WO2009069825A1 - エチレン-α-オレフィン共重合体および成形体 - Google Patents
エチレン-α-オレフィン共重合体および成形体 Download PDFInfo
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- WO2009069825A1 WO2009069825A1 PCT/JP2008/072002 JP2008072002W WO2009069825A1 WO 2009069825 A1 WO2009069825 A1 WO 2009069825A1 JP 2008072002 W JP2008072002 W JP 2008072002W WO 2009069825 A1 WO2009069825 A1 WO 2009069825A1
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- zirconium dichloride
- diphenylmethylene
- fluorenyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
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- 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
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- 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
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- 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
- C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Definitions
- the present invention relates to an ethylene 1 ⁇ -olefin copolymer and a molded product obtained by extruding the ethylene 1 ⁇ -olefin copolymer.
- Ethylene mono ⁇ -olefin copolymers are formed into films, sheets, bottles, etc. by various molding methods and used for various applications such as food packaging materials.
- ethylene monoolefin copolymer As an ethylene monoolefin copolymer, it is known that a copolymer polymerized using a meta-mouth catalyst is excellent in mechanical strength such as impact strength and tensile strength. Therefore, by reducing the thickness of the molded product, it can be expected to reduce the weight and cost of the molded product while maintaining the mechanical strength. Therefore, the use of the copolymer for various applications has been studied.
- an ethylene- ⁇ -olefin copolymer polymerized using a conventional metallocene catalyst has a high extrusion load at the time of extrusion, and the melt tension ratio is small, so that the moldability is sufficient. Rather, its use was limited.
- Japanese Patent Application Laid-Open No. 2 093-9 6 1 2 5 discloses a transition metal compound having a ligand in which two groups having a cyclopentagen type anion skeleton are bonded through a bridging group.
- a polymer of ethylene polymerized using a meta-octacene catalyst comprising a transition metal compound having a group having two substituted cyclopentagen type anion skeletons that are not bonded to each other and an activating co-catalyst component.
- Japanese Patent Application Laid-Open No. 2 044 _ 1 4 9 7 6 1 discloses a promoter component obtained by contacting silica, hexamethyldisilazane, jetyl zinc, pentafluorophenol and water, An ethylene_ ⁇ -olefin copolymer polymerized using a meta-octacene catalyst consisting of isobutylaluminum and racemic ethylene bis (11 ⁇ f) zirconium dibuenoxide is described. JP 2 No.
- 006-233206 discloses a transition metal compound having a ligand in which two groups having a pentopen pentagen type anion skeleton are bonded via a bridging group, a group having a chicopen pentagen type anion skeleton, and a fluorenyl group.
- a meta-acrocene catalyst comprising a combination of a transition metal compound having a ligand in which a group having a type guanion skeleton is bonded via a bridging group, and methylalumoxane as a co-catalyst supported on porous silica. comprising polymerized using a carrier ethylene one alpha - Orefin copolymer is described.
- the ethylene- ⁇ -olefin copolymers described in JP-A-2003-96125 and JP-A-2004-149761 are still not sufficiently satisfactory in terms of extrusion load and swell ratio during molding.
- the ethylene- ⁇ -olefin copolymer described in JP-A-2006-233206 has an insufficient swell ratio and a long relaxation time of the molten ethylene-olefin copolymer molecular chain.
- the appearance of the molded body obtained by molding and the take-up property at the time of molding were not yet satisfactory.
- the problem to be solved by the present invention is that ethylene- ⁇ -olefin has excellent extrusion load, swell ratio and mechanical strength, and has a sufficiently short molecular chain relaxation time in the molten state.
- An object of the present invention is to provide a copolymer, and a molded body obtained by extrusion molding the copolymer. As a result of intensive studies to solve these problems, the present inventors have completed the present invention.
- the first of this book has a monomer unit based on ethylene and a monomer unit based on ⁇ -olefin having 3 to 20 carbon atoms, and the density (d) is 860 to 950 kgZm 3
- the melt flow rate (MFR) is :! ⁇ 100 g / 10 min.
- the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (MwZMn) is 4 to 30; the Z average molecular weight (Mz) and the weight average molecular weight (Mw)
- the ratio (Mz-Mw) is 2 to 5
- the Swell ratio (SR) is 1.8 or more
- the characteristic relaxation time () determined by linear viscoelasticity measurement is 0.01 to 10 seconds. 1. It relates to an ⁇ -olefin copolymer.
- a second aspect of the present invention relates to a molded product obtained by extruding the above ethylene- ⁇ -aged olefin copolymer.
- the ethylene- ⁇ -olefin copolymer of the present invention impairs the effects of the present invention in addition to the above-mentioned monomer units based on ethylene and monomer units based on ⁇ -aged olefins having 3 to 20 carbon atoms. As long as there is no monomer unit, it may have a monomer unit based on another monomer.
- Other monomers include, for example, conjugated genes (for example, butadiene and isoprene), non-conjugated genes (for example, 1,4_pentagen), acrylic acid, acrylic acid esters (for example, methyl acrylate, ethyl acrylate), Examples thereof include methacrylic acid, methacrylic acid esters (for example, methyl methacrylate ethyl methacrylate), vinyl acetate and the like.
- the ethylene- ⁇ -olefin copolymer of the present invention is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on ⁇ -olefin having 4 to 20 carbon atoms, Preferably, it is a copolymer having a monomer unit based on ethylene and a monomer unit based on ⁇ -olefin having 5 to 20 carbon atoms, more preferably a monomer unit based on ethylene and a carbon atom. It is a copolymer having monomer units based on ⁇ -olefins of formula 6-8.
- Examples of the ethylene-1- ⁇ -olefin copolymer of the present invention include ethylene-1-butene. Copolymer, ethylene 1-hexene copolymer, ethylene 4-methyl-1- 1-pentene copolymer, ethylene 1-octene copolymer, ethylene 1-butene _ 1-hexene copolymer Ethylene 1-butene 1-methyl-1-pentene copolymer, ethylene 1-butene 1-octene copolymer, ethylene 1-hexene 1-octene copolymer, etc., preferably Ethylene 1-hexene copolymer, Ethylene 1-methyl-1-pentene copolymer, Ethylene 1-butene 1-hexene copolymer, Ethylene 1-butene 1-octene copolymer
- the density of the ethylene 1-ct-olefin copolymer of the present invention which is an ethylene-1-hexene-1-1-oc
- the density is measured in accordance with the method specified in the ⁇ method of JIS K71 1 2-1980 after annealing described in JIS K6760 — 195. Further, the density of the ethylene / ⁇ -olefin copolymer can be changed depending on the content of the monomer unit based on ethylene in the ethylene / ⁇ -olefin copolymer.
- the melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene- ⁇ -olefin copolymer of the present invention is usually 1 to 100 gZl 0 minutes.
- the melt flow rate is preferably 1.5 g / l 0 min or more from the viewpoint of reducing the extrusion load during molding. Further, from the viewpoint of increasing the mechanical strength of the obtained molded article, it is preferably 50 gZ for 10 minutes or less, more preferably 20 g / 10 minutes or less, and further preferably 10 gZ for 10 minutes or less.
- the melt flow rate is a value measured by the A method under the conditions of a temperature of 1900C and a load of 21.18 N in the method specified in JIS K72 10-1995.
- melt flow rate of the ethylene 1 ⁇ -olefin copolymer can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later.
- the melt flow rate of the ethylene- ⁇ -olefin copolymer increases.
- the weight average molecular weight (hereinafter sometimes referred to as “Mw”) and the number average molecular weight (hereinafter sometimes referred to as “Mn”) of the ethylene- ⁇ -olefin copolymer of the present invention is 4 to 30, and the Z average molecular weight (hereinafter sometimes referred to as “Mz”) and the weight average molecular weight (Mw)
- the ratio (hereinafter sometimes referred to as “Mz / Mw”) is 2-5. If Mw / Mn is too small, the extrusion load during molding may increase.
- Mw / Mn is preferably 4.5 or more, more preferably 5.5 or more, and further preferably 6 or more.
- Mz Mw is too large, the relaxation time of the molecular chain of the polymer in the molten state may be long.
- Mz Mw is preferably 4.5 or less, more preferably 4 or less. If Mw No Mn is too large or Mzw is too small, the mechanical strength of the resulting molded product may be lowered.
- MwZMn is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 12 or less.
- Mz / Mw is preferably 2.5 or more.
- the MwZMn and the MzZMw are obtained by measuring the number average molecular weight (Mn), the weight average molecular weight (Mw) and the Z average molecular weight (Mz) by gel permeation chromatography (GPC) method. It is obtained by dividing by Mn and dividing M z by Mw.
- the MwZMn can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. When the hydrogen concentration or the polymerization temperature is increased, the MwZMn of the ethylene- ⁇ -olefin copolymer increases. Become.
- MzZMw represents the molecular weight distribution of the high molecular weight component.
- (Mw / Mn) — (Mz / Mw) is preferably 1 or more, more preferably (Mw / Mn)-(Mz Mw ) Is 2 or more.
- (MwZ Mn)-(Mz Mw) can be changed depending on, for example, the ratio of transition metal compound ( ⁇ ) and transition metal compound (A 2). The ratio of transition metal compound (A 2) is increased. Then, (Mw / Mn)-(Mz Mw) of ethylene-c-olefin copolymer increases. Also, (MwZMn)-(Mz / Mw) can be increased by carrying out prepolymerization.
- the swell ratio (hereinafter sometimes referred to as “SR”) of the ethylene- ⁇ -olefin copolymer of the present invention is 1.8 or more. If the swell ratio is too small, the neck-in may increase when forming a T-die film.
