WO2009069823A1 - 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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- WO2009069823A1 WO2009069823A1 PCT/JP2008/072000 JP2008072000W WO2009069823A1 WO 2009069823 A1 WO2009069823 A1 WO 2009069823A1 JP 2008072000 W JP2008072000 W JP 2008072000W WO 2009069823 A1 WO2009069823 A1 WO 2009069823A1
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- zirconium dichloride
- diphenylmethylene
- ethylene
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
Definitions
- the present invention relates to an ethylene-1- ⁇ -olefin copolymer and a molded body obtained by extrusion-molding 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-ct-olefin copolymer As an ethylene-ct-olefin copolymer, it is known that a copolymer polymerized using a metallocene 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. However, the ethylene- ⁇ -olefin copolymer polymerized using a conventional metallocene catalyst has a high extrusion load at the time of extrusion and a low melt tension ratio due to its low melt ratio. 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.
- An ethylenic polymerized by using a metallocene catalyst comprising a transition metal compound having a group having two substituted cyclene pentagen type anion skeletons that are not bonded to each other and an activating co-catalyst component.
- Japanese Patent Application Laid-Open No. 2 0 4 -1 4 9 7 6 1 discloses a co-catalyst component obtained by contacting silica, hexamethyldisilazane, jetyl pentafluorophenol and water, and triisobutylaluminum. And ethylene mono-alpha-olefin copolymer polymerized using a meta-octene catalyst comprising racemic ethylene bis (1-endenyl) zirconium diphenoxide.
- JP 2 The 006-233206 publication discloses a transition metal compound having a ligand in which two groups having a pentapentane type anion skeleton are bonded via a bridging group, a group having a cyclopentagen 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 problem to be solved by the present invention is that ethylene- ⁇ -olefin has excellent extrusion load, high-speed take-off property and balance of melt tension, swell ratio, mechanical strength, and good appearance.
- An object of the present invention is to provide a polymer, 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 the present invention 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 1 to 100 gZl 0 min
- the flow activation energy (E a) is 60 kj / mo 1 or more
- It relates to an ethylene- ⁇ -olefin copolymer having a swell ratio (SR) of 1.55 or more and less than 1.8.
- a second aspect of the present invention relates to a molded product obtained by extruding the ethylene- ⁇ -
- the ethylene / ⁇ -olefin copolymer of the present invention is an ethylene- ⁇ -olefin copolymer containing a monomer unit based on ethylene and a monomer unit based on ⁇ -olefin having 3 to 20 carbon atoms. .
- the ⁇ -olefin include propylene, 1-butene, and 1 pentene. 1-hexene, 1_heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4_methyl_1_pentene, 4-methyl-1-hexene, etc. These may be used alone or in combination of two or more.
- the ⁇ -olefin is preferably 1-butene, 1-hexene, 4-1methyl-1-1-pentene, or 1-octene.
- the ethylene- ⁇ -olefin copolymer of the present invention does not impair the effects of the present invention in addition to the above-described monomer units based on ethylene and monomer units based on ⁇ -olefin having 3 to 20 carbon atoms. In the range, 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-pentagene), acrylic acid, alk., And lauric acid esters (for example, methyl acrylate) Acid ethyl), methacrylic acid, methacrylic acid ester (for example, methyl methacrylate methyl ethyl methacrylate), and butyl acetate.
- conjugated genes for example, butadiene and isoprene
- non-conjugated genes for example, 1,4-pentagene
- acrylic acid alk.
- lauric acid esters for example, methyl acrylate
- Acid ethyl methacrylic acid
- methacrylic acid ester for example, methyl methacrylate methyl ethyl methacrylate
- butyl acetate for example, conjugated genes (for example, butadiene and isoprene), non-conjugated
- Ethylene present invention the content of ⁇ - Orefin copolymer of ⁇ styrene based monomer units relative to the total weight of the ethylene one ⁇ - Orefin copolymer (1 0 0 wt 0/0), Usually 50 to 99.5% by weight.
- 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 monoolefins of formula 6-8.
- Examples of the ethylene-1- ⁇ -olefin copolymer of the present invention include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-methyl-1-pentene copolymer, an ethylene- 1-octene copolymer, ethylene 1-butene 1 1-hexene copolymer, ethylene 1-butene 4 1-methyl 1 1-pentene copolymer, ethylene 1-butene 1-octene copolymer Ethylene 1-hexene 1-otaten copolymer, etc.
- ethylene 1-hexene copolymer ethylene 4-methyl-1- 1-pentene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butylene 1-
- the density of the ethylene- ⁇ -olefin copolymer of the present invention which is an octene copolymer, ethylene-1-hexene-1-1-octene copolymer (hereinafter sometimes referred to as “d”) is 860- 950 k gZm 3 .
- the ethylene / ⁇ -olefin copolymer can be changed by the content of monomer units based on ethylene in the ethylene / ⁇ -olefin copolymer.
- the melt flow rate (hereinafter sometimes referred to as “MFR j”) of the ethylene- ⁇ -olefin copolymer of the present invention is usually 1 to 100 g / 10 min. From the viewpoint of increasing the mechanical strength, it is preferably 50 gZl 0 min or less, more preferably 20 g 10 min or less, even more preferably 10 g Z 10 min or less, and particularly preferably 5 g / 10 min.
- the melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C and a load of 21.18 N in the method specified in JIS K7210-1 995.
- the melt flow rate of the ⁇ -olefin copolymer can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later.
- the hydrogen concentration or the polymerization temperature is increased, ethylene- ⁇ Combined melt flow The game becomes bigger.
- 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- ⁇ -aged refin copolymer of the present invention is 5.5 to 30 and the Z average
- the ratio of the molecular weight (hereinafter sometimes referred to as “Mz”) to the weight average molecular weight (Mw) (hereinafter sometimes referred to as “MzZMw”) is 2 to 5. If MwZMn is too small, the extrusion load during molding may increase. If Mz / Mw is too large, the appearance of the product may deteriorate.
- MwZMn is preferably 6 or more, and Mz Mw is preferably 4.5 or less, more preferably 4.0 or less, and even more preferably 3.5 or less. If Mw / Mn is too large or MzZMw is too small, the mechanical strength of the resulting molded product may be lowered. Mw / Mn is preferably 25 or less, more preferably 20 or less, and MzZMw is preferably 2.5 or more.
