction is separated by filtration or decantation and then thoroughly washed with an inert hydrocarbon solvent to remove unreacted substances or by-products.
• transition metal compound component [B-1] used in this embodiment will be explained.
• Examples of the transition metal compound component [B-1] used in the present embodiment are not particularly limited, but include, for example, a compound represented by the following (Formula 3). L 1 j W k M 1 X 1 p X 2 q ...
• X 1 is each independently a monovalent anionic ⁇ -bond ligand, a divalent anionic ⁇ -bond ligand that binds to M in a divalent manner, and a monovalent each to L and M.
• each X 2 independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms; j is 1 or 2, provided that when j is 2, the two ligands L are optionally bonded to each other via a divalent group having up to 20 non-hydrogen atoms, and the 2
• the valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and a hydrocarbyleneamino group having 1 to 12 carbon atoms.
• k is 0 or 1
• p is 0, 1 or 2
• X 1 is a monovalent anionic ⁇
• p is an integer that is at least 1 smaller than the formal oxidation number of M
• p is an integer that is at least (j+1) smaller than the formal oxidation number of M
• q is 0, 1 or 2).
• Examples of the ligand X 1 in the compound of (Formula 3) above are not particularly limited, but include, for example, hydride, halide, hydrocarbon group having 1 to 60 carbon atoms, hydrocarbyloxy group having 1 to 60 carbon atoms, Examples thereof include a hydrocarbylamide group having 1 to 60 carbon atoms, a hydrocarbyl phosphide group having 1 to 60 carbon atoms, a hydrocarbyl sulfide having 1 to 60 carbon atoms, a silyl group, and a composite group thereof.
• Examples of the neutral Lewis base coordinating compound X 2 in the compound of (Formula 3) above are not particularly limited, but include, for example, phosphine, ether, amine, olefin having 2 to 40 carbon atoms, and olefin having 1 to 40 carbon atoms. and divalent groups derived from these compounds.
• the structure of the transition metal compound component [B-1] used in this embodiment is not particularly limited, but from the viewpoint of reducing the mobility of branched chains of polyethylene, a compound capable of polymerizing ultra-high molecular weight polyethylene may be used. is preferred.
• transition metal compound component [B-1] used in this embodiment are not particularly limited, but include, for example, the compounds shown below.
• transition metal compound component [B-1] used in this embodiment are not particularly limited, but include, for example, the "dimethyl” part (this is , which appears at the end of each compound's name, that is, immediately after the "zirconium” or “titanium” part, and is the name corresponding to the X 1 or X 2 part in (Formula 3) above) Compounds with names that can be replaced with any of the following are also included.
• transition metal compound component [B-1] bis(pentamethylcyclopentadienyl)titanium dichloride is preferable.
• the transition metal compound component [B-1] used in this embodiment is not particularly limited, and can be synthesized by a generally known method.
• the transition metal compound component [B-2] used in this embodiment is not particularly limited, but from the viewpoint of macromonomer uptake efficiency, a compound represented by the following (Formula 4) is preferred.
• M2 represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and whose formal oxidation number is +2, +3, or +4,
• R 5 each independently represents 1 to 20 groups selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof.
• X3 each independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a silyl group having 1 to 18 carbon atoms.
• two substituents X 3 work together to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms
• Y 1 represents -O-, -S-, -NR 6 - or -PR 6 -, provided that R 6 is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms.
• transition metal compound component [B-2] used in the present embodiment are not particularly limited, but include, for example, the compounds shown below.
• transition metal compound component [B-2] used in this embodiment are not particularly limited, but for example, the "dimethyl" part of the name of each titanium compound listed above (this is The last part of the name of the compound, that is, the part that appears immediately after the part "titanium” and is the name corresponding to the part X3 in (Formula 4) above, can be changed to any of the following: Also included are compounds with alternative names.
• transition metal compound component [B-2] As a specific example of such transition metal compound component [B-2], a [(Nt-butylamide)(tetramethyl- ⁇ 5-cyclopentadienyl)dimethylsilane]titanium complex is preferable.
• the transition metal compound component [B-2] used in this embodiment is not particularly limited, and can be synthesized by a generally known method.
• activator [C] and organometallic compound component [D] which are capable of forming a complex that exhibits catalytic activity by reacting with the transition metal compound used in this embodiment, will be explained.
• the activator [C] in this embodiment is not particularly limited, but includes, for example, a compound (C-1) defined by the following (Formula 5).
• [L 2 -H] d+ is a protonating Br ⁇ nsted acid
• L 2 is a neutral Lewis base.