- the swell ratio is preferably 1.85 or more, more preferably 1.9 or more, and further preferably 2.0 or more. Further, the swell ratio is preferably 2.5 or less from the viewpoint of improving the take-up property at the time of extrusion molding.
- the swell ratio is determined by measuring the melt flow rate (MFR) at a temperature of 190 ° C and a load of 21.18 N.
- the swell ratio can be changed by, for example, the hydrogen concentration at the time of polymerization, the ethylene pressure or the electron donating compound concentration in the production method described later. When the hydrogen concentration is increased or the ethylene pressure is decreased, The swell ratio of the monoolefin copolymer increases. In addition, the swell ratio can be controlled by performing prepolymerization at the time of polymerization.
- the number of branches having 5 or more carbon atoms (hereinafter sometimes referred to as “NLCBJ”) of the ethylene_one-year-old refin copolymer of the present invention is preferably from the viewpoint of further reducing the extrusion load during the molding process. Is from 0.1 to 1000 C, more preferably from 0.1 2 1000 C. Also, from the viewpoint of increasing the mechanical strength of the obtained molded product, it is preferably 1100 C or less, more preferably Is 0.7Z1000 C or less, and the NLCB is In the production method described later, for example, the concentration of the electron donating compound or the transition metal compound
- NLCB is based on the 13 C-NMR spectrum measured by the carbon nuclear magnetic resonance ( 13 C_NMR) method.
- the total area of all peaks observed at 5 to 50 ppm is 1000 and the number of carbon atoms is 7 or more. It is obtained by calculating the area of the peak derived from the methine carbon to which the branch is bonded.
- the peak derived from methine carbon with a branch of 5 or more carbon atoms attached is around 38.2 ppm (Reference: Scientific literature “Macromolecules”, (USA), American Chemical Society, 1999, Vol. 32, p.3817). — Observed at 3819).
- the position of the peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded may vary depending on the measurement device and measurement conditions, the standard is usually measured for each measurement device and measurement conditions. Decide. For spectrum analysis, it is preferable to use a negative exponential function as the window function.
- the characteristic relaxation time (hereinafter sometimes referred to as “ ⁇ ”) of the ethylene- ⁇ -aged refin copolymer of the present invention is 0 from the viewpoint of improving the take-up property during molding and the appearance of the molded product. 01 to 10 seconds.
- the characteristic relaxation time is a numerical value indicating the length of the long chain branch of the ethylene- ⁇ -olefin copolymer.
- the long chain branch is short, and the characteristic relaxation time is a small value, and the long chain branch is The long and characteristic time is large.
- the characteristic relaxation time is preferably 0.1 seconds or longer.
- the characteristic relaxation time is preferably 5 seconds or less.
- the characteristic relaxation time can be changed, for example, depending on the polymerization conditions such as hydrogen concentration and ethylene pressure, and the use ratio of the transition metal compound (A1) and the transition metal compound ( ⁇ 2), and the use of the transition metal compound ( ⁇ 2). If the ratio is reduced, the characteristic relaxation time of the ethylene- ⁇ -aged refin copolymer can be shortened.
- Characteristic relaxation time is created based on the superposition principle of temperature for one hour. Master showing the dependence of the melt complex viscosity (unit: Pa ⁇ sec) at 190 ° C on the angular frequency (unit: rad / sec) It is a numerical value calculated from one curve. Specifically, melting complex viscosity angular frequency curve (melting complex) of ethylene 1 ⁇ -olefin copolymer at 130 ° C, 150 ° C, 170 ° C and 190 ° C (T, unit: C). The unit of viscosity is P a-sec, the angular frequency The unit is rad / sec. ) Is superimposed on the melt complex viscosity angular frequency curve at 190 ° C based on the temperature-time superposition principle, and the obtained master curve is approximated by the following formula (I) Is a value calculated by.
- ⁇ angular frequency (unit: r a d / s e c)
- ⁇ Constant determined for each ethylene- ⁇ -olefin copolymer (Unit: P a ⁇ se c)
- n Constant determined for each ethylene- ⁇ -olefin copolymer
- calculation software examples include Rhio s V.4.4.4 manufactured by Rheomoterics.
- the melt complex viscosity angular frequency curve is measured using a viscoelasticity measuring device (for example, R heome trics Mechanical Spectr om eter RMS—8 0 0, etc., manufactured by R heom etrlcs).
- a viscoelasticity measuring device for example, R heome trics Mechanical Spectr om eter RMS—8 0 0, etc., manufactured by R heom etrlcs.
- geometry parallel Plate
- plate diameter 25 mm
- plate interval 1.5 to 2 mm
- strain 5%
- angular frequency 0:!
- To 100 0 radZ seconds To 100 0 radZ seconds.
- an appropriate amount of an antioxidant for example, 100 ppm
- the g * defined by the following formula (II) of the ethylene mono- ⁇ -olefin copolymer of the present invention is preferably from 0.76 to 0.95 (refer to the following literature for g *) Developments in Polymer Characterization-4 ,. J. v .. Dawkins ,. Ed.,. Applied Science London ,. 1983, Chapter. I ,. "Characterization, of. Long Chain Branching in
- [ ⁇ ] represents the intrinsic viscosity (unit: d 1 / g) of the ethylene- ⁇ -aged refin copolymer, and is defined by the following formula (I 1 _ 1). It was defined by the following formula (I I _I I). gscB * is defined by the following formula (I I 1 I I I).
- ⁇ ⁇ represents the viscosity average molecular weight of ethylene- ⁇ -aged refin copolymer.
- GscB * (1 -A) 1725 (II-III)
- [ ⁇ ] GPC is the intrinsic viscosity of the polymer (unit: d 1 / g Represents).
- gscB * represents the contribution to g * caused by the introduction of short chain branching in the ethylene- ⁇ -aged refin copolymer.
- the viscosity-average molecular weight ( ⁇ ) of ethylene- ⁇ -olefin copolymer is expressed by the following formula (I I— I V
- y is the number of short chain branches per 1000 carbon atoms determined by MR or infrared spectroscopy
- A ((12 X n + 2 n + 1) X y) / ((1000— 2 y— 2) X 14 + (y + 2) X 1 5 + y X 13)
- g * is an index that represents the degree of contraction of molecules in solution due to long chain branching. The greater the amount of long chain branching per molecular chain, the greater the shrinkage of the molecular chain. Becomes smaller.
- Ethylene one alpha - old Refuin copolymer g * from the viewpoint of reducing the extrusion load, preferably at 0.95 or less, more preferably 0.85 or less. When g * is large, long-chain branching is not sufficiently contained, so the extrusion load cannot be reduced sufficiently.
- g * of the ethylene- ⁇ -olefin copolymer is preferably 0.76 or more from the viewpoint of improving the mechanical strength and shortening the relaxation time.
- g * can be controlled, for example, by performing a reserve weight ⁇ :.
- the flow activation energy (hereinafter sometimes referred to as “ ⁇ a”) of the ethylene- ⁇ -alpha olefin copolymer of the present invention is preferable from the viewpoint of further reducing the extrusion load during the molding process. Is 50 kJ / mo 1 or more, more preferably 60 kJ / mo 1 or more.
- the flow activation energy is preferably 150 kJ / mo 1 or less, more preferably 130 kJ / o 1 or less, more preferably, from the viewpoint of enhancing the take-up property during extrusion molding. 1 10 k J / mo 1 or less, most preferably 100 k J / mo 1.
- the flow activation energy can be changed, for example, by the ratio of the transition metal compound (A1) and the transition metal compound (A 2) used in the production method described later.
- the use of the transition metal compound (A2) Increasing the ratio increases the Ea of the ethylene ct 1 year old refin copolymer.
- the flow activation energy (E a) is the angular frequency (unit: rad, sec) of the melt complex viscosity (unit: P a ⁇ sec) at 190 ° C, based on the temperature one hour superposition principle. This is a numerical value calculated from the shift factor (aT) when creating a master curve that shows the dependency, using the Arrhenius type equation, and obtained by the following method.
- Melt complex viscosity—angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer ter RMS—800, etc., manufactured by Rheome trlcs). Plate diameter: 25mm, plate spacing: 1.5 to 2mm, strain: 5%, angular frequency: 0:! To 100 rad / sec. The measurement is performed under a nitrogen atmosphere, and It is preferable to mix an appropriate amount of an antioxidant (for example, 1 00 ppm) in advance in the measurement sample.
- an antioxidant for example, 1 00 ppm
- the method for producing the ethylene- ⁇ -olefin copolymer of the present invention includes a transition metal compound (A1) represented by the following general formula (1) and a transition metal compound (A) represented by the following general formula (3) (A 2) and a cocatalyst component (B) to be described later, and a polymerization catalyst formed by contacting the transition metal compound (A1) and the transition metal compound (A2) with a molar ratio ((Al) / A method of copolymerizing ethylene and ⁇ -olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst to be brought into contact with (A2)) at 1 to 30 can be mentioned.
- (Al) / ( ⁇ 2) is ethylene in the molten state - alpha - in view of enhancing the short relaxation times of the molecular chains of Orefuin copolymer, and mechanical strength, preferably, 5 or more, more preferably 10 or more It is. Further, (Al) / ( ⁇ 2) is preferably 20 or less from the viewpoint of increasing SR.
- ⁇ 1 represents a transition metal atom of Group 4 of the periodic table of elements, and ⁇ and Ri are each independently substituted with a hydrogen atom, a halogen atom, or a carbon atom number of 1-20. Or a hydrocarbanoloxy group having 1 to 20 carbon atoms, an optionally substituted hydrocarbyloxy group, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms.