- the MwZMn and Mz / Mw were measured for number average molecular weight (Mn), weight average molecular weight (Mw) and Z average molecular weight (Mz) by gel 'permeation' chromatograph (GPC) method. Mw is divided by Mn, and Mz is divided by Mw.
- the Mw / Mn can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. Become.
- the MzZMw can be changed in the production method described later, for example, depending on the use ratio of the transition metal compound (A1) and the transition metal compound (A2).
- the Mz / Mw of ethylene- ⁇ -olefin copolymer decreases.
- MzZMw represents the molecular weight distribution of the high molecular weight component.
- the smaller Mz / Mw compared to Mw-no-Mn means that the molecular weight distribution of the high molecular weight component is narrow and the molecular weight distribution is very high, that is, the relaxation time is very long.
- Mz / Mw is small
- Mz / Mw is large compared to Mw / Mn
- the molecular weight distribution of the high molecular weight component is wide, very high, and the component ratio of the molecular weight with a very long relaxation time is high.
- (Mw / Mn)-(Mz / Mw) is preferably 1 or more, more preferably (Mw / Mn)-(Mz / Mw) is 2 or more.
- (Mw / Mn) — (Mz Mw) can be changed depending on, for example, the ratio of transition metal compound (A1) and transition metal compound (A2), and the ratio of transition metal compound (A2) is increased. Then, (MwZMn)-(Mz Mw) of ethylene- ⁇ -aged refin copolymer increases. Also, (Mw / Mn) (Mz Mw) can be increased by carrying out prepolymerization.
- the swell ratio (hereinafter sometimes referred to as “SR”) of the ethylene- ⁇ -aged olefin copolymer of the present invention is 1.55 or more and less than 1.8. If the swell ratio is too small, the neck-in may increase when forming a T-die film.
- the swell ratio is preferably 1.6 or more.
- the swell ratio is less than 1.8, preferably less than 1.75, from the viewpoint of improving the take-up property at the time of extrusion molding.
- MFR melt flow rate
- the strand of the copolymer was cooled in air, and the obtained solid strand was measured for the diameter D (unit: mm) of the strand at a position about 5 mm from the upstream end of the extrusion. This is the value (DZDo) obtained by dividing D by the orifice diameter 2.095mm (Do).
- 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, and when the hydrogen concentration is increased or the ethylene pressure is decreased, ethylene (1) The swell ratio of the ⁇ -olefin copolymer is increased. In addition, the swell ratio can be controlled by performing prepolymerization at the time of polymerization.
- the flow activation energy of the ethylene- ⁇ -olefin copolymer of the present invention (hereinafter sometimes referred to as “ ⁇ a”) is 6 O k from the viewpoint of further reducing the extrusion load during molding. J / mo 1 or more.
- the flow activation energy is preferably 150 k jZmo 1 or less, more preferably 140 k J / mo 1 or less, more preferably 130 k, from the viewpoint of enhancing the take-up property during extrusion molding. J / mo 1 or less.
- the flow activation energy can be changed according to the ratio of the transition metal compound (A 1) and the transition metal compound (A2) used in the production method described later, for example, of the transition metal compound (A2). When the use ratio is increased, Ea of the ethylene-ct-olefin copolymer increases.
- the activation energy of flow (E a) is the angular frequency (unit: ra dZs ec) of the melt complex viscosity (unit: P a ⁇ sec) at 190 ° C, based on the temperature one hour superposition principle It is a numerical value calculated by the Arrhenius equation from the shift factor (a T ) when creating a master curve showing dependency, and is obtained by the following method.
- calculation software examples include Rhio os V.4.4.4 manufactured by Rheometrics.
- the correlation coefficient when calculating equation (I) from the four points of 1 30 ° C, 150 ° C, 170 ° C and 190 ° C by the least square method is usually 0.99 or more. is there.
- the melt complex viscosity angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RM RMS-800, etc.), and usually the geometry: parallel plate, plate diameter : 25mm, plate interval: 1.5 to 2mm, strain: 5%, angular frequency: 0.1 to 100 radZ seconds.
- the measurement is performed under a nitrogen atmosphere, and It is preferable to mix an appropriate amount of antioxidant (for example, 1000 ppm) with the measurement sample in advance.
- the number of branches having 5 or more carbon atoms (hereinafter sometimes referred to as “NLCBJ”) of the ethylene monolith refin copolymer of the present invention is preferably from the viewpoint of further reducing the extrusion load during the molding process. Is 0.1 1000 C or more, more preferably 0.1 2/1000 C or more, and preferably 1 or less, more preferably from the viewpoint of increasing the mechanical strength of the obtained molded article.
- the N LCB varies depending on, for example, the concentration of the electron-donating compound or the use ratio of the transition metal compound (A1) and the transition metal compound (A2) in the production method described later. It can also be controlled by carrying out prepolymerization.
- NLCB is calculated from the 13 C-NMR spectrum measured by carbon nuclear magnetic resonance ( 13 C-NMR) method, where the sum of the areas of all peaks observed at 5-50 p pm is 1000 and the number of carbon atoms It is obtained by calculating the area of the peak derived from methine carbon to which 7 or more branches are bonded.
- the peak derived from methine carbon with a branch of 5 or more carbon atoms bonded is around 38.2 ppm (Reference: Scientific document “Macromolecules”, (USA), American Chemical Society, 1999, 32nd, p. 3817—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. In the spectrum analysis, it is preferable to use a negative exponential function as the window function.
- g * defined by the following formula (III) of the ethylene- ⁇ -olefin copolymer of the present invention is from 0.76 to 0.95 (for g *, the following literature was referred to: Developments in Polymer Characterisation-4,. JV. Dawkins ,. ⁇ ⁇ ”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 (III-I). Determined by the following formula (III-II) It was to be justified.
- gscB * is defined by the following formula (III-III).
- ⁇ r e 1 represents the relative viscosity of the ethylene- ⁇ -olefin copolymer.
- Mv represents the viscosity average molecular weight of ethylene- ⁇ -aged refin copolymer.