• [M 3 r Q s ] d- is a compatible non-coordinating anion
• M 3 is a metal or metalloid selected from Groups 5 to 15 of the periodic table
• Q is each It is independently a hydride, a dialkylamide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms
• the number of Q that is a halide is one or less.
• r is an integer from 1 to 7
• s is an integer from 2 to 14
• non-coordinating anions include, but are not limited to, the following compounds. tetrakis phenylborate, tri(p-tolyl)(phenyl)borate, tris(pentafluorophenyl)(phenyl)borate, tris(2,4-dimethylphenyl)(hydrophenyl)borate, tris(3,5-dimethylphenyl)(phenyl)borate, tris(3,5-di-trifluoromethylphenyl)(phenyl)borate, tris(pentafluorophenyl)(cyclohexyl)borate, tris(pentafluorophenyl)(naphthyl)borate, Tetrakis(pentafluorophenyl)borate, triphenyl (hydroxyphenyl) borate, diphenyl-di(hydroxyphenyl)borate, triphenyl (2,4-dihydroxyphenyl)borate, tri(
• Examples of other preferred non-coordinating anions include, but are not particularly limited to, borates in which the hydroxy group of the borate exemplified above is replaced with an NHR group.
• R is preferably a methyl group, an ethyl group or a tert-butyl group.
• protonating Br ⁇ nsted acids include, but are not particularly limited to, triethylammonium, tripropylammonium, tri(n-butyl)ammonium, trimethylammonium, tributylammonium, tri(n-octyl)ammonium, and the like.
• Trialkyl group-substituted ammonium cations include N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,6-pentamethylanilinium, N,N-dimethyl N,N-dialkylanilinium cations such as benzylanilinium and the like are also suitable.
• dialkylammonium cations such as di-(i-propyl)ammonium, dicyclohexylammonium, etc. are also suitable, and triaryl cations such as triphenylphosphonium, tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium, etc.
• triaryl cations such as triphenylphosphonium, tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium, etc.
• phosphonium cations or dimethylsulfonium, diethylfluoronium, diphenylsulfonium, and the like.
• the activator (C-1) used in this embodiment may be a reactant with an organoaluminum compound.
• the organoaluminum compound is not particularly limited, but includes, for example, trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., or these alkylaluminums and methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol.
• reaction products with alcohols such as hexyl alcohol, octyl alcohol, and decyl alcohol, such as dimethylmethoxyaluminum, diethyl ethoxyaluminum, dibutylbutoxyaluminum, and the like.
• alcohols such as hexyl alcohol, octyl alcohol, and decyl alcohol, such as dimethylmethoxyaluminum, diethyl ethoxyaluminum, dibutylbutoxyaluminum, and the like.
• the reactants with the above-mentioned organoaluminum compounds may be used alone or in combination.
• an organometallic oxy compound having a unit represented by the following (Formula 6) can also be used as the activator [C].
• (Formula 6) (However, M 4 is a metal or metalloid from Group 13 to Group 15 of the periodic table, R 7 is each independently a hydrocarbon group or substituted hydrocarbon group having 1 to 12 carbon atoms, and t is a metal M The valence is 4 , and u is an integer greater than or equal to 2.)
• the activator (C-2) is not particularly limited, but includes, for example, an organoaluminumoxy compound represented by the following formula (7).
• R 8 is a hydrocarbon group having 1 to 12 carbon atoms.
• R 8 is not specifically limited, but includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group.
• organoaluminumoxy compounds composed of one type of alkyl aluminum unit include, but are not particularly limited to, methylalumoxane, ethylalumoxane, n-propylalumoxane, isopropylalumoxane, Examples include n-butylalumoxane, isobutylalumoxane, pentylalumoxane, hexylalumoxane, octylalumoxane, decylalumoxane, cyclohexylalumoxane, and cyclooctylalumoxane. Among these, methylalumoxane and ethylalumoxane are preferred, and methylalumoxan
• the organoaluminumoxy compounds used in this embodiment include those composed of alkyloxyaluminum units represented by the above formula, but are not necessarily limited to compounds composed of one type of constitutional unit. , may be composed of multiple types of structural units. Specific examples thereof include, but are not limited to, methylethyl alumoxane, methylpropylalumoxane, methylbutylalumoxane, etc., and the ratio of various structural units can be set arbitrarily within the range of 0 to 100%. Alternatively, it may be a mixture of a plurality of types of organoaluminumoxy compounds each consisting of one type of structural unit.
• v and w can take arbitrary numbers, but from the viewpoint of ease of manufacture, the ratio v/w of v and w is preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 5 or less. .