- a plurality of X 1 may be the same or different from each other; a plurality of R 1 may be the same or different from each other;
- Qi represents a bridging group represented by the following general formula (2); To express.
- R 2 is a hydrogen atom, a halogen atom, or a substitution of 1 to 20 carbon atoms.
- a substituted amino group, and a plurality of R 2 may be the same or different from each other.
- M 2 represents a transition metal atom of Group 4 of the periodic table of the elements
- X 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 20 optionally substituted hydrocarbinole group, 1 to 20 carbon atoms optionally substituted hydrocanolevinoleoxy group, 1 to 20 carbon atoms substituted silyl group or carbon atom
- a plurality of X 2 may be the same as or different from each other; a plurality of R 3 may be the same as or different from each other; 4 may be the same as or different from each other, and Q 2 represents a bridging group represented by the following general formula (4).
- n is an integer of 1 to 5
- J 2 represents an atom belonging to Group 14 of the periodic table
- R 5 represents , A hydrogen atom, a halogen atom, an optionally substituted hydride carbyl group having 1 to 20 carbon atoms, an optionally substituted hydride carbyloxy group having 1 to 20 carbon atoms, and a substitution having 1 to 20 carbon atoms
- a silyl group or a substituted amino group having 120 carbon atoms, and the plurality of R 5 may be the same or different from each other;
- M 2 of M 1 and of general formula (1) (3) represents a Group 4 transition metal atom of the periodic table of elements, for example, generally titanium atom, zirconium atom, hafnium atom
- X 1 R 1 in the formula ( 1 ) and X 2 R3 R4 in the general formula (3) are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 120 carbon atoms, An optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms or a substituted amino group having 1 to 20 carbon atoms, and a plurality of X 1 are the same as each other
- the plurality of R 1 may be the same as or different from each other
- the plurality of X 2 may be the same or different from each other
- the plurality of R 3 are the same as each other or different even multiple of R 4 is a same as each other It may be a different summer.
- Examples of the halogen atom of X 1 RX 2 R 3 and R 4 include a fluorine atom, a chlorine atom, a fluorine atom, and an iodine atom.
- X 1 R 1 , X 2 R 3 and R 4 may have a substituted 1-20 carbon atom-containing carbyl group including an alkyl group having 1 to 20 carbon atoms and a halogen having 1 to 20 carbon atoms.
- alkyl group having 120 carbon atoms examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group , Isopentyl group, n xyl group, n butyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group Group, n-pentadecyl group, nxadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-ei
- halogenated alkyl group having 1 to 20 carbon atoms include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromo Methyl group, odomethyl group, jodomethyl group, triodomethyl group, fluorethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethinole group, dichloroethyl group, trichloroethino Rhe group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group
- Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylenophenyl) methyl group, and (2,3-dimethylphenyl).
- a halogenated aralkyl group in which these aralkyl groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or a silicon atom.
- aryl groups having 6 to 20 carbon atoms include phenyl, 2-tolyl, 3-tolyl, 4_tolyl, 2,3-xylyl, 2,4-xylyl, 2,5 —Xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2, 3, 6_trimethylphenyl group, 2, 4, 6-trimethylenophenol group, 3, 4, 5_trimethylphenyl group, 2, 3, 4, 5-tetramethylphenyl group, 2, 3, 4, 6-tetramethylphenyl group, 2, 3, 5, 6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, jetylphenyl group, triethylphenyl group, n-propylphenyl group Enyl group, isopropylphenyl group, n-butylphenyl group, sec
- examples of the hydrocarbyl group having 1 to 20 carbon atoms which may be substituted include a hydrocarbinole group substituted with a substituted silyl group, a hydropower norevir group substituted with a substituted amino group,
- examples of the hydrocarbyl group substituted with a substituted silyl group include a trimethylsilylmethyl group, a trimethylsilylethyl group, a trimethylsilylpropyl group, and a trimethylsilylbutyl group.
- trimethylsilyl phenyl group bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, triphenylsulfonyl Examples include methyl groups.
- hydrocarbyl group substituted with a substituted amino group examples include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a dimethylaminobutyl group, a dimethylaminophenyl group, and a bis (dimethylamino) methyl group.
- Hydrocarbyl groups substituted with a hydrocarbyloxy group include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, sec-butoxymethyl group, tert —Butoxymethyl group, phenoxymethyl group, methoxetyl group, ethoxyethyl group, n-propoxychetyl group, isopoxypoxyl group, n-butoxychetinore group, sec-butoxychetyl group, tert-butoxysyl group, phenoxychetyl group, methoxy 1 n-propyl group, ethoxy _ n-propyl pill group, n-propoxyl n-propyl group, isopropoxyn n-propyl group, n_butoxyl n-propyl group, sec-butoxy-n-propyl group, tert —Butoxy —n-propyl,
- X 1 , RX 2 , R 3 and R 4 may have a substituted 1 to 20 carbon atom-containing carbyloxy group, an alkoxy group having 1 to 20 carbon atoms, a carbon atom number 7 to Examples include a 20 aralkyloxy group and an aryloxy group having 6 to 20 carbon atoms.
- halogenated alkoxy group in which these alkoxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2, 3— (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3, 4_Dimethinophenyl) methoxy group, (3,5-Dimethylphenyl) methoxy group, (2, 3, 4-trimethylphenyl) methoxy group, (2, 3, 5-trimethylphenyl) meth Toxyl group, (2, 3, 6-trimethylphenyl) methoxy group, (2, 4, 5-trimethylphenyl) methoxy group, (2, 4, 6-trimethylphenyl) methoxy group, (3 , 4, 5-Trimethylphenol) Xy group, (2,
- these aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom. And a halogenated aralkyloxy group substituted with a child.
- Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4_methylphenoxy group, 2,3_dimethylphenoxy group, 2,4-dimethylphenoxy group.
- a halogenated aryloxy group in which these aryloxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- disubstituted silyl groups trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropyl-silyl, tri-n-butylsilyl, tri-sec —Butylsilyl group, tri-tert-butylsilyl group, Riisobuchirushiri Le group, tert- butyl one dimethylsilylene Honoré group, tri one n- butylsilyl group, tree n Examples thereof include tri-substituted silyl groups such as monohexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group.
- Examples of the substituted amino group having 1 to 20 carbon atoms of X 1 , RX 2 , R 3, and R 4 include an amino group substituted with two carbyl groups such as an alkyl group and an aryl group. I can raise it. Specifically, for example, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group, isobutylamino group, n-hexylamino group, n —Octinoreamino group, n-decinoreamino group, phenylamino group, benzylamino group, dimethylamino group, jetylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di- —
- R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom.
- X 2 is preferably a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, Trif / Rheolomethoxy group, phenyl group, phenoxy group, 2, 6— Tert-butylphenoxy group, 3,4,5_trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxy group, benzyl group.
- R 3 a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and more preferred details, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom.
- R 4 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom.
- Q i in the general formula (1) represents a cross-linking group represented by the general formula ( 2 ), and Q 2 in the general formula (3) represents a cross-linking group represented by the general formula (4).
- M in the general formula (2) and n in the general formula (4) are integers of 1 to 5.
- m is preferably 1 to 2
- n is preferably 1 to 2.
- J 2 of J 1 and of the general formula (2) (4) represents the first transition metal atom of Group 4 of the periodic table of elements, carbon atoms, Kei atom, such as a germanium atom. Preferably, it is a carbon atom or a key atom.
- R 2 in the general formula (2) and R 5 in the general formula (4) are each independently a hydrogen atom, a halogen atom, an optionally substituted hydride carbyl group having 1 to 20 carbon atoms, carbon An optionally substituted hydrocarbyloxy group having 1 to 20 atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R 2 May be the same or different from each other, and a plurality of R 5 may be the same or different from each other.
- Q 1 and Q 2 include methylene, ethylidene, ethylene, propylidene, propylene, butylidene, butylene, pentylidene, pentylene, hexylidene, isopropylidene, methylethylmethylene, Methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) .methylene group, bis (dimethyl) Phenyl) methylene group, bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (jetinorephenyl) methylene group, phenyl (propinorephenyl) methylene group.
- Q 1 is preferably a methylene group, an ethylene group, an isopropylidene group, a bis (cyclohexyl) methylene group, a diphenylmethylene group, a dimethylsilanezyl group, or a bis (dimethylmethyl) diyl group, and more preferably Ethylene group, dimethylsilane diyl group.
- Q 2 is preferably a methylene group, an ethylene group, an isopropylidene group, a bis (cyclohexyl) methylene group, a diphenylmethylene group, a dimethylsilanediyl group, or a bis (dimethylsilane) diyl group, and more preferably. Is a diphenylmethylene group.
- the 2-position, 3_-position, 4_-position, 5-position, 6-position and 7 Includes substitutions at the _ position and includes all combinations in the same way, even if the bridge position is other than the 1-position.
- di- or higher-substituted products include all combinations of substituents and crosslinking positions.
- X 1 in Jikurori de the Ziv Ruorai de of the transition metal compound Jiburomai de, Jiaiodai de, dimethyl, Jechiru, diisopropyl, dimethyl Tokishido, Jetokishido, Jipuropokishido, Jibutokishido, bis (Torifuruorome Tokishido), diphenyl, Jifuenokishido, bis ( 2,6-di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide) ), And a compound changed to dibenzyl or the like.