- GscB * (1-A) 1725 (III—III)
- GPC is the intrinsic viscosity of a polymer (unit: dl / g) assuming that the molecular weight distribution is the same as that of ethylene- ⁇ -olefin copolymer and the molecular chain is linear. Represents.
- gscB * represents the contribution to g * produced by introducing short chain branching into the ethylene- ⁇ -aged olefin copolymer.
- Ethylene _ ⁇ - old Refuin copolymer relative viscosity ( ⁇ re 1) is the Buchiruhi mud carboxymethyl toluene (BHT) tetralin 100 m 1 containing 0.5 wt 0/0 as a thermal degradation inhibitor, O Refuin polymer 10 Omg was dissolved at 135 ° C to prepare a sample solution. Using an Ubbelohde viscometer, 0.5 wt. Calculated from the descent time of the blank solution consisting of tetralin containing only / 0 .
- BHT carboxymethyl toluene
- the viscosity average molecular weight (Mv) of ethylene- ⁇ -olefin copolymer is expressed by the following formula (I I I— I V)
- NM When the number of short chain branches per 1000 carbon atoms determined by R or infrared spectroscopy is y
- 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.
- g * of the ethylene- ⁇ -olefin copolymer is preferably 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.
- the 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 * If g * is too small, the molecular chain spread when the crystal is formed is too small, so the probability of tie molecule formation decreases and the strength decreases.In addition, the relaxation time of the molecular chain due to the long chain branching structure It becomes too long and the appearance of the compact deteriorates. g * can be lowered, for example, by carrying out prepolymerization under suitable conditions.
- (Al) / ( ⁇ 2) is preferably 50 to 80 from the viewpoint of further improving the take-up property at the time of extrusion molding of the ethylene- ⁇ -olefin copolymer in the molten state.
- Mi represents a group 4 transition metal atom in the periodic table
- ⁇ ⁇ and R 1 are each independently substituted with a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 20 Hydrocarbyl group optionally having 1 to 20 carbon atoms, optionally substituted hydrocarbyloxy group, substituted silyl group having 1 to 20 carbon atoms, or substituted amino 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;
- Q i is represented by the following general formula (2): Represents a crosslinking group.
- 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 hydrocarbyl group, 1 to 20 carbon atoms optionally substituted hydrocarbyloxy group, 1 to 20 carbon atoms substituted silyl group or 1 to 20 carbon atoms 20 is a substituted amino group
- the plurality of X 2 may be the same or different from each other
- the plurality of R 3 may be the same or different from each other
- the plurality of R 4 are from each other
- Q 2 may be the same or different
- Q 2 represents a crosslinking group represented by the following general formula (4).
- n is an integer of 1 to 5
- J 2 represents an atom of Group 14 of the Periodic Table of Elements
- R 5 is a hydrogen atom, a halogen atom, or a substitution of 1 to 20 carbon atoms.
- a substituted amino group, and the plurality of R 5 may be the same or different from each other.
- M 1 in the general formula (1) and M 2 in the general formula (3) represent a group 4 transition metal atom in the periodic table of elements, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom.
- X 1 and R 1 in formula ( 1 ) and X 2 , R 3 and R 4 in formula (3) are each independently a hydrogen atom, a halogen atom or a carbon atom having 1 to 20 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 may be the same as or different from each other, the plurality of R 1 may be the same or different from each other, and the plurality of X 2 may be the same or different from each other.
- a plurality of R 3 may be the same or different from each other, and a plurality of R 4 may be the same or different from each other.
- halogen atom of XRX 2 , R 3 and R 4 examples 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 be a substituted or unsubstituted carbyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a carbon atom Examples thereof include a halogenated alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
- alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, Neopentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-nonyl, n_decyl, n-dodecyl, n-dodecyl, n-tridecyl Group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.
- 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, chloroethyl group, dichloroethyl group, trichloro group Ethynole group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group
- Monofluorooctyl group Perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, monochloropropizole group, no 0 —chlorobuty / le group, no ——pentopentyl group, no 0 — Hexyl group, perchlorooctyl group, park port rhododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromo An octyl group, a perb mouth mododecyl group, a perbromopentadecyl group, a perbromoeicosyl group, and the like.
- Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) 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 group, 2-trinole group, 3 Monotolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group Group, 2, 3, 4 trimethylphenyl group, 2, 3, 5-trimethylphenyl group, 2, 3, 6_trimethylphenyl group, 2, 4, 6_trimethylphenyl 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, isopropylphenyl group, n-butyl
- hydrocarbyl group having 1 to 20 carbon atoms which may be substituted include a hydrocarbyl group substituted with a substituted silyl group, and a hydrocarbyl group substituted with a substituted amino group.
- hydrocarbyl groups substituted with hydrocarbyloxy groups include trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylbutyl group, and the like.
- Examples include enyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, and triphenylsilylmethyl group. It is done.
- Hydrocarbyl groups substituted with substituted amino groups include dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, Bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group And diphenylaminophenyl group.
- Hydrocarbyl groups substituted with hydrocarbyloxy groups include methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, tert-butoxy Methyl group, phenoxymethyl group, methoxetyl group, ethoxyethyl group, n-propoxychetyl group, isopoxypoxycetyl group, n-butoxycetyl group, sec-butoxycetyl group, tert-butoxychelyl group, phenoxycetyl group, methoxy-n Propyl group, ethoxy 1-n-propyl group, n-propoxy _ n-propyl group, isopropoxy 1-n-propyl group, n-butoxy n-propyl group, sec-butoxy 1-n-propyl group, tert-butoxy — n-propyl group, phenoxy 1-propyl group, methoxy Is
- X 1 , RX 2 , R 3, and R 4 may be a substituted carbyloxy group having 1 to 20 carbon atoms, such as an alkoxy group having 1 to 20 carbon atoms, and 7 to 2 carbon atoms. 0 aralkyloxy group, 6-20 carbon atom aryloxy group and the like.
- alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n -butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentenoreoxy group.
- Neopentyloxy group n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group Group, n_pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n -nonadecyloxy group, n —eicosoxy group Etc.
- alkoxy groups are substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom. Examples include a ruxoxy group.