• the organoaluminumoxy compound used in this embodiment may contain unreacted chemical substances resulting from its manufacturing method. That is, although organoaluminumoxy compounds are generally obtained by the reaction of trialkylaluminum and H 2 O, it is acceptable for some of these raw materials to remain as unreacted chemical substances. Specifically, although not particularly limited, for example, trimethylaluminum and H 2 O are used as raw materials in the synthesis of methylalumoxane, but one or both of these raw materials may be present as unreacted chemicals in methylalumoxane.
• Examples include cases where it is included in In the method for producing an organoaluminumoxy compound exemplified above, trialkylaluminum is usually used in a larger amount than H 2 O, and thus trialkylaluminum is often contained in the organoaluminumoxy compound as a residual chemical substance.
• the organometallic compound component [D] in this embodiment is a compound containing at least one metal selected from the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table. are preferred, and organoaluminum compounds and/or organomagnesium compounds are particularly preferred.
• organoaluminum compound it is preferable to use compounds represented by the following (Formula 8) alone or in combination.
• (Formula 8) (In formula 8, R 8 is a hydrocarbon group having 1 to 20 carbon atoms, Z 2 is any group belonging to the group consisting of hydrogen, halogen, alkoxy, allyloxy, and siloxy groups, and l is 2 to 3 )
• the hydrocarbon group having 1 to 20 carbon atoms represented by R 8 is not particularly limited, but may include, for example, an aliphatic hydrocarbon, an aromatic hydrocarbon, or an alicyclic hydrocarbon.
• Specific examples include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tri(2-methylpropyl)aluminum (or triisobutylaluminum), tripentylaluminum, tri(3-methylbutyl) )
• Trialkylaluminum such as aluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; halogenation of diethylaluminum chloride, ethylaluminum dichloride, bis(2-methylpropyl)aluminum chloride, ethylaluminum sesquichloride, diethylaluminum bromide, etc.
• Aluminum compounds such as diethylaluminum ethoxide and bis(2-methylpropyl)aluminum butoxide; siloxyaluminum compounds such as dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, and mixtures thereof are listed as preferred. Particularly preferred are trialkyl aluminum compounds.
• the organomagnesium compound it is preferable to use the organomagnesium compound (A-1) represented by the above (Formula 1) alone or in combination.
• ⁇ , ⁇ , e, f, g, M 1 , R 1 , R 2 , and OR 3 in the above (Formula 1) are as described above, but this organomagnesium compound is dissolved in an inert hydrocarbon solvent. Since higher properties are preferable, ⁇ / ⁇ is preferably in the range of 0.5 to 10, and compounds in which M 1 is aluminum are more preferable.
• organomagnesium compounds (D-2) represented by the following (Formula 9) can be used alone or in combination.
• (Formula 9) (In formula 9, M 5 is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, and R 9 and R 10 are hydrocarbon groups having 2 to 20 carbon atoms.
• inorganic solid particles [A], transition metal compound component [B-1], transition metal compound component [B-2], activator [C] and/or organometallic compound component [D] An example of a method for producing a polyethylene polymerization catalyst from.
• the inorganic solid particles [A], the transition metal compound component [B-1], the transition metal compound component [B-2], the activator [C] and A polyethylene polymerization catalyst is produced by reacting/or the organometallic compound component [D].
• the reaction is preferably carried out in an inert hydrocarbon solvent.
• Inert hydrocarbon solvents are not particularly limited, but specifically include aliphatic hydrocarbons such as pentane, hexane, and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic carbonates such as cyclohexane and methylcyclohexane. Examples include hydrogen. Among these, it is more preferable to conduct the reaction in an aliphatic hydrocarbon solvent such as hexane or heptane.
• transition metal compound component [B-1] and transition metal compound component [B-2] may be used in the reaction after being dissolved in an inert hydrocarbon solvent from the viewpoint of reaction efficiency.
• concentration during dissolution is not particularly limited, but from the viewpoint of avoiding segregation on the surface of the inorganic solid particles [A], it is preferably 0.01 mol/L or more and 5 mol/L or less, and 0.05 mol/L or more. More preferably, it is 2 mol/L or less.
• the type and amount of the activator [C] and organometallic compound component [D] are preferably changed for each transition metal compound component from the viewpoint of facilitating control of the amount of long chain branching of polyethylene.
• the concentrations of the activator [C] and the organometallic compound component [D] are not particularly limited, but from the viewpoint of reactivity with the transition metal compound component, it is preferably 0.01 mol/L or more and 5 mol/L or less, More preferably 0.05 mol/L or more and 2 mol/L or less. Note that it is preferable to use an inert hydrocarbon solvent for diluting the activator [C] and the organometallic compound component [D].