- the zirconium M 1 of the transition metal compound may be exemplified compound was changed to titanium or Hafuniumu.
- the transition metal compound (A 1) represented by the general formula (1) is preferably ethylenebis (indenyl) zirconium diphenoxide, ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indul) zirconium dichloride.
- M 2 is a zirconium atom
- X 2 is a chlorine atom
- the bridging group Q 2 is a diphenylmethylene group.
- Diphenylenomethylene (2 _ethyl 1-cyclopentaenyl) (2,7-Dimethylolene 9-Fonoleleninole) Direconium dichloride, Diphenol / ⁇ Remethylene (3-Ethanolol 1-Cyclopentaenyl ) (2,7-Dimethyl-9_fluorenyl) Zirconium Dichloride, Diphenylmethylene (2,4-Detyl_1-cyclopentagel) (2,7-Dimethyl-9_Fluorenyl) Zirconium Dichloride , Diphenylmethylene (2,5-Detyl _ 1-Cyclopentaenyl) (2,7-Dimethyl-9-Fluorenyl) Zinoleconium Dichloride, Diphenyldimethylene (3,4-Jetyl-1-cyclopentaenyl) (2,7-Dimethyl-1-9-Fluorenyl) Zirconium Dichloride, Di
- Diphenylenomethylene (2-Ethyl _ 1-Cyclopentaenyl) (2,7-Jetylu 9-Funoreoleni ⁇ ⁇ Ginoleconium dichloride, Diphninoremethylene (3-Ethinore 1-Cyclopentadienyl) ( 2,7-Jetyl 9-Fluorenyl) Zirconium Dichloride, Diphenylmethylene (2,4-Ethinole_1-Cyclopentaenyl) (2,7-Jetyl 9-Fluorenyl) Zirconium Dichloride, Diphenyl Methylene (2,5_Jetinole-1-cyclopentageninole) (2,7-Getenore-1-9-Fluoreninole) Zirconium dichloride, Diphenylmethylene (3,4-Jetyl_1-cyclopentagenyl) (2, 7-Jetinore 9-Fluoreny
- Diphenylemethylene (2-n-propyl-1- 1-cyclopentadenyl (2,7-di-tert-butyl-9-1-fluorenyl) Zirconium dichloride, diphenylmethylene (3-n-propynole-1-cyclopentageni (2, 7-di-tert-butynol 9-fluorenyl) Zirconium dichloride, diphenylmethylene (2, 4-di-n-propyl 1-cyclopentadienyl) (2, 7-di-l) t-Butyl 9-Fluorenyl) Zirconium Dichloride, Diphenylmethylene (2,5-Diol n-propyl _ 1-Cyclopentadienyl) (2,7-Di t _Butyl _ 9 _Fluorenyl) Zirconium Dichloride Diphenylmethylene (3,4-di-n-propyl _ 1-cycl
- the Jikurori de of X 2 in the transition metal compound Jifuruorai de, dibromide, Giay Odai de, dimethyl, Jechiru, diisopropyl, dimethyl Tokishido, Jetokishido, Jipu Ropokishido, Jibutokishido, bis (Torifuruorome Tokishido), diphenyl, Jifueno Kishido, bis (2,6-di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6— Examples thereof include tetrafluoro-4-pentafluorophenyl phenoxide), dibenzyl and the like.
- the diphenylmethylene group of Q 2 of the above transition metal compound is changed to methylene group, ethylene group, isopropylidene group, methylphenylmethylene group, dimethylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl.
- Examples thereof include compounds that have been changed to a ru group, a silacyclohexane diyl group, or the like.
- compounds in which the transition metal compound M 2 zirconium is changed to titanium or hafnium can also be exemplified.
- the co-catalyst component ( ⁇ ) used for the preparation of the polymerization catalyst used in the production of the ethylene- ⁇ -olefin copolymer of the present invention includes the following component (b 1), the following component (b 2), Examples thereof include a solid catalyst component formed by contacting the following component (b 3) and the following component (b 4).
- M 3 is a lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom, A lead atom, an antimony atom, or a bismuth atom is represented, and X represents a number corresponding to the valence of M 3 .
- L represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group, and when a plurality of L are present, they may be the same or different from each other.
- Ti represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and t represents a number corresponding to the valence of Ti.
- R 6 represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom or a group having an electron-withdrawing group, and when a plurality of R 6 are present, they may be the same as or different from each other.
- T 2 represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and s represents a number corresponding to the valence of T 2 .
- R 7 is a halogen atom, a hydrocarbyl group or a halogenated high Represents a drocarbyl group.
- M 3 in the general formula (5) is lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom , Lead atom, antimony atom or bismuth atom.
- Preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, more preferred is a magnesium atom, sub-atom, tin atom or bismuth atom, and still more preferred. Is a zinc atom.
- X in the general formula (5) represents a number corresponding to the valence of M 3 .
- M 3 is a zinc atom
- X is 2.
- L in the general formula (5) represents a hydrogen atom, a halogen atom or an optionally substituted hydryl carbyl group, and when a plurality of L are present, they may be the same as or different from each other.
- halogen atom for L examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the optionally substituted hydryl carbyl group of L includes an alkyl group, an aralkyl group, an aryl group, a halogenated alkyl group and the like.
- an alkyl group having 1 to 20 carbon atoms is preferable.
- the halogenated alkyl group for L is a halogenated alkyl group having 1 to 20 carbon atoms.
- Monofluoroeicosyl group perchloropropyl group, norchlorobutyl group, monochloropentinole group, peripheraloxyhexenole group, perchlorooctinole group, no 0- chlorododecyl group, perchloropentadecyl Group, perchloroeicosyl group, perbromopropynole group, no.
- an aralkyl group having 7 to 20 carbon atoms is preferable.
- it is a benzyl group.
- examples thereof include a halogenated aralkyl group having 7 to 20 carbon atoms in which these aralkyl groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- the aryl group of L is preferably an aryl group having 6 to 20 carbon atoms.
- L is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably an alkyl group.
- T 1 in the general formula (6) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, more preferably an oxygen atom.
- t represents the valence of Ti.
- T 1 is an oxygen atom or a sulfur atom
- t is 2.
- Ti is a nitrogen atom or a phosphorus atom
- t is 3.
- R 6 in the general formula (6) represents a halogen atom, an electron withdrawing group, a group containing a halogen atom, or a group having an electron withdrawing group, and represents a group containing an electron withdrawing group or an electron withdrawing group.
- R 6 When a plurality of R 6 are present, they may be the same or different.
- Hammett's rule substituent constant ⁇ and the like are known, and a functional group having Hammett's rule substituent constant ⁇ being positive can be cited as an electron withdrawing group.
- halogen atom of R 6 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the electron withdrawing group for R 6 include a cyano group, a nitro group, a carbonyl group, a hydrocarbyloxycarbonyl group, a sulfone group, and a phenyl group.
- Examples of the group containing a halogen atom of R 6 include halogenated hydrocarbyl groups such as halogenated alkyl groups, halogenated aralkyl groups, halogenated aryl groups, and (halogenated alkyl) aryl groups; A group: a hydrogenated hydropower rubyroxycarbonyl group and the like.
- Examples of the group having an electron-withdrawing group for R 6 include cyanated hydrocarbyl groups such as cyanated aryl groups and nitrated hydrocarbyl groups such as nitrated aryl groups.
- halogenated alkyl group of R 6 examples include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a odomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a jodomethyl group, a trifluoromethyl group, a trichloromethyl group, a trichloromethyl group, Bromomethyl group, triodomethyl group, 2, 2, 2_trifnoreo octyl group, 2, 2, 2-trichloro octyl group, 2, 2, 2-tribromoethyl group, 2, 2, 2-triiodoethyl group, 2 , 2, 3, 3, 3-pentafluoropropyl group, 2, 2, 3, 3, 3_pentachloropropyl group, 2, 2, 3, 3, 3-pentabromopropyl group, 2, 2, 3, 3, 3-pentapropylpropyl group, 2, 2, 2-trifluoro-1
- halogenated aryl group of R6 examples include 2-fluorophenyl group, 3-fluorophenyl group, 4-funoleolophenylenole group, 2,4-difunoleolopheninole group, 2,6-difluoride Phenyl group, 3, 4-difluorophenyl group, 3, 5-difluorophenyl group, 2, 4, 6-trifluorophenylol group, 3, 4, 5-trifluorophenyl group, 2, 3, 5, 6- Tetrafluorophenyl group, pentafluorophenyl group, 2, 3, 5, 6-tetrafluoro mouthpiece 4-trifluoromethylphenyl group, 2, 3, 5, 6-tetrafluoro-4-pentafluorophenyl phenyl Group, perfluoro- 1 _ naphthyl group, perfluo 2-naphthinole group, 2 _ black-mouth pheinole group, 3 _ black-mouth phe
- R 6 (halogenated alkyl) aryl group includes 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4 (trifluoromethyl) phenyl group, 2, 6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoro) (Romethyl) phenyl group and the like.
- Examples of the cyanated aryl group of R 6 include 2_cyanophenyl group, 3-cyanophenyl group, 4_cyanophenyl group and the like.
- Examples of the nitrated aryl group of R 6 include 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.
- halogenated hydrocarbyloxycarbonyl group of R 6 examples include a halogenated alkoxycarbonyl group, a halogenated aralkyloxycarbonyl group, a halogenated aralkyloxycarbonyl group, and more specifically, trifluoromethoxy. Examples thereof include a carbonyl group and a pentafluorophenoxycarbonyl group.