- 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 —Dimethylphenyl) methoxy group, (3,5-Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5_trimethylphenyl) methoxy group , (2, 3, 6-trimethylphenyl) methoxy group, (2, 4, 5_trimethylphenyl) methoxy group, (2, 4, 6-trimethylphenyl) methoxy group, (3, 4, 5-Trimethylphenyl) Xoxy group, (2,
- a halogenated aralkyloxy group in which these aralkyloxy 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 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. 2,5-Dimethylphenoxy group, 2,6-Dimethylphenoxy group, 3,4-Dimethylphenoxy group, 3,5-Dimethylphenoxy group, 2,3,4-Trimethylphenoxy group 2, 3, 5-trimethylphenoxy group, 2, 3, 6-trimethylphenoxy group, 2, 4, 5-trimethylphenoxy group, 2, 4, 6-trimethylphenoxy group, 3 , 4, 5-trimethylphenoxy group, 2, 3, 4, 5-tetramethylphenoxy group, 2, 3, 4, 6-tetramethylphenoxy group, 2 , 3, 5, 6-Tetramethylphenoxy group, Pentamethylphenoxy group, Ethylphenoxy group, ⁇ -Propylphenoxy group, Isopropylphenoxy group, ⁇ -Butylphenoxy group, sec-Butylphenoxy group, Examples thereof include
- 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.
- Examples of the substituted silyl group having 1 to 20 carbon atoms of X 1 , R 1 , X 2 , R 3 and R 4 include silyl groups substituted with hydrocarbyl groups such as alkyl groups and aryl groups. it can.
- 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 _Octylamino group, n-decylamino group, phenylamino group, benzylamino group, dimethylamino group, jetylamino group, di-n-propylamino group, diisopropylamino group, di 1 n-Ptylamino group, Di 1 sec-Butylamino group, Di
- X 1 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, Trifluoromethoxy group, phenyl group, phenoxy group, 2, 6-di tert-butylphenoxy group, 3, 4, 5-trifluorotrifluoro group, pentafluorophenoxy group, 2, 3, 5, 6-tetrafluoro group 4_Pentafluorophenylphenoxy group, benzyl group.
- 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, Trifluoromethoxy group, phenyl group, phenoxy group, 2, 6-di-tert-butylphenoxy group, 3, 4, 5-trifluorophenoxy group, pentafluorophenoxy group, 2, 3, 5, 6-tetrafluoro group Rho 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 still more preferably a hydrogen atom.
- Q 1 in the general formula (1) represents a bridging group represented by the general formula ( 2 )
- Q 2 in the general formula (3) represents a bridging 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 1 in the general formula (2) and J 2 in the general formula (4) represent group 14 transition metal atoms in the periodic table of elements, and examples thereof include a carbon atom, a key atom, and 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 hydrocarbyl group having 1 to 20 carbon atoms, A hydrocarbyloxy group having 1 to 20 carbon atoms which may be substituted, 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.
- R 2 and R 5 halogen atom, optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, carbon atom
- the substituted silyl group having 1 to 20 carbon atoms and the substituted amino group having 1 to 20 carbon atoms are substituted with halogen atoms of XR 1 , X 2 , R 3 and R 4 , or substituted with 1 to 20 carbon atoms.
- Hydrocanolevir group which may be substituted, Hydrodynamic force optionally substituted with 1 to 20 carbon atoms, Rubyloxy group, substituted silyl group with 1 to 20 carbon atoms and substituted amino group with 1 to 20 carbon atoms Can be mentioned as examples.
- 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 (dimethylphenyl) Enyl) methylene group, bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (jetylphenyl) methylene group, phenyl (propylphenyl) methylene group, di ( R
- Silane diyl group disilane diyl group, trisilane diyl group, tetrasilane diyl group, dimethyl silane diyl group, bis (dimethylsilane) diyl group, jetyl silane diyl group, diprovir silane diyl group, dibutyl silane diyl group, diphenyl silane diyl group And cyclocyclobutadyl group, silacyclohexane diyl group, divinylsilane diyl group, diaryl silane diyl group, (methyl) (bulu) silane diyl group, (aryl) (methyl) silane diyl group, and the like.
- 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.
- Mi is a zirconium atom
- X 1 is a chlorine atom
- methylenebis (indenyl) zirconium dichloride isopropylidenebis (indul) zirconium Dichloride
- (Methyl) (Phenyl) Methylenebis (Indur) Zirconium Dichloride Diphenylmethylene Bis (Indenyl) Zirconium Dichloride, Ethylenebis (Indenyl) Zirconium Dichloride,
- the substituted Tj 5 -indenyl group has the 2--position, 3-position, 4-position, 5-position, 6-position and the mono-substitution when the bridging group is in the 1-position. Includes substitutions at the 7-position and includes all combinations in the same way, even if the Tachibana position is other than the 1st position. Similarly, di- or higher-substituted products include all combinations of substituents and crosslinking positions.
- X 1 dichloride of the above transition metal compound is difluoride, dibromide, diaiodide, dimethyl, jetyl, diisopropyl, dimethoxide, methoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide, 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 Jirukoniumu of M 1 in the transition metal compound may be exemplified compound was changed to titanium or hafnium.
- the transition metal compound (A 1) represented by the general formula (1) is preferably ethylenebis (indenyl) zirconium diphenoxide, ethylenebis (indul) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride. is there.
- M 2 is a zirconium atom
- X 2 is a chlorine atom
- the bridging group Q 2 is a diphenylmethylene group.