• the method of adding the transition metal compound component [B-1], the transition metal compound component [B-2], the activator [C], and the organometallic compound component [D] is not particularly limited. From the viewpoint of forming a layer between the component and the activator and/or organometallic compound component, a mixture of the transition metal compound component and the activator and/or organometallic compound component in advance is used as inorganic solid particles [A]. It is preferable to add the transition metal compound component and the activator and/or the organometallic compound component to the inorganic solid particles [A] at the same time.
• the reaction temperature of the reaction is not particularly limited, but from the viewpoint of reaction efficiency, it is preferably -20°C or more and 100°C or less, more preferably 0°C or more and 80°C or less.
• the molar ratio ([B-2]/[B-1]) between the transition metal compound component [B-1] and the transition metal compound component [B-2] is not particularly limited; From the viewpoint of controlling the amount of chain branching to a very small amount, it is preferably 1 or more and 1000 or less, and more preferably 5 or more and 100 or less.
• the molar ratio ([C]/[B-1]) between the transition metal compound component [B-1] and the activator [C] is not particularly limited; In the case of C-1), it is preferably 0.1 or more and 1 or less, more preferably 0.1 or more and 0.5 or less, from the viewpoint of controlling the amount of long chain branching of polyethylene to a very small amount.
• the molar ratio ([C]/[B-1]) between the transition metal compound component [B-1] and the activator [C] is not particularly limited; -2), from the viewpoint of controlling the amount of long chain branching of polyethylene to a minute amount and suppressing the amount of metal residue in polyethylene, it is preferably 1 or more and 60 or less, more preferably 1 or more and 30 or less. preferable.
• the molar ratio ([D]/[B-1]) of the transition metal compound component [B-1] and the organometallic compound component [D] is not particularly limited; From the viewpoint of controlling and suppressing the amount of metal residue in polyethylene, it is preferably 1 or more and 60 or less, and more preferably 1 or more and 30 or less.
• the molar ratio ([C]/[B-2]) between the transition metal compound component [B-2] and the activator [C] is not particularly limited; In the case of C-1), from the viewpoint of controlling the amount of long chain branching of polyethylene to a very small amount, it is preferably 0.5 or more and 1.5 or less, and more preferably 0.9 or more and 1.1 or less. .
• the molar ratio ([C]/[B-2]) between the transition metal compound component [B-2] and the activator [C] is not particularly limited;
• C-2 from the viewpoint of controlling the amount of long chain branching of polyethylene to a very small amount and suppressing the amount of metal residue in polyethylene, it is preferably 2 or more and 200 or less, and preferably 5 or more and 100 or less. More preferred.
• the molar ratio ([D]/[B-1]) of the transition metal compound component [B-2] and the organometallic compound component [D] is not particularly limited; From the viewpoint of controlling and suppressing the amount of metal residue in polyethylene, it is preferably 1 or more and 60 or less, and more preferably 1 or more and 30 or less.
• the impurity scavenger used in the polymerization of the polyethylene powder of this embodiment is not particularly limited, but it is preferable to use the organometallic compound component [D].
• the impurity scavenger used in the polymerization of the polyethylene powder of this embodiment is not particularly limited, but it is preferable to use the organometallic compound component [D].
• the organometallic compound component [D] There is no particular restriction on the method of adding the organometallic compound component [D] into the polymerization system under polymerization conditions. It may be added to the polymerization system after the reaction.
• the concentration of the organometallic compound component [D] in the polymerization system is not particularly limited, but from the viewpoint of completely capturing impurities and the amount of metal residue in the polymer, it is 0.001 mmol/L or more and 10 mmol/L or less. It is preferably 0.01 mmol/L or more and 5 mmol/L or less, and even more preferably 0.05 mmol/L or more and 2 mmol/L or less.
• the organometallic compound component [D] may be used alone or in combination of two or more types.
• the method of polymerizing the ethylene polymer constituting the polyethylene powder of this embodiment is not particularly limited, but for example, ethylene is polymerized by a suspension polymerization method or a gas phase polymerization method, or ethylene and a comonomer are copolymerized. One method is to do so. Among these, a suspension polymerization method is preferred since it can efficiently remove polymerization heat.
• an inert hydrocarbon medium can be used as a solvent, and furthermore, the olefin itself can also be used as a solvent.
• the inert hydrocarbon medium is not particularly limited, but includes, for example, aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methyl.
• aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene
• cyclopentane cyclohexane
• examples include alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene, and
• the polymerization temperature in the polymerization of ethylene is generally preferably 30°C or higher and 100°C or lower, more preferably 35°C or higher and 95°C or lower, and particularly preferably 40°C or higher and 90°C or lower.
• the polymerization temperature is set to 30° C. or higher, industrially efficient production becomes possible.
• the polymerization temperature is set to 100° C. or less, it is possible to suppress the formation of lumpy scales due to melting of a portion of the polymer, and it is possible to perform continuous and stable production without clogging piping.