- R 6 is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl group or a halogenated aryl group, and still more preferably a fluorinated alkyl group, a fluorinated aryl group, or a chlorinated alkyl group.
- Group or a chlorinated aryl group particularly preferably a fluorinated alkyl group or a fluorinated aryl group.
- fluorinated alkyl group a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2, 2, 2-trifluoroethyl group, 2, 2, 3, 3, 3, 3-pentafluoropropyl group, 2, 2,2-trifluoro-1- 1-trifluoromethylethyl group or 1,1-bis (trifluoromethyl) -1,2,2-trifluoroethyl group, more preferably trifanol Oromethyl group, 2,2,2-trifluoro-1-hydroxymethyl It is a thiol group or 1,1,1bis (trifluoromethyl) -1,2,2,2-trifluoroethyl group.
- the fluorinated aryl group is 2_fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difunoleolopheninole group, 3, 4 —Difunoleolophenoleol group, 3,5-Diph / Leo mouth phenol group, 2, 4,6-trifluorophenyl group, 3, 4,5-trifluorophenyl group, 2, 3, 5, 6 —Tetrafluorophenyl group, pentafluorophenyl group, 2, 3, 5, 6-tetrafluoro-4-trifluoromethylphenyl group, 2, 3, 5, 6-tetrafluoro4 one pentafluorophenylphenyl group A perfluoro-1-naphthyl group or a perfluoro-2-naphthyl group, more preferably a 3,5-difluorophenol group, a
- T 2 in the general formula (7) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, more preferably an oxygen atom.
- the s of the general formula (7) represents a valence of T 2, if T 2 is an oxygen atom or a sulfur atom, s is 2, if T 2 is a nitrogen atom or a phosphorus atom, s is 3 .
- the general formula (7) represents a hydrocarbyl group or a halogenated hydrocarbyl group.
- the carbyl group of R 7 include an alkyl group, an aralkyl group, and an aryl group, and examples of the alkyl group, aralkyl group, and aryl group of L can be given.
- halogenated Hyde port carbyl group R 7 Nono halogenated alkyl group, halogenated Ararukiru group, halogenated Ariru group, halogenated high Dorokarubiru groups such as (alkyl halide) Ari Le group and the like, R 6 Examples of groups exemplified as alkyl halide groups, halogenated aryl groups, (halogenated alkyl) aryl groups Can be shown.
- R 7 is preferably a halogenated hydrocarbyl group, and more preferably a fluorinated hydrocarbyl group.
- the compound represented by the general formula (5) of the component (bl) is a compound in which M 3 is a zinc atom, such as dimethyl zinc, jetyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl.
- the compound represented by the general formula (5) of the component (bl) is preferably dialkyl zinc, and more preferably dimethyl zinc, jetyl zinc, di-n-propyl zinc, di-propyl zinc, di-n-butyl.
- Examples of the compound represented by the general formula (6) of the component (b 2) include ammine, phosphine, alcohole, 'thiol, phenol, thiof; X nore, naphthonore, naphthinoretinol, and powerful rubonic acid compounds. .
- Amines include di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifnoreolomethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3, 3-Pentafluoropropyl) amine, bis (2,2,2,2-trifluoro-1_trifluoromethylethyl) amine, bis (1,1-monobis (trifluoromethyl) -2,2,2,2-trifluoro Oloethyl), bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) Amines, Bis (2,6-difluorophenyl) Amines, Bis (3,5-difluorophenyl) Amines, Bis (2,4,6-trifluorophenyl) Amines, Bis (3,4,5-Trifluoronorolo Phenylamine, bis (pentafluororenopheny
- phosphine examples include compounds in which the nitrogen atom of the amine is changed to a phosphorus atom.
- Those phosphines are compounds represented by replacing the amine in the amine with phosphine.
- Alcohols include methanolic methanol, difluoromethanol, trifluoroethanol, 2, 2, 2_trifluoroethane, 2, 2, 3, 3, 3-pentaphenolic propanol, 2, 2, 2-trifluoro- 1_trifluoromethylethanol, 1,1 bis (trifluoromethinole) -2,2,2-trifluoroethanol, 1 ⁇ , 1 ⁇ -perfluorobutanol, 1H, 1 ⁇ -par Fluoropentanol, 1 ⁇ , 1 ⁇ - Perfluoro oral hexanol, 1H, 1 ⁇ —Perfluorooctanol, 1H, 1H—Perfluoro dodecanol, 1 ⁇ , 1 ⁇ —Perfluoropentadecanol 1H, 1H— Perfluoroeicosanol and the like.
- thiol examples include compounds in which the oxygen atom of the alcohol is changed to a sulfur atom.
- Those thiols are compounds represented by replacing thiols in the alcohols with thiols.
- phenol examples include 2-fluorophenol, 3-fluorophenol, 4-phenol, orophenol, 2,4-difluorophenol, 2,6-diphenolophenol, 3,4-difluorophenol 3, 5-difluorophenol, 2, 4, 6-trifluorophenol, 3, 4, 5-trifluorophenol, 2, 3, 5, 6-tetraphenol, phenol, pentafunoleol, 2, 3, Examples include 5, 6-tetrafluoro oleo 4-trifluoromethyl phenol, 2, 3, 5, 6-tetrafluoro-4 _ pentafluoro pheno phenol.
- phenols in which the fluorine mouth of these phenols is changed to black mouth, bromo or iodine can be mentioned.
- thiophenol examples include compounds in which the oxygen atom of the phenol is changed to a sulfur atom.
- Those thiophenols are compounds represented by replacing phenol in the above phenol with thiophenol.
- Naphthol includes perfluoro-1-naphthol, perfluoro-2-naphtho nore, 4, 5, 6, 7, 8—pentaph / leo mouth 2_naphtho nore, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) Phenols, 4- (Trifluoromethyl) Phenols, 2, 6-bis (Trifluoromethyl) Phenols, 3, 5_bis (Trifluoromethyl) Phenols, 2, 4, 6-Tris (Trifluoronorolomethinore) Examples include phenol, 2-cyanophenol, 3_cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like.
- naphthol in which the fluor of these naphthols is changed to black, bromo or odoid can be mentioned.
- naphthylthiol examples include compounds in which the oxygen atom of the naphthol is changed to a sulfur atom.
- Those naphthols are compounds represented by replacing naphthol in the naphthol with naphthylthiol.
- carboxylic acid compound examples include pentafluoric benzoic acid, perfluoroethanotic acid, and perfluoropropanoic acid. Tanoic Acid, Perfluoropentanoic Acid, Perfluoro Hexanoic Acid, Perfluoroheptanoic Acid, Perfluorooctanoic Acid, Perfluorononanoic Acid, Perfect For example, it is possible to use a wide variety of decanoic acid, perfluorodedecanoic acid, and perfluorodedecanoic acid.
- the compound represented by the general formula (6) of the component (b 2) is preferably an amine, an alcohol or a phenol compound, and as the amine, bis (trifluoromethyl) amine, bis (2, 2, 2— Trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,2-trifnoreo 1-trifluoromethylethyl) amine, Bis (1,1 bis (trifnoleolomethyl) -2,2,2-trifluoroethyl) amine or bis (pentafluorophenyl) amine, and the alcohol is preferably trifluoromethanol, 2, 2, 2—Trifnoreo Oral ethanol, 2, 2, 3, 3, 3—Pentafluoropropanol, 2, 2, 2—Trifluoro 1—Trifluoromethylethanol or 1,1_bis (G Fluoromethyl) 1,2,2,2-trifluoroethanol, and preferably phenol, 2-fluorophenol,
- Examples of the compound represented by the general formula (7) of the component (b 3) include water, hydrogen sulfide, an amine, an a phosphorus compound, and the like.
- Amamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butynoleamine, tert-butylamine, isobutyramine, n-pentylamine, neopentynoleamine, isopentylamine, n-hexylamine, n —Octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, and other alkylamines; benzylamine, (2-methinophenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine, (2, 3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl
- Amines include fluoromethylamine, difluoromethylamine, trifluoromethylamine, 2, 2, 2-trifluoroethylamine, 2, 2, 3, 3, 3-pentafluoro.
- Ropropylamine 2, 2, 2—trifluoro- 1-trifluoromethylethylamine, 1,1-bis (trifluoromethyl) -2, 2, 2_trifluoroethylamine, norfluro 0- Fluorobutylamine, perfluorobutylamine, perfluoropentylamine, norfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeico And halogenated alkylamines such as sylamine.
- amines obtained by changing the fluoro of these amines to black, bromo or iodide can be mentioned.
- the aniline compounds include aniline, naphthylamine, anthracenylamine, 2_methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2, 6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,3,4-trimethinoaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2, 4, 6-trimethylaniline, 3, 4, 5— trimethylaniline, 2, 3, 4, 5—tetramethylaniline, 2, 3, 4, 6—tetramethylaniline, 2, 3, 5, 6 —Tetramethylaniline, Pentamethylaniline, 2-Ethylaniline, 3-Ethylaniline, 4-Ethylaniline, 2,3-Ethylaniline, 2,4_Jetylaniline, 2,5-Di Ethylaniline, 2, 6_Jetylanilin, 3,4_Jetylan
- the ethyl of these aniline compounds is Nore, isopropyl, n-butinole, sec-butinole, tert-butyre, n-pentinole, neopentinole, n-hexynole, n-octinore, n-decinole, n-doorsinole, n-tetradecyl, etc. can give.