- Diphenylenomethylene (2-ethylene 1-cyclopentageninole) (9-funoleoreninole) Zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentagenylene) (9-fluorenyl) Zirconium dichlorine Diphenylmethylene (2,4-diethyl-1-cyclopentaenyl) (9-fluorenyl) Zirconium dichloride, Diphenylenomethylene (2,5-ethynoleyl 1-cyclopentadenyl) (9 —Funoleyl) Zirconium dichloride, diphenylmethylene (3, .4-ethyl-1-cyclopentagenyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (2, 3, 4-triethyl _ 1-cyclopenta Genyl) (9-Fluorenyl) Zirco dichloride, Diphenyl Methylene (2,3,5-triethyl
- Diphenyl methylene (2—Echi ⁇ le 1—Cyclopentage 2 (2, 7—Dimethi / ⁇ Lee 9—Fonolereni / ⁇ ) Di ⁇ “Conium dichloride, Diphen ⁇ methylene (3—Ethenole 1 _ Cyclo (Pentageninore) (2, 7-dimethinole 9-funoleoreninole) Di ⁇ / conium dichloride, diphenylmethylene (2, 4-jetyl- 1-cyclopentagenyl) (2, 7 — dimethyl 9 _fluorure) Zirconium Dichloride, Diphenylmethylene (2,5-Detyl-1- 1-Cyclopentaenyl) (2,7-Dimethyl-1-9-Fluorenyl) Zirconium Dichloride, Diphenylmethylene (3,4-Jetinore _ 1— (Cyclopentagenyl) (2,7-dimethyl-9-fluorenyl
- Diphenylenomethylene (2-Methyl _ 1-Cyclopentaenyl) (2, 7-Gethinoreol 9 _Fluorenyl) Zirconium Dichloride
- Diphenylmethylene (3-Methyl-1-cyclopentaenyl) (2, 7-Jetyl _ 9-Fluorenyl) Zirconium dichloride
- Diphenylmethylene (2,4-Dimethyl _ 1-Cyclopentagenyl) (2, 7 One jeti ⁇ —9-Funolereni ⁇ ⁇ ) Di ⁇ / Conium dichloride
- Diphenyl methylene (2,5-Dimethinole _ 1-Cyclopentageninore) (2,7 _Getinore _9-Fonoleleninole) Zirconium dichloride
- Diphenylmethylene (3,4-Dimethyl-1- 1-cyclopentageninole) ( 2, 7-jety
- Diphenylenomethylene (2-Fuenyl ⁇ Lay 1-Cyclopentageninore) (2,7-Jetinore—9-Funolerenore) 2 (2,7-Jetinore 9-Fuzoleleninole) Dinoleconum dichloride, Diphenylmethylene (2,4-Diphenyl-1- 1-cyclopentagenyl) (2,7-Jeti ⁇ Le 9-Fonoleleni Ginoreconium dichlor Dipheni ⁇ / methylene (2,5-diphenyl 2-cyclopentaenyl) (2,7-jetinore 9 _fluorenyl) dinorecum-dichloride, diphenenoremethylene (3,4-diphenyl 1) -Cyclopentadienyl) (2,7-Jetyl_9-Fluorenyl) Zirconium dichloride, diphenenolemethylene (2,3, 4-triphenyl- 1-cyclopent
- 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 group, silacyclo
- compounds in which the transition metal compound M 2 zirconium is changed to titanium or hafnium can also be exemplified.
- the transition metal compound (A 2) represented by the general formula (3) is preferably diphenylmethylene (1-cyclopentageninole) (9-funoleoreni / re) dinoreconium dichloride.
- the co-catalyst component ( ⁇ ) used in the preparation of the polymerization catalyst used in the production of the ethylene- ⁇ -aged refin copolymer of the present invention includes the following component (b 1), the following component (b 2), Solid catalyst component formed by contacting component (b 3) and the following component (b 4) (b 1): Compound represented by the following general formula (5)
- M 3 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
- 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 as or different from each other.
- 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 represents a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl 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, zinc atom, tin atom or bismuth atom, still more preferred.
- X in the general formula (5) represents a number corresponding to the valence of M 3 . For example, when 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 there are a plurality of L, they may be the same 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.
- a halogenated alkyl group having 1 to 20 carbon atoms is preferable, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, Bromomethyl group, dibromomethyl group, tribromomethyl group, chodomethyl group, jodomethyl group, triodochinole group, fluorethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoro oral cetyl group, pentafluoroethyl group, Chloroethyl group, dichloroethyl group, trichloropolyethyl group, tetrachlorodiethyl group, pentachloroethyl group, bromoethyl group, dibumethyl group, tribrom
- an aralkyl group having 7 to 20 carbon atoms is preferable, for example, a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methylol group , (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl, (2,5-dimethylphenyl) methyl, (2,6-dimethylphenyl) methyl, ( (3,4-dimethylphenyl) methyl group, (4,6nidimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, ( 2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5— Tetramethylenophenyl) methyl
- 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 T i
- t is 2 when T 1 is an oxygen atom or sulfur atom
- t is 3 when T 1 is a nitrogen atom or phosphorus atom .
- 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 may be the same as or different from each other.
- 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.
- Examples of the halogen atom of R 6 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 group, an iodoquinolenobinoxycarbonyl 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 carbyloxy group; a halogenated hydropower, a noreviroxycarbonyl group, and the like.
- Examples of the group having an electron-withdrawing group of R 6 include cyanated hydrocarbyl groups such as cyanated aryl groups and nitrated hydrocarbyl groups such as nitrated aryl groups.
- halogenated alkyl group for R 6 examples include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a odomethyl group, a difunoleolomethyl group, a dichloromethyl group, a dibromomethyl group, a jodomethyl group, a trifluoromethyl group, and a trichloromethyl group.
- R6 halogenated aryl groups include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 4-Difluorophenyl group, 3,5-Difluorophenyl group, 2,4,6-Trifluorophenyl group, 3,4,5-Trifunoleolophenyl group, 2,3,5,6 Phenyl group, pentafluorophenyl group, 2, 3, 5, 6-tetrafluoro-4-trifluoromethylphenyl group, 2, 3, 5, 6-tetrafluoro- 4-pentafluorophenylenophenyl group, .perfluoro 1-naphthyl group, perfluoro 1-naphthyl group, 2-black 2-phenyl group, 3-black 2-phenol group, 4-black 2-phenyl group, 2, 4-dichlorophenyl group, 2, 6-dichlorophenyl group
- the R6 (halogenated alkyl) aryl group includes 2_ (trifluoromethyl) phenyl group, 3-(trifluoromethyl) phenyl group, 4-(trifluoromethyl) phenyl group, 2 , 6_bis (trifluoromethyl) phenyl 3 ⁇ 4, 3,5-bis (trifluoromethyl) phenyl group, 2, 4, 6-tris (trifluoromethyl) phenyl group, 3, 4, 5-tris (Trifluoromethyl) phenyl group and the like.