• the polymerization pressure of the ethylene polymer is preferably at least normal pressure and at most 2 MPaG, more preferably at least 0.2 MPaG and at most 1.5 MPaG, and even more preferably at least 0.2 MPaG and at most 1.5 MPaG. It is 3 MPaG or more and 0.9 MPaG or less.
• antistatic agents such as Stadis and STATSAFE manufactured by Innospec (distributed by Maruwa Bussan) are used to suppress static electricity adhesion of the polymer to the polymerization reactor. You can also do that.
• An antistatic agent such as Stadis or STATSAFE can be diluted in an inert hydrocarbon medium and added to the polymerization reactor using a pump or the like.
• the antistatic agent can be added by adding it to the solid catalyst in advance or adding it to the polymerization reactor, and the amount added is determined based on the amount of ethylene polymer produced per unit time. , 1 ppm or more and 500 ppm or less, more preferably 10 ppm or more and 100 ppm or less.
• the molecular weight of the ethylene polymer can be controlled by including hydrogen in the polymerization system or by changing the polymerization temperature, as described in West German Patent Application No. 3127133. .
• hydrogen as a chain transfer agent into the polymerization system, it is possible to control the molecular weight of the ethylene polymer within an appropriate range.
• the molar fraction of hydrogen is preferably 0 mol% or more and 50 mol% or less, more preferably 0 mol% or more and 30 mol% or less, and 0 mol% or more and 20 mol% or less. It is even more preferable.
• the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods, and is preferably carried out in a continuous manner.
• the polymerization reaction of the ethylene polymer may be a single-stage polymerization method using one polymerization reactor, or a multi-stage polymerization method in which the polymerization is carried out sequentially and continuously in two or more polymerization reactors connected in series. It's okay.
• the suspension containing the ethylene polymer constituting the polyethylene powder of this embodiment is quantitatively extracted from the polymerization reactor, transferred to a flash tank, and unreacted ethylene, hydrogen, comonomer (unreacted ethylene, hydrogen, comonomer) (limited to cases in which the
• any of the decantation method, centrifugation method, filter filtration method, etc. can be applied, but the centrifugation method has a high separation efficiency between the ethylene polymer and the solvent. More preferred.
• the method for deactivating the catalyst used in the polymerization process of the ethylene polymer constituting the polyethylene powder of this embodiment is not particularly limited, but the catalyst may be deactivated after separating the ethylene polymer and the solvent. is preferred.
• Agents for deactivating the catalyst include, but are not particularly limited to, oxygen, water, alcohols, glycols, phenols, carbon monoxide, carbon dioxide, ethers, carbonyl compounds, alkynes, and the like.
• the drying step it is preferable to carry out a drying step after separating the ethylene polymer from the solvent.
• the drying step it is preferable to use a rotary kiln method, a paddle method, a fluidized dryer, or the like.
• the drying temperature is preferably 50°C or more and 150°C or less, more preferably 70°C or more and 110°C or less.
• the ethylene polymer constituting the polyethylene powder of this embodiment After drying the ethylene polymer constituting the polyethylene powder of this embodiment, it may be sieved to remove coarse powder.
• the polyethylene powder of this embodiment may be a mixture of a plurality of polyethylene powders containing the ethylene polymer obtained by the above-mentioned manufacturing method.
• additives such as slip agents, neutralizers, antioxidants, light stabilizers, antistatic agents, and pigments.
• slip agent or neutralizing agent examples include, but are not limited to, aliphatic hydrocarbons, higher fatty acids, higher fatty acid metal salts, fatty acid esters of alcohols, waxes, higher fatty acid amides, silicone oils, rosins, and the like.
• stearates such as calcium stearate, magnesium stearate, and zinc stearate can be mentioned as suitable additives.
• the antioxidant is not particularly limited, but for example, a phenol compound or a phenol phosphoric acid compound is preferable. Specifically, 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene), n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, tetrakis Phenolic antioxidants such as (methylene (3,5-di-t-butyl-4-hisaloxyhydrocinnamate))methane; 6-[3-(3-t-butyl-4-hydroxy-5-methyl) Phenolphosphorus antioxidants such as -2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine; tetrakis(2,4 -di-t-butylphenyl)-4,4'-biphenylene-di-phosphonite
• Light stabilizers include, but are not particularly limited to, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro Benzotriazole light stabilizers such as benzotriazole; bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino- 1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4- Examples include hindered amine light stabilizers such as piperidyl)imino].
• the antistatic agent is not particularly limited, but includes, for example, aluminosilicate, kaolin, clay, natural silica, synthetic silica, silicates, talc, diatomaceous earth, and glycerin fatty acid ester.