- aniline compounds include 2-fluoroaroline, 3-fluoroaniline, 4 monofluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2, 4, 6-trifluoroaniline. 3, 4, 5—trifluoroaniline, pentafunoleroaniline, 2— (trifluoromethyl) aniline, 3— (trifluoromethyl) aniline, 4 (trifluoromethyl) aniline, 2, 6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2, 4, 6-tri (methyl trifnoreo) aniline, 3, 4, 5—tri (trifluoro) (Romethyl) aniline.
- an aniline compound in which the fluoro of these aniline compounds is changed to black mouth, bromo, iodide or the like can be mentioned.
- the compound represented by the general formula (7) of the component (b 3) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine.
- a solvent for preparing the polymerization catalyst or a solid substance insoluble in the polymerization solvent is preferably used, a porous substance is more preferably used, an inorganic substance or Organic polymers are more preferably used, and inorganic substances are particularly preferably used.
- the particulate carrier of component (b 4) is preferably of a uniform particle size, and the volume-based geometric standard deviation of the particle size of the particulate carrier of component (b 4) is preferably 2.5 or less More preferably, it is 2.0 or less, more preferably 1.7 or less.
- Examples of the inorganic substance of the particulate carrier of component (b 4) include inorganic oxides, clays, and clay minerals. You can also use a mixture of these.
- Inorganic oxides include S i 0 2 , A ⁇ 2 ⁇ 3 , MgO, ⁇ r 0 2 , ⁇ i 0 2 , ⁇ 2 0 3 , C aO, ⁇ , B a O, h h ⁇ 2 , S i 0 2 — MgO, S i O2-A 1 2 0 3 S i O2 ⁇ T i 0 2 , S i O2— V 2 0 5 , S i O2-C r 2 0 3 S i O2— T i O2— MgO, and A mixture of two or more of these can be mentioned.
- Triaryl / silane such as chlorochlorosilane; Triarylchlorosilane such as triphenylchlorosilane; Dialkyldichlorosilane such as dimethyldichlorosilane; Diaryldichlorosilane such as diphenyldichlorosilane; Anolequinoletri such as methyltrichlorosilane Chlorosilanes; arylenotrichlorosilanes such as phenyltrichlorosilane; trialkylalkoxysilanes such as trimethylmethoxysilane; triarylalkoxysilanes such as triphenylmethoxysilane; dialkyl dialkoxysilanes such as dimethyldimethoxysilane; diphenyldimethoxysilane Diallyalkoxysilanes; alkyltrialkoxysilanes such as methyltrimethoxysilane; aryls such as pheny
- inorganic alkyl oxides such as dialkylamines such as jetylamine and diphenylamine, alcoholenols such as methanol and ethanol, and phenols can be exemplified.
- inorganic oxides may have increased strength due to hydrogen bonding between hydroxyl groups.
- the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate.
- the method for changing the substitution rate of the surface hydroxyl group is not particularly limited. Examples of the method include a method of changing the amount of the compound used for contact. Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, alofen, hysingerite, bairofilaite.
- Tanorek Unmo group, Smectite, Monmoronite group, Hectrite, Labonite, Sabonite, Bamiquilite, Lyotada stone group, Palygorskite, Kaolinite, Nakrit, Datekite, Halloisa You can give it.
- An inorganic oxide is preferably used as the inorganic substance.
- the inorganic substance is preferably dried and substantially free of water, and preferably dried by heat treatment.
- the heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 ° C. for inorganic substances whose moisture cannot be visually confirmed. Performed at ⁇ 800 ° C.
- the heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
- Examples of the heat drying method include a method in which an inert gas dried during heating (for example, nitrogen or argon) is circulated and dried at a constant flow rate, a method in which heat is reduced under reduced pressure, and the like.
- the average particle size of the inorganic substance is usually 1 to 500,000 ⁇ m, preferably 5 to 100 00 ⁇ , more preferably 10 to 50 O / zm, more preferably Is from 10 to 100 ⁇ m.
- the pore volume is preferably 0.1 ml Zg or more, more preferably 0.3 to: 1 O m 1 / g.
- the specific surface area is preferably 10 to: 10 00 m 2 Z g, more preferably 10 00 to 500 m 2 / g.
- the organic polymer of the particulate carrier of component (b 4) is preferably a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group.
- Examples of functional groups having active hydrogen include primary amino groups, secondary amino groups, imino groups, amide groups, hydrazide groups, amidino groups, hydroxy groups, hydroperoxy groups, carboxyl groups, formyl groups, force Examples include rubamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group and carbazolyl group.
- These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
- a non-proton-donating Lewis basic functional group is a Lewis base moiety that does not have an active hydrogen atom.
- heterocyclic group Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring.
- Particularly preferred are a pyridyl group, an N_substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group.
- These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
- the content of the functional group having active hydrogen or the non-proton donating Lewis basic functional group is preferably 0.0 as the molar amount of the functional group per gram of polymer unit constituting the organic polymer. 1 to 5 O mm o 1 / g, more preferably 0.1 to 20 mm o 1 g.
- Examples of the method for producing a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group include, for example, a functional group having active hydrogen or a non-proton-donating Lewis basic functional group. And a monomer having one or more polymerizable unsaturated groups, and a method of copolymerizing the monomer with another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.
- Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group; alkynyl groups such as ethyne group and the like.
- Monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amine compounds, vinyl group-containing hydroxyls. Compound etc. can be mentioned.
- the monomer examples include N- (1-etulyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) one N-methylamine, N- (2-propenyl) one N-methylamine, 1-ethenyl amide, 2-propenyl amide, N-methyl mono (1-ethul) amide, N-methyl- (2— Propenyl) amide, bier alcohol, 2-propene 1-ol, 3-butene-1 monool.
- Monomers having a functional group having a Lewis base that does not have an active hydrogen atom and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole, and the like. I can give you.
- Examples of the other monomer having a polymerizable unsaturated group include ethylene, ⁇ -olefin, an aromatic vinyl compound, and cyclic olefin. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, nonolebornene, and dicyclopentagen. Two or more of these monomers may be used. Of these, ethylene and styrene are preferable. Further, examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include dibutenebenzene.
- the average particle size of the organic polymer is usually 1 to 5000 ⁇ m, preferably 5 to 1000 ⁇ , and more preferably 10 to 500 / zm.
- the pore volume is preferably 0.3 lm lZg or more, and more preferably 0.3 to 10 m 1.
- the specific surface area is preferably 10 to 1000 m 2 / g, more preferably 50 to 50 Om 2 g.
- the organic polymer is preferably dried and substantially free of moisture, and is preferably dried by heat treatment.
- the temperature of the heat treatment is usually 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed.
- the heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
- Examples of the heat drying method include a method in which a dry inert gas (for example, nitrogen or argon) is circulated at a constant flow rate during drying, a method in which heat drying is performed
- the promoter component (B) is formed by bringing the component (b.l), the component (b 2), the component (b 3) and the component (b4) into contact with each other.
- the contact order of component (b 1), component (b 2), component (b 3) and component (b4)) is as follows.
- Component (bl) and component (b 2) are contacted, the contact product resulting from the contact is contacted with component (b 3), and the contact product resulting from the contact is contacted with component (b 4).
- component (bl) and the component (b 2) are contacted, the contact product resulting from the contact and the component (b4) are contacted, and the contact product resulting from the contact and the component (b 3) are contacted.
- Component (b 2) is contacted with component (b4), the contact product resulting from the contact is contacted with component (b 1), and the contact product resulting from the contact is contacted with component (b 3). .
- the solvent can be used in other stages. In other words, the solvents at each stage are the same or different from each other.
- the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, two Tolyl solvents, nitro compounds, amine solvents
- polar solvents such as sulfur compounds.
- Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylenopentane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene Dichloromethane, difunoleolomethane, chlorohonolem, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,1,2,2-trifluoroethane, tetrachloroethylene, chloro Logenated solvents such as oral benzene, bromobenzene, o-dichlorobenzene; dimethyl ether, jetyl ether, diisopropyl ether, di-n-butyl etherol, methyl mono-tert-butyl monoether, anisole, 1,
- Phenol solvents such as phenol and p-cresol; acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pi Carbonyl solvents such as redone; Phosphoric acid derivatives such as hexamethyl phosphate triamide, triethyl phosphate, etc .; Nitrile solvents such as acetonitrile, propionitryl, succinonitrinole, benzonitrile; Two-necked compounds such as nitromethane and nitrobenzene Aminic solvents such as pyridine, piperidine, morpholine; dimethylsulfo Sulfur compounds such as xoxide and sulfolane can be mentioned.
- the solvent (si) for producing the contact product (c) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.
- a polar solvent is preferable as the solvent (s 2) when the contact product (c) and the component (b 4) are contacted.
- E T N value C. R eichardt, S olventsand S olvents E ffectsin O rganic Ch em istry ", 2 nde d., VCH V er 1 ag (19 88).)
- solvent satisfying 0. 8 ⁇ ⁇ ⁇ 0. 1 scope particularly good preferable.
- Such polar solvents include, for example, dichloromethane, dichlorodifluoromethane tank rohonorem, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro mouth 1,2,2-trifunoleoroethane.
- the solvent (s 2) is preferably dimethyl ether, jetyl ether, diisopropinoleethenole, di-n-butinoleether, methylol-tert-butinoleether, nitrosyl, 1,4-dioxane, 1, 2-Dimethoxetane, Bis (2-Methoxychetinore) Aete ⁇ Tetrahydrofuran, Tetrahydropyran, Methanol, Ethanol; ⁇ , 1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, 2-Methyl-1 Propanole, 3-methinole 1-butanol, cyclohexanol, benzylazulecoleol, ethylene glycolate, propylene glycolone, 2-methoxyethanol, 2 ethoxyethanol, diethylene glycol, triethylene glycol, particularly preferred Is 1 n-butyl ether, methyl 1 tert-butinoleether
- the solvent (s 2) a mixed solvent of these polar solvents and hydrocarbon solvents can be used.