- Examples of the cyanylated 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 Re include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4_nitrophenyl group.
- hydrocarbyloxycarbonyl group of R 6 examples include an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aralkyloxycarbonyl group, and the like, and more specifically, a methoxycarbonyl group, Examples thereof include an ethoxycanoleboninole group, an n_propoxycarbonyl group, an isopropoxycarbonyl group, and a phenoxycarbonyl group.
- halogenated hydrocarbyloxycarbonyl group of R 6 examples include a halogenated alkoxycarbonyl group, a nonogenated aralkyloxycarbonyl group, and a nonogenated aryloxycarbonyl group. Examples thereof include trifluoromethoxycarbonyl group, pentafluorophenoxycarbonyl group and the like.
- R 6 is preferably a halogenated hydride carbyl group, more preferably a halogenated alkyl group or a halogenated aryl group, and more preferably a fluorinated alkyl group, a fluorinated aryl group, or a chlorinated alkyl 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 trifluoromethylol group, a 2,2,2-triphenyleoethyl group, a 2,2,3,3,3_pentafluoropropyl group, a 2,2 , 2-trifluoro- 1_trifluoromethylethyl group or 1,1 bis (trifluoromethyl) -1,2,2,2-trifluoroethyl group, more preferably trifluoroethylene It is a methyl group, a 2,2,2-trifunoleo 1-trifluoromethylethyl group, or a 1,1-bis (trifluoromethyl) -1,2,2,2-trifluoroethylol group.
- fluorinated aryl group a 2-fluorophenyl group, a 3-phenolo orophenylol group, a 4-phenololenophenyl group, a 2,4-diphenololophore group, a 2,6-diphenylorenophenol group, a 3, 4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5_trifluorophenolo group, 2,3,5,6-tetrafluorophenyl group, Pentafunoleolophenyl group, 2,3,5,6-tetrafluoro-4_trifluoromethylphenyl group, 2,3,5,6-tetrafluororeorol 4-pentafluorophenylphenyl group, no.
- Monofluoro-1-naphthyl group or perfluoro-2-naphthyl group more preferably> 3,5-difluorophenyl Group, 3, 4, 5-trifluorophenyl group or pentafluorophenyl group.
- a chlorinated alkyl group a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a 2,2,2-trichloroethyl group, a 2,2,3,3,3_pentachloropropyl group, a 2, 1,2-trichloromethyl 1_trichloromethylethyl group or 1,1 bis (trichloromethyl) 1-2,2,2-trichloromethyl group.
- the chlorinated aryl group is preferably a 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5 -A triclonal phenyl group or a pentachlorophenyl group.
- 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 .
- R 7 in the general formula (7) represents a hydrocarbyl group or a halogenated hydrocarbyl group.
- the hydride carbyl group of R 7 include an alkyl group, an aralkyl group, and an aryl group, and examples thereof include the groups exemplified as the alkyl group, aralkyl group, and aryl group of L.
- alkyl group, the halogenated aryl group, and the (halogenated alkyl) aryl group are exemplified.
- 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.
- Dialkyl zinc such as zinc, diisobutyl zinc, di-n_hexyl zinc, diphenyl zinc, dinaphthyl zinc, bis (pentafluorophenyl) zinc such as zinc; dialkenyl zinc such as diallyl zinc; Pentazenyl) zinc; methylzinc chloride, ethylzinc chloride, n-propylzinc chloride, isopropylzinc chloride, salt N_Butylzinc, Isobutylzinc chloride, n-Hexylzinc chloride, Methylzinc bromide, Oxygenated til zinc, n-Propylzinc bromide, Isopropylzinc bromide, N-Butylzinc bromide, Isobutylzinc bromide , N-hexyl zinc bromide, methyl zinc iodide, chilled zinc iodide, n-propyl zinc
- the compound represented by the general formula (5) of the component (bl) is preferably dialkyl zinc, more preferably dimethyl zinc, jetyl zinc, di-n-propyl dumbbell, di-propyl zinc, di-n-butyl zinc. Diisobutyl zinc, or di-n-hexyl zinc, particularly preferably dimethyl zinc or jetyl zinc.
- Examples of the compound represented by the general formula (6) of the component (b 2) include ammine, phosphine, alcohole, thionole, huaenore, thioenore, naphthonoreno, naphthinoretinoenole, and powerful rubonic acid compounds.
- Amines include di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifluoromethyl) amine, bis (2,2,2_trifluoroethyl) amine, bis (2,2,3,3, 3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2,2-trifluoro Oloechinole) Amine, Bis (2-Fluorophenorinole) Amine, Bis (3-Henoleo-Fuenole) Amine, Bis (4-Henoreolophenolinore) Amine, Bis (2, 6-Difluorophenyl) Amines, bis (3,5-difluorophenyl) Amines, bis (2,4,6-trifluorophenyl) Amines, bis (3,4,5-Trifluoronorolophenore) Amines ,
- phosphine examples include compounds in which the nitrogen atom of the above amine is changed to a phosphorus atom.
- Those phosphines are compounds represented by replacing the amine in the amine with phosphine. '
- 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 alcohol with thiols.
- the phenols include 2_fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-diphenoleolofenore, 2,6-diphlore-enoenole, 3,4-diphenoleolophenol , 3, 5-difluorophenol, 2, 4, 6-trifanolol, phenol 3, 4, 5 _trifanolol, 2, 3, 5, 6-tetraphenol, phenol, pentafunoleol, 2 , 3, 5, 6-tetrafluorool 4-trifluoromethylphenol, 2, 3, 5, 6-tetrafluoro 4-pentafluoro Mouth fuel phenol etc. can be mentioned.
- 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 thiofeils are compounds represented by replacing phenol in the above phenol with thiophenol.
- Naphthol includes perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7, .8_pentafluoro_2-naphthol, 2_ (trifluoromethyl) phenol, 3- (trifluoromethyl) ) Phenol, 4 (Trifluoromethyl) Phenol, 2, 6-bis (Trifluoromethyl) Phenol, 3, 5-bis (Trifluoromethinore) Phenol, 2, 4, 6-Tris (Trifunoleololomethinore) ) Phenol, 2-Chanophenol, 3-Chanophenol, 4-Chanophenol, 2-Nitrophenol, 3_Nitrophenol, 4_Nitrophenol, etc.