• the polyethylene powder of this embodiment can be used as a raw material for various molded bodies such as microporous membranes, fibers, especially high-strength fibers, sintered bodies, press molded bodies, and ram-pressed bodies.
• the polyethylene powder of this embodiment is suitable as a raw material for microporous membranes for battery separators.
• the molded body of this embodiment is a molded body of the polyethylene powder of this embodiment described above.
• molded body examples include, but are not particularly limited to, microporous membranes, especially microporous membranes that are battery separators, fibers, especially high-strength fibers, sintered bodies, press-formed bodies, and ram-pressed bodies.
• the method for producing the molded body is not particularly limited, but includes, for example, a molding method that involves extruding a resin using a wet extrusion method, stretching, extraction, and drying steps.
• the above-mentioned battery separator is not particularly limited, but includes, for example, a separator for lithium ion secondary batteries, a separator for lead-acid batteries, and the like.
• decalin nitrogen-substituted decalin
• the decalin solution was put into a Cannon-Fenske viscometer (manufactured by Shibata Kagaku Kikai Kogyo Co., Ltd./viscosity meter number: 100) in a constant temperature liquid bath at 135°C, and the falling time (t s ) between the marked lines was measured. It was measured. Further, as a blank, the falling time (t b ) of only decalin without polyethylene powder was measured, and the specific viscosity ( ⁇ sp ) was determined according to the following (formula A).
• Tm2 end was calculated using the following procedure. ⁇ Tm2 end calculation procedure> (1) Differentiate the amount of endotherm obtained in the second heating process with respect to temperature. (2) Regarding the absolute value of the differential value obtained in (1), the temperature at which it becomes 0.01 or less for the first time counted from Tm2 top was defined as Tm2 end .
• ⁇ Sample concentration> If Mv is less than 300,000: 10mg/10mL If Mv is 300,000 or more and less than 1 million: 3mg/10mL If Mv is 1 million or more and less than 2 million: 2mg/10mL If Mv is 2 million or more and less than 3 million: 1.5mg/10mL If Mv is 3 million or more: 1.5mg/15mL Further, the prepared sample solution was heated and shaken according to the following ⁇ dissolution conditions>. The sample solution after dissolution was placed in an autosampler heated to 160°C without cooling.
• ⁇ Dissolution conditions> (1) Let stand for 1 hour while heating to 150°C (2) Shake for 2 hours while heating to 150°C (3) Leave to stand for 30 minutes while heating to 150°C Next, ⁇ GPC measurement conditions> shown below. Measurements were carried out according to the following.
• RI Differential refractometer
• PL-BV400 type Detector connection method Connected in parallel
• g' IV sample /IV linear (Formula H)
• g' z ⁇ (Conc i ⁇ MW i ⁇ g' i )/ ⁇ (Conc i ⁇ MW i ) (Formula I)
• Conc i is the solution concentration in the i-th fraction
• MW i is the molecular weight in the i-th fraction
• g' i is g' in the i-th fraction.
• the z-average shrinkage factor g z was calculated using the following (Formula J).
• z - Average shrinkage factor g z g' z (1/0.75) (Formula J)
• This measurement sample was measured using a Fourier transform far-infrared spectrometer (manufactured by JASCO Corporation, model: VIR-F4000) under the ⁇ terahertz measurement conditions> shown below.
• ⁇ Terahertz measurement conditions> Wavenumber region: 50 to 600cm -1
• the absorption coefficient at each wave number is calculated using the following (formula K), and the absorption coefficient at 400 cm -1 to 450 cm -1 is calculated. did.
• the elemental content of the polyethylene powder was measured by high frequency plasma mass spectrometry in accordance with JIS K0133.
• the samples were prepared by pressure acid decomposition with nitric acid using a microwave decomposition device (model ETHOSTC, manufactured by Milestone General Co., Ltd.).
• ETHOSTC microwave decomposition device
• the aluminum content and silicon content in the polyethylene powder were determined using an internal standard method using ICP-MS (Inductively Coupled Plasma Mass Spectrometer, Model X Series X7, manufactured by Thermo Fisher Scientific). was quantified.
• the density of polyethylene powder was determined by methods (1) to (7) shown below.
• a 20 mm x 20 mm x 2 mm thick section was cut from the obtained press sheet. (5) The cut sections were placed in a test tube and heated at 120° C. for 1 hour in a nitrogen atmosphere.
• the content (mol) of the central metal M contained in the transition metal compound component [B-1] and/or the transition metal compound component [B-2] in the catalyst component, and the content (mol) of the central metal M and Al molar ratio (Al/M) with the content (mol) of The element content in the catalyst component was measured using a microwave plasma atomic emission spectrometer (manufactured by Agilent, model: 4210 MP-AES/G8007A).