- hydrocarbon solvent compounds exemplified as the aliphatic hydrocarbon solvent and the aromatic hydrocarbon solvent are used.
- the mixed solvent of polar solvent and hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane 2-propanol mixed solvent, heptane / methanol.
- hexane methanol mixed solvent hexane // ethanol mixed solvent, heptane methanol mixed solvent, heptane ethanol mixed solvent, toluene // methanol mixed solvent, toluene / ethanol mixed solvent, xylene methanol mixed solvent, xylene / Ethanol mixed solvent.
- hexane methanol mixed solvent, hexane ethanol mixed solvent, toluene methanol mixed solvent, toluene / ethane It is a mixed solvent.
- Most preferred is a toluene / ethanol mixed solvent.
- the preferable range of the ethanol fraction from 10 to 50 vol%, even more preferably 15-30 vol 0/0.
- component (b4) When contact (c) formed by contacting component (b 1), component (b 2) and component (b 3) is contacted with component (b4), that is, In the methods 3> and ⁇ 7>, a hydrocarbon solvent can be used as the solvent (si) and the solvent (s 2).
- a hydrocarbon solvent can be used as the solvent (si) and the solvent (s 2).
- the shorter time from contact of the obtained contact product (c) to component (b 4) is shorter Is preferred.
- the time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour.
- the temperature at which the contact (c) and the component (b4) are contacted is usually from 100 ° C to 40 ° C, preferably from 20 ° C to 20 ° C, and most preferably from 1 to 1 ° C. O: ⁇ 10 ° C.
- both the above nonpolar solvents and polar solvents must be used. Can do.
- it is a nonpolar solvent. This is because the contact between component (b 1) and component (b 3), or the contact between component (b 1) and component (b 2) and component (b 3) is In general, since the solubility in non-polar solvents is low, if the component (b 4) is present in the reaction system when these contact products are formed, the contact product precipitates on the surface of the component (b 4) This is because it is considered to be fixed more easily.
- Component (bl) Use amount
- the amount of component (b2) and component (b3) used per mole is preferably the following relational expression (V).
- M3 valence—molar amount of component (b 2) 2 molar amount of component X (b 3) I ⁇ 1 (V) and component (bl) used per component of component (b 2)
- the amount used is preferably from 0.01 to 1.99 mol, more preferably from 0.1 to 1.8 mol, still more preferably from 0.2 to 1.5 mol, and most preferably 0. 3 to 1 mole.
- Component (bl) used amount Preferred amount of component (b 3) used per mole, more preferred amount, more preferred amount, and most preferred amount are the valence of M 3 and the above component (b 1 ) Consumption per 1 mol of component (b 2) and the above formula (I)
- the amount used is preferably from 0.01 to 1.99 mol, more preferably from 0.1 to 1.8 mol, still more preferably from 0.2 to 1.5 mol, and most preferably 0. 3 to 1 mole.
- component (b 1) and component (b 2) used depends on the component (b
- the amount of metal atoms derived from 1) is preferably such that the number of moles of metal atoms contained in 1 g of promoter component (B) is not less than 0.1 lmmo, more preferably 0.5-20 mmo. The amount is 1.
- a heating step at a higher temperature may be added after the contact as described above.
- the heating step it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature.
- the solvent used in the contact may be replaced with another solvent having a higher boiling point.
- the total amount of the transition metal compound (A1) and the transition metal compound (A2) is usually 1 to 10000 mo 1 Zg, preferably 10 to: L 00 0 ⁇ 1 per lg of the promoter component (B). Zg, more preferably 20 to 500 / mo 1 Zg.
- the organoaluminum compound (C) may be contacted in addition to the transition metal compound (A1), the transition metal compound (A2) and the promoter component (B).
- the amount of organoaluminum compound (C) used is transition metal compound (A1) and transition metal compound (A)
- Total number of moles of aluminum atoms of organoaluminum compound (C) per mole Is preferably 0.11 1 0 0 0, more preferably 0.5 5 0 0, and even more preferably:! ⁇ 1 0 0.
- organoaluminum compounds (C) include trimethylaluminum, triethylarminium, tri-n-propinoreanololium, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- Trialkylaluminum such as octylaluminum; dimethylaluminum chloride, dimethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, Dialkyl aluminum chlorides such as di-n-hexylalminum chloride; methylaluminum dichloride, ethyl aluminum dichloride, n-propylaluminum dichloride n_butylaluminum dichloride Alkyl aluminum dichlorides such as ride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride; di
- the organoaluminum compound (C) is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri_n-butyl.
- the electron donating compound (D) may be contacted in addition to the transition metal compound (A 1), the transition metal compound (A 2) and the promoter component (B).
- the amount of electron donating compound (D) used is preferably the number of moles of electron donating compound (D) per mole of the total number of transition metal compound (A 1) and transition metal compound (A 2) 0 1 1 0 0, more preferably 0.1 5 0, and still more preferably 0.2 5 5.
- Examples of the electron donating compound (D) include triethylamine and trinormaloctylamine.
- the contact temperature is usually _ 1 0 0 3 0 0 ° C, preferably 1 8 0 2 0 0 ° C.
- the contact time is usually 1 minute to 200 hours, preferably 30 minutes to 100 hours. Further, the contact may be carried out in the polymerization reactor with each component being charged separately into the polymerization reaction tank.
- the gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion.
- a stirring blade may be installed in the reaction vessel.
- a method for supplying a polymerization catalyst and each catalyst component to a polymerization reaction tank a method of supplying an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a moisture-free state is usually used. Is used by dissolving or diluting in a solvent and supplying the solution in a slurry state.
- the polymerization temperature is usually ethylene. The temperature is below the melting temperature of the ⁇ -olefin copolymer, preferably 0 to 150 ° C, more preferably 30 to 100 ° C.
- An inert gas may be introduced into the polymerization reaction tank, or hydrogen may be introduced as a molecular weight regulator.
- an organoaluminum compound (C) or an electron donating compound (D) may be introduced.
- the monoolefins used for polymerization are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene.
- the combination of ethylene and ⁇ -olefin is ethylene Zl—butene, ethylene 1-hexene, ethylene Z4—methyl ⁇ ⁇ — 1—pentene, 'ethylene 1-octene, ethylene 1-butene / ⁇ 1—hexene, Ethylene / 1-butene / 4—Methylenole 1-pentene, ethylene ⁇ 1-butene ⁇ 1-octene, ethylene / 1-hexene / 1-octene, etc., preferably ethylene Z1-hexene, ethylene / 4- 1-pentene, ethylene ⁇ 1-butene ⁇ 1-hexene, ethylene ⁇ ⁇ ⁇ -butene
- the method for producing the ethylene_ ⁇ _olefin copolymer of the present invention includes a transition metal compound (A1), a transition metal compound ( ⁇ 2), a promoter component ( ⁇ ), and, if necessary, an organic albumin compound ( Using C) and an electron donating compound (D), a prepolymerized solid component obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) is used as a polymerization catalyst component or a polymerization catalyst.
- the preferred method is to use ethylene as a catalyst to copolymerize ethylene and refine.
- olefins used in the pre-polymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methylolene 1-pentene, cyclopentene, and cyclohexene. . These can be used alone or in combination of two or more.
- the content of the prepolymerized polymer in the prepolymerized solid component is preferably 0.01 to 1000 8 per lg of the promoter component (B), more preferably 0.05 to 500 g. More preferably, it is 0.1 to 200 g.
- a saturated aliphatic hydrocarbon compound is usually used as the solvent.
- the saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C or lower at normal pressure, and has a boiling point of 90 ° C or lower at normal pressure. More preferred are propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, and cyclohexane.
- the slurry concentration is such that the amount of the promoter component (B) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5. ⁇ 3 0 0 g.
- the prepolymerization temperature is usually 120 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed.
- the partial pressure of olefins in the gas phase during the prepolymerization is usually from 0.001 to 2 MPa, preferably from 0.01 to IMPa.
- the prepolymerization time is usually 2 minutes to 15 hours.
- a method of supplying the prepolymerized prepolymerized solid catalyst component to the polymerization reaction tank a method of supplying an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a water-free state, A method of dissolving or diluting the components in a solvent and supplying them in a solution or slurry state is used.
- Ethylene one ⁇ of the present invention - the Orefuin copolymer may be including chromatic known additives.
- the additive include an antioxidant, a weathering agent, a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, a drip-free agent, a pigment, and a filler.
- the ethylene- ⁇ -olefin copolymer of the present invention is molded by a known molding method such as an extrusion molding method such as an inflation film molding method or a ⁇ die film molding method, a hollow molding method, an injection molding method, a compression molding method, or the like. Is done.
- an extrusion molding method or a hollow molding method is preferably used, an extrusion molding method is more preferably used, and a saddle die film molding method is particularly preferably used.
- the ethylene- ⁇ -olefin copolymer of the present invention is used after being molded into various forms.
- the form of the molded product is not particularly limited, but it is used for films, sheets, containers (tray, bottle, etc.).
- the molded article is also suitably used for food packaging materials; pharmaceutical packaging materials; electronic component packaging materials used for packaging semiconductor products, etc .; surface protection materials.