- 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 pentafluorobenzoic acid, perfluoronorethanoic acid, perfluoropropanoic acid, perfluoronorobutanoic acid, perfluoropentanoic acid, and perfluoic mouth.
- Kisanoic Acid, Perfluoroheptanoic Acid, Perfone Leorokotanoic Acid, Perfluoronano Acid Acid, Perfluorodeanoic Acid, PA Fluoroundecanoic Acid, No Fluorododecanoic acid can be raised.
- the compound represented by the general formula (6) of the component (b 2) is preferably an amine, an alcohol or a phenol compound, and the amine is preferably bis (trifluoromethylenole) amamine, bis (2, 2, 2 —Trifunoleoretinore) Amine, Bis (2, 2, 3, 3, 3, 3-Pentafluoropropyl) Amine, Bis (2, 2, 2, 2-Trifunoleo 1-tri Fluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -1,2,2,2-trifluoroethyl) amine or bis (pentafluorophenyl) amine, preferably as alcohol Is trifluoromethanol, 2, 2, 2-trifluoroethanol, 2, 2, 3, 3, 3_pentafluoropropanol, 2, 2, 2_trifluoro-1-trifluoromethylethanol or 1 , 1_bis (trifluoromethyl) -2,2,2-trifluoroethanol, preferably phenol, 2-funo
- Examples of the compound represented by the general formula (7) of the component (b 3) include water, hydrogen sulfide, ammine, and a phosphorus compound.
- Amamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutynoleamine, n-pentenoreamine, neopentyl / ⁇ reamine, isopentyl ⁇ ⁇ amine, ⁇ — Alkylamins such as xylamine, ⁇ -octylamine, ⁇ -decylamine, ⁇ -dodecylamine, ⁇ -pentadecylamine, ⁇ -eicosylamine; Methylolamine, (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methyl
- the amines include fluoromethylamine, difluoromethylamine, trifluoromethylamine, 2, 2, 2-trifluoroethylamine, 2, 2, 3, 3, 3, 3-pentafluoro.
- Funoleo mouth pen Examples include halogenated alkylamines such as tyramine, perfluorinated hexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, and perfluoroeicosylamine.
- the amines in which these amines are changed to black, bromo, or iodine can be listed.
- the aniline compounds include aniline, naphthylamine, anthracenylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2 , 6-Dimethylaurine, 3, 4-Dimethylaniline, 3, 5-Dimethylaniline, 2, 3, 4 Trimethylaniline, 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-ethylamineaniline, 3-ethylaniline, 4-ethylaniline, 2,3-jetylaniline, 2,4-jetylurine, 2,5-jetylua Phosphorus, 2, 6-Jetylaniline, 3, 4-Jetylaniline, 3,5-Jetylaniline
- aniline compounds can be mentioned.
- ethyl of these aniline compounds can be converted into n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentinole, n-hexyl, n_octyl, n-decinole, n-dodecinole. , N-tetradecyl, etc., an aniline compound.
- aniline compounds examples include 2-fluoroarin, 3-fluoroarin, 4-fluoroaurine, 2,6-difluoroarin, 3,5-difluoroarin, 2, 4, 6-trifluoroarin, 3 , 4, 5_Trifluoroaniline, Pentafluoroaniline, 2— (Trifluoromethyl) aniline, 3_ (Trifluoromethyl) aniline, 4 1 (Trifluoromethyl) aniline, 2, 6-Di (Trifluoromethyl) aniline, 3, 5-di (trifluoromethyl) aniline, 2, 4, 6-tri (Trifunoleo mouth Examples include methyl) aniline and 3,4,5-tri (trifluoromethyl) aniline.
- the aniline compounds in which the fluoro of these aniline compounds is changed to black mouth, bromo, or iodide can be listed.
- 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 a 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. A plurality of these may be mixed and used.
- Inorganic oxides include S i 0 2 , A 1 2 0 3 , MgO, Z'r 0 2 , T i 0 2 , B 2 0 3 CaO, ZnO, B a 0, Th02, S i 0 2 _MgO, S i ⁇ 2 — A 1 2 0 3 , S i ⁇ 2 — T i 0 2 , S i 0 2 — V 2 0 5 , S i O2-C r 2 O3, S i O2 — T i O2 — MgO, and a mixture of two or more of these.
- S i 0 2 and / or A 1 2 0 3 are preferable, and S i 0 2 (silica) is particularly preferable.
- the above inorganic oxides are small amounts of Na 2 C0 3 , K2 COs, C a COg, Mg CO3, Na 2 S 0 4 , A 12 (S0 4 ) 3, B a S04, KN0 3 , Mg (NO3) 2, a 1 ( NO3) 3, Na 2 0, K 2 0, L i 2 0 such carbonates, sulfates, nitrates, may contain oxide components.
- hydroxyl groups are usually formed on the surface of inorganic oxides, but modified inorganic oxides in which active hydrogen of the surface hydroxyl groups are substituted with various substituents can be used as inorganic oxides.
- modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane; triarylchlorosilanes such as triphenylchlorosilane; dialkyldichlorosilanes such as dimethyldichlorosilane; diphenyldichlorosilane and the like.
- examples thereof include dialkylamines such as jetylamine and diphenylamine, alcohols such as methanol and ethanol, and inorganic oxides contacted with phenol.
- 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.
- clays or clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, alofen, hysingenorite, istirophyllite, tanolec, unmo group, smectite, monmoronite group, hectolite, labonite, Savonites, vermiculites, lyoday stones, palygorskite, kaolinite, nacrites, dickites, and halloy sites can be listed.
- preferred are smectite, montmorillonite, hectolite, labnite and saponite, and more preferred are montmorillonite and hectolite.
- an inorganic oxide is preferably used as the inorganic substance.
- the inorganic substance is preferably dried and substantially free of water, and is preferably dried by heat treatment.
- the heat treatment is usually performed at temperatures 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.
- Heat drying methods include inert gas dried during heating (for example, nitrogen or Argon etc.) can be circulated and dried at a constant flow rate, and can be heated and depressurized under reduced pressure.