• a microwave plasma atomic emission spectrometer manufactured by Agilent, model: 4210 MP-AES/G8007A.
• the content (mol) of the central metal M and the content (mol) of Al contained in the transition metal compound component [B-1] and/or the transition metal compound component [B-2] in the catalyst component are determined by the external standard method. ) was quantified and their molar ratio (Al/M) was calculated.
• ⁇ MP-AES measurement conditions Standard solution for device calibration: ICP-OES & MP-AES Wavecal: Al, As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Se, Sr, Zn (5mg/L); K( 50mg/L) in 5% HNO3 Background correction: Auto Read time: 3s Observation position: 0 Nebulizer flow rate: M (0.5-1.0L/min), Al (0.95L/min) Number of measurement repetitions: 3 Pump speed: 15rpm Intake time: 15s Stabilization time: 15s Number of pixels: 3 Standard solution for creating a calibration curve: Standard solution for atomic absorption spectrometry corresponding to each element (manufactured by Kanto Kagaku Co., Ltd.) Calibration curve concentration: 8 points: 0.5mg/L, 1mg/L, 2mg/L, 5mg/L, 10mg/L, 20mg/L, 50mg/L, 100mg/L
• the mold was preheated at 1 kg/cm 2 for 3 minutes using a press machine with a set temperature of 180° C., defoaming was performed three times, and pressed at 10 kg/cm 2 for 2 minutes.
• the gel sheet thus obtained is subjected to simultaneous biaxial stretching at 115°C (when the viscosity average molecular weight of polyethylene is 100,000 to 2,500,000) or 120°C (when the viscosity average molecular weight of polyethylene is 2,500,000 to 4,000,000).
• a stretched film was obtained by stretching the film to 7 ⁇ 7 times.
• this stretched film was immersed twice in n-hexane for 20 minutes, and after extracting and removing liquid paraffin, it was air-dried. Further heat setting was performed at 125° C. for 3 minutes to obtain a microporous membrane. However, the stretching temperature and heat setting temperature were adjusted as appropriate for each microporous membrane within the specified temperature range.
• thermo shrinkage rate of the microporous membrane at high temperatures was evaluated. Specifically, from the microporous membrane obtained by the above-mentioned [microporous membrane manufacturing method], eight 100 mm x 50 mm membranes were punched out from 250 mm x 250 mm, and placed in an oven set at 140°C for 60 minutes. I placed it. After cooling at room temperature for 15 minutes after heating and standing, the dimensions of the microporous membrane were measured, and the thermal shrinkage rate (%) was calculated from the following formula. Then, the average of the measured values at 8 points in total was calculated, and the heat resistance was evaluated using the following evaluation criteria.
• the thermal shrinkage rate of the microporous membrane was evaluated as an evaluation index of dimensional stability. Specifically, from the microporous membrane obtained by the above-mentioned [microporous membrane manufacturing method], eight 100 mm x 50 mm membranes were punched out from 250 mm x 250 mm, and placed in an oven set at 120°C for 60 minutes. I placed it. After cooling at room temperature for 15 minutes after heating and standing, the dimensions of the microporous membrane were measured, and the thermal shrinkage rate (%) was calculated from the following formula. Then, the average of the measured values at a total of 8 points was calculated, and the dimensional stability was evaluated using the following evaluation criteria.
• Raw material (A-1) was an organic magnesium compound with a magnesium concentration of 0.704 mol/L.
• transition metal compound component [B-2] (b-1)
• Isopar E Exxon Chemical Co., Ltd. 1 mol/L ethylbutylmagnesium (hexane solution) was added thereto.
• hexane was added to adjust the titanium complex concentration to 0.08 mol/L to obtain a transition metal compound component (b-1).
• Example 1 Preparation of catalyst component (A)
• Cp * 2 TiCl 2 bis(pentamethylcyclopentadienyl) titanium dichloride
• MMAO modified methyl Aluminoxane
• a-1 to a-3 represent the inorganic solid particles (a-1) to (a-3) prepared above in order, and b-1 represents the transition metal compound component prepared above.
• b-1 represents [(Nt-butyramide)(tetramethyl- ⁇ 5-cyclopentadienyl)dimethylsilane]titanium dichloride, and c-1 represents the activated activated agent (c-1), c-2 represents N,N'-dimethylanilinium tetrakis(pentafluorophenyl)borate, and d-1 represents the organometallic compound component (d-1) synthesized above.