- the ethylene- ⁇ -olefin copolymer of the present invention is excellent in extrusion load, swell ratio and mechanical strength during molding. For this reason, the necking when forming a die film can be lowered. Also, the take-up property at the time of extrusion molding is good.
- the ethylene- ⁇ -olefin copolymer of the present invention is an ethylene polymer inferior to neck-in.
- it can be blended in an appropriate amount with a conventional ethylene polymer.
- neck-in can be greatly improved.
- the test load was 211.82 mm
- the melt flow rate (MFR) measured at 18 N and a temperature of 190 ° C was measured, and the value obtained by dividing H—MFR by MFR was determined.
- z-average molecular weight (Mz), weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured, and MwZMn and Mz / Mw were determined.
- the baseline on the chromatogram consists of a stable horizontal region point with a retention time sufficiently shorter than the appearance of the sample elution peak and a stable horizontal region with a retention time sufficiently longer than the solvent elution peak was observed. A straight line formed by connecting the points of the region.
- a force nuclear magnetic resonance spectrum (i 3 C_NMR) was measured by the carbon nuclear magnetic resonance method under the following measurement conditions, and obtained by the following calculation method.
- Pulse repetition time 4 seconds
- the peak area of a peak having a peak top near 27 p pm was determined.
- the peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side.
- the peak top position of the peak derived from methine carbon having 6 branched carbon atoms was 38.21 ppm.
- the number of short-chain branches in the ethylene_ ⁇ _olefin copolymer was determined from the infrared absorption spectrum. Measurement and calculation were carried out by utilizing characteristic absorption derived from ⁇ -olefin, according to the method described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, MA, Madams, W. F.). The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR 7300 manufactured by JASCO Corporation).
- melt complex viscosity angular frequency curve Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RM S-800 manufactured by Rheometrics), measure the melt complex viscosity angular frequency curve at 1 90 ° C under the following measurement conditions. The melt complex viscosity measured at an angular frequency of 100 rad seconds was determined. The lower the melt complex viscosity, the better the extrusion load during extrusion molding. It is.
- the extruded molten ethylene- ⁇ -olefin copolymer was taken up into a filament shape by a take-up roll at a take-up rate of 6.3 (m / min) / min.
- the take-up speed when the filamentous ethylene- ⁇ -olefin copolymer was cut was defined as the maximum take-up speed. The higher the value, the better the take-off property at the time of extrusion molding.
- the mixture was stirred at 5 ° C for 1 hour, then heated to 40 ° C, and stirred at 40 ° C for 1 hour. Thereafter, the mixture was cooled to 22 ° C, and 0.1 kg of H 2 O was dropped in 1.5 hours while maintaining the reactor temperature at 22 ° C. After completion of dropping, the mixture is stirred for 1.5 hours at 22 ° C, then heated to 40 ° C, stirred for 2 hours at 40 ° C, further heated to 80 ° C, and then for 2 hours at 80 ° C. Stir. After stirring, the supernatant was withdrawn to a remaining amount of 16 L at room temperature, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours.
- the supernatant liquid was extracted at room temperature to obtain a solid product.
- the obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the solid catalyst component was obtained by drying.
- Example 2 Next, after 28 g of ethylene was charged and the system was stabilized, 10.6 g of the solid catalyst component obtained in Example 1 (1) was added, and then the concentration of triisobutylaluminum was lmmo 1 / mL. Polymerization was initiated by adding 4.2 mL of a heptane solution of triisobutylaluminum. Prepolymerization was carried out at 50 ° C for 100 minutes while continuously supplying a mixed gas of ethylene and hydrogen with a hydrogen concentration of 0.2%.
- a prepolymerization was carried out at 50 ° C. for 80 minutes while continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 17.5 g of polyethylene per 1 g of the solid catalyst component.
- prepolymerization was carried out at 50 ° C for 100 minutes. After the polymerization was completed, ethylene, butane, hydrogen, and the like were purged, and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 15.9 g of polyethylene per 1 g of the solid catalyst component.
- a nitrogen-substituted 5-liter four-necked flask was charged with 2 liters of tetrahydrofuran and hexane solution of dimethyl zinc (2M) 1.35 liters (2. 7 mo 1) and cooled to _50 ° C. .
- a solution prepared by dissolving 251.5 g (1.37 mo 1) of pentafluorophenol in 390 ml of tetrahydrofuran was added dropwise thereto over 25 minutes. After completion of the dropping, the temperature was gradually raised to room temperature and stirred for 3 hours. Then, it heated to 45 degreeC and stirred for 1 hour. The temperature was lowered to 20 ° C. in an ice bath, and H 2 0 37.72 g (2.
- the solid product (374 g) and tetrahydrofuran (3 liters) were placed in a 5-liter four-necked flask purged with nitrogen and stirred.
- an ethylene- ⁇ -age-lefin copolymer having excellent extrusion load, swell ratio and mechanical strength, and sufficiently short relaxation time of a molecular chain in a molten state, and the copolymer are extruded.
- a molded article can be provided.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
Description
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Priority Applications (3)
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US12/744,857 US8871885B2 (en) | 2007-11-30 | 2008-11-27 | Ethylene-a-olefin copolymer and molded article |
DE112008003231T DE112008003231T5 (de) | 2007-11-30 | 2008-11-27 | Ethylen-α-Olefin-Copolymer und Formgegenstand |
CN200880118462.6A CN101878236B (zh) | 2007-11-30 | 2008-11-27 | 乙烯-α-烯烃共聚物和成型体 |
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JP2007310080 | 2007-11-30 | ||
JP2007-310080 | 2007-11-30 |
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WO2009069825A1 true WO2009069825A1 (ja) | 2009-06-04 |
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PCT/JP2008/072002 WO2009069825A1 (ja) | 2007-11-30 | 2008-11-27 | エチレン-α-オレフィン共重合体および成形体 |
Country Status (5)
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US (1) | US8871885B2 (ja) |
JP (1) | JP5407300B2 (ja) |
CN (1) | CN101878236B (ja) |
DE (1) | DE112008003231T5 (ja) |
WO (1) | WO2009069825A1 (ja) |
Cited By (1)
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US20130005930A1 (en) * | 2010-03-15 | 2013-01-03 | Sumitomo Chemical Company, Limited | ETHYLENE-alpha-OLEFIN COPOLYMER AND MOLDED ARTICLE |
Families Citing this family (12)
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KR20110084217A (ko) * | 2008-11-11 | 2011-07-21 | 스미또모 가가꾸 가부시끼가이샤 | 에틸렌-α-올레핀 공중합체 및 이의 성형품 |
DE112010002182T5 (de) | 2009-05-29 | 2012-07-26 | Sumitomo Chemical Co., Ltd. | Ethylen-α-Olefin-Copolymer, Formgegenstand, Katalysator für die Copolymerisation und Verfahren zur Herstellung eines Ethylen-α-Olefin Copolymers |
JP2010276128A (ja) * | 2009-05-29 | 2010-12-09 | Sumitomo Chemical Co Ltd | チューブ |
WO2010137740A1 (ja) * | 2009-05-29 | 2010-12-02 | 住友化学株式会社 | エチレン-α-オレフィン共重合体及び成形体 |
JP2011006677A (ja) * | 2009-05-29 | 2011-01-13 | Sumitomo Chemical Co Ltd | 押出しラミネート用エチレン−α−オレフィン共重合体およびその積層体 |
JP2011006676A (ja) * | 2009-05-29 | 2011-01-13 | Sumitomo Chemical Co Ltd | フィルム用エチレン−α−オレフィン共重合体、フィルムおよび食品包装用フィルム |
JP2011132402A (ja) * | 2009-12-25 | 2011-07-07 | Sumitomo Chemical Co Ltd | 発泡用エチレン−α−オレフィン共重合体、発泡用樹脂組成物および発泡体 |
JP5803336B2 (ja) * | 2010-06-29 | 2015-11-04 | 住友化学株式会社 | エチレン−α−オレフィン共重合体 |
CN103709297B (zh) | 2012-10-02 | 2018-01-09 | 住友化学株式会社 | 乙烯‑α‑烯烃共聚物 |
CN109109421B (zh) * | 2017-06-22 | 2022-08-09 | 东曹株式会社 | 层叠体及容器用盖体材料 |
US10703838B2 (en) | 2017-10-31 | 2020-07-07 | Exxonmobil Chemical Patents Inc. | Mixed catalyst systems with four metallocenes on a single support |
JP2022519109A (ja) * | 2019-09-27 | 2022-03-18 | エルジー・ケム・リミテッド | エチレン/α-オレフィン共重合体およびその製造方法 |
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- 2008-11-27 JP JP2008302284A patent/JP5407300B2/ja active Active
- 2008-11-27 WO PCT/JP2008/072002 patent/WO2009069825A1/ja active Application Filing
- 2008-11-27 DE DE112008003231T patent/DE112008003231T5/de not_active Withdrawn
- 2008-11-27 US US12/744,857 patent/US8871885B2/en active Active
- 2008-11-27 CN CN200880118462.6A patent/CN101878236B/zh active Active
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US8841396B2 (en) * | 2010-03-15 | 2014-09-23 | Sumitomo Chemical Company, Limited | Ethylene-α-olefin copolymer and molded article |
Also Published As
Publication number | Publication date |
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CN101878236B (zh) | 2014-05-07 |
JP2009149872A (ja) | 2009-07-09 |
US8871885B2 (en) | 2014-10-28 |
DE112008003231T5 (de) | 2010-10-14 |
CN101878236A (zh) | 2010-11-03 |
US20100305292A1 (en) | 2010-12-02 |
JP5407300B2 (ja) | 2014-02-05 |
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