• Cp * 2TiCl2 represents bis(pentamethylcyclopentadienyl ) titanium dichloride
• Cp2TiCl2 represents bis(cyclopentadienyl)titanium dichloride
• nBuCp2ZrCl2 represents bis ( n -butylcyclopentadienyl) zirconium dichloride
• Cp * 2 ZrCl 2 represents bis(pentamethylcyclopentadienyl) zirconium dichloride
• TiCl 4 represents titanium tetrachloride
• Ti(OBu) 4 It stands for titanium (IV) tetrabutoxide (monomer)
• EtAlCl 2 stands for ethylaluminum dichloride
• Et 2 AlCl stands for diethylaluminum chloride
• MMAO stands for modified methylaluminoxane
• MAO stands for methylaluminoxane.
• Polymerization was carried out for 30 minutes while stirring at a stirring speed of 1200 rpm while maintaining an internal pressure of 0.65 MPa and an internal temperature of 60°C.
• the reaction mixture (polymer slurry) was extracted from the polymerization reactor, and the catalyst was deactivated with methanol. Thereafter, the reaction mixture was filtered, washed, and air-dried to obtain polyethylene powder (A).
• the polymerization activity in the polymerization reactor was 3,500 g/g of catalyst.
• Table 5 shows the results of the various evaluations described above for the polyethylene powder (A) and the microporous membrane of the polyethylene powder (A) manufactured by the above-mentioned [method for manufacturing a microporous membrane].
• Example 12 to 20 and Comparative Examples 7, 8, 11, 12 Polyethylene powder and a microporous membrane thereof were produced in the same manner as in Example 11, except that the polymerization conditions were changed as shown in Tables 3 and 4, and the various evaluations described above were performed. The results are shown in Tables 5 and 6.
• Example 15 and Comparative Example 12 0.05 mol% of 1-butene was copolymerized as a comonomer.
• the polymerization slurry was continuously sent to a centrifuge so that the level in the polymerization reactor was kept constant to separate the polyethylene powder and other solvents.
• the separated polyethylene powder was dried at 78° C. while blowing with nitrogen.
• steam was sprayed onto the powder after polymerization to deactivate the catalyst and co-catalyst.
• 1,000 ppm of calcium stearate manufactured by Dainichi Chemical Co., Ltd., C60
• Polyethylene powder (K) was obtained by using a sieve with an opening of 425 ⁇ m to remove what did not pass through the sieve.
• the polymerization activity in the polymerization reactor was 20,000 g/g of catalyst.
• Table 6 shows the results of the various evaluations described above for the polyethylene powder (K) and the microporous membrane of the polyethylene powder (K) manufactured by the above-mentioned [method for manufacturing a microporous membrane].
• Hydrogen was continuously supplied by a pump so that the gas phase concentration was 2000 ppm.
• the stirring speed was 230 rpm.
• a 100 mmol/L hexane solution of n-butanol was supplied so that the amount of n-butanol was 1 ppm/h for a polymerization rate (production rate) of 10 kg/h to obtain a polymerization slurry.
• the obtained polymerization slurry was sent to a centrifuge to separate the polyethylene powder from other solvents, and then the polyethylene powder was brought into contact with methanol at 60° C. for 1 hour while stirring.
• a polymerization slurry containing polyethylene powder and methanol was sent to a centrifuge to separate the polyethylene powder and other solvents.
• the separated polyethylene powder was dried at 70° C. while blowing with nitrogen.
• Polyethylene powder (L) was obtained by using a sieve with an opening of 425 ⁇ m to remove the polyethylene powder that did not pass through the sieve.
• the polymerization activity in the polymerization reactor was 30,000 g/g of catalyst.
• Table 6 shows the results of the various evaluations described above for the polyethylene powder (L) and the microporous membrane of the polyethylene powder (L) manufactured by the above-mentioned [method for manufacturing a microporous membrane].
• d-1 represents the organometallic compound component (d-1) synthesized above, Et 3 Al represents triethylaluminum, and iBu 3 Al represents triisobutylaluminum.
• the polyethylene powder of the present invention has excellent heat resistance, film uniformity, dimensional stability, and high heat resistance rate when made into a microporous film, and has industrial applicability.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88202421

Family Applications (1)

Country Status (5)

Citations (7)

Family Cites Families (2)

• 2023
  • 2023-03-31 CN CN202380023600.7A patent/CN118765289A/zh active Pending
  • 2023-03-31 US US18/852,537 patent/US20250215120A1/en active Pending
  • 2023-03-31 WO PCT/JP2023/013646 patent/WO2023191080A1/ja not_active Ceased
  • 2023-03-31 KR KR1020247028348A patent/KR20240135850A/ko active Pending
  • 2023-03-31 JP JP2024512929A patent/JPWO2023191080A1/ja active Pending

Patent Citations (7)

Also Published As

Similar Documents

Legal Events