- the average particle size of the inorganic substance is usually 1 to 500,000 ⁇ m, preferably 5 to 100 00 im, more preferably 10 to 500 / zm, more preferably 1 0 to 1 0 0 ⁇ m.
- the pore volume is preferably 0.1 ml Zg or more, more preferably 0.3 to 10 ml / g.
- the specific surface area is preferably 10 to 100 O m 2 g, more preferably 10 00 to 50 O n ⁇ Z 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, honolemino groups, strong rubamoyl groups.
- 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 functional group having a Lewis base part that does not have an active hydrogen atom.
- Examples include canolebonino group, alkoxy group, alkyloxy group carbonyl group, N, N-substituent rubamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, and substituted sulfonic acid group.
- These groups are halogen atoms and carbon. It may be substituted with a hydrocarbyl group having 1 to 20 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 ⁇ 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 groups and allyl groups; alkynyl groups such as ethyne groups.
- 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. Specific examples of the monomer include N- (1-ethenyl) amine, N- (2-probe) amine, N- (1-ethulyl) -N-methylamine, N- (2-propenyl).
- Monomers having no active hydrogen atom, functional groups having a Lewis base moiety and one or more polymerizable unsaturated groups include vinylpyridine, bur (N-substituted) imidazole, vinyl (N-substituted). Indazol etc. can be given.
- Examples of other monomers having a polymerizable unsaturated group include ethylene, ⁇ -olefin, aromatic bur compound, and cyclic olefin. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentagen. These monomers are Two or more kinds may be used. Of these, ethylene and styrene are preferable.
- examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.
- the average particle size of the organic polymer is usually 1 to 5000 ⁇ m, preferably 5 to 1 ° 00 / zm, more preferably 10 to 500 / m.
- the pore volume is preferably 0.3 lm l / g or more, and more preferably 0.3 to 10 ml.
- the specific surface area is preferably 10 to 100 Om 2 / g, more preferably 50 to 500 m 2 Zg.
- 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 under reduced pressure, and the like. .
- the promoter component (B) is formed by bringing the component (b 1), the component (b 2), the component (b 3) and the component (b 4) into contact with each other.
- the contact order of component (b 1), component (b 2), component (b 3) and component (b 4)) is as follows.
- the component (b 2) and the component (b 3) are contacted, the contact product resulting from the contact is contacted with the component (b 1), and the contact product resulting from the contact is contacted with the component (b 4).
- Component (b 2) and component (b 3) are contacted, and the contact product resulting from the contact is contacted with component (b 4), and the contact product resulting from the contact is contacted with component (bl). .
- Component (b 2) and component (b4) are contacted, 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 i (b 3). .
- the component (b 3) is contacted with the component (b4), the contact product due to the contact is contacted with the component (b 1), and the contact product due to the contact is contacted with the component (b 2).
- the contact with the component (b 1), the component (b 2), the component (b 3) and the component (b 4) is preferably carried out in an inert gas atmosphere.
- the contact temperature is usually from 100 to 300 ° C, preferably from _80 to 200 ° C.
- the contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.
- a solvent may be used for the contact, and these compounds may be directly contacted without being used.
- a component that does not react with component (b 1), component (b 2), component (b 3) and component (b 4), and their contact materials is used.
- 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 examples 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 Examples include polar solvents such as tolyl solvents, nitro compounds, amine solvents, and sulfur compounds. Specific examples include butane, pentane, hexane, heptane, octane, 2, 2, 4-trimethylenopentane, cyclohexane.
- Aliphatic hydrocarbon solvents such as benzene, toluene, xylene, etc .; Dichloromethane, diphenololeomethane, chlorohonolem, 1,2-dichloroethane, 1,2_dibromoethane, 1, 1, 2— 1, 2, 2_Trifluoroethylene, tetrachloroethylene, black benzene, bromobenzene, o-dichlorobenzene, and other halogenated solvents; dimethyl ether, jetyl ether, diisopropyl ether, di n-butinoreethenole, methinole tert-butinole ethenore, anisole, 1,4-dioxane, 1,2-dimethoxetane, bis (2-methoxychechinole) etherol, tetrahydrofuran, tetrahydropyran, etc.
- Dichloromethane diphenolole
- Solvent methanol, ethanol, 1-propanol, 2-propa 1-butanol, 2-butanol, 1-propanol, 3-methyl _ 1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2 -Alcohol solvents such as methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, glycerin, etc .; Phenolic solvents such as phenol, p-taresol; acetone, ethyl methyl ketone, cyclohexanone, anhydrous Carbonyl solvents such as acetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; hexamethylphosphorus Phosphoric acid derivatives such as acid triamide and triethyl
- 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.
- ⁇ ⁇ value C. Reichardt, Solventsandsolvents E iiects ⁇ nOrganic Chemistry ”, 2 nde d., VCH V erlag (1 9 8 8).
- Etc. are known, and a solvent satisfying the range of 0.8 ⁇ E T N ⁇ 0.1 is particularly preferred.
- Examples of such polar solvents include dichloromethane, dichlorodifluoromethane tank rohonorem, 1,2-dichloroethane, 1,2_dibromoethane, 1,1,2-trichloro port, 1,2,2-trifluororeethane.
- the solvent (s 2) is dimethyl ether, jetyl ether, diisopropynoleatenore, di-n-butinoreether, methinore tert-butinoreether, ether, 1,4-dioxane, 1, 2 —Dimethoxetane, bis (2-methoxychel) ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methinole — 1-propanol, 3-methyl-1- 1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2 monoethoxyethanol, diethylene glycol, triethylene glycol, particularly preferably Di-n_Butyl Ether, methyl tert-butyl ether, 1, 4— Dioxane, Tetrahydro
- 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 Z methanol mixed solvent, xylene ethanol mixed solvent is there. More preferable are a hexane / methanol mixed solvent, a hexane Z ethanol mixed solvent, a toluene methanol mixed solvent, and a toluene ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent. Further, the preferable range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, more preferably 15 to 30% by volume.
- a hydrocarbon solvent can be used as the solvent (si) and the solvent (s2).
- the time until the obtained contact product (c) and the component (b 4) are contacted is short. Is preferred.
- the time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably It is preferably 0 to 1 hour.
- the temperature at which the contact (c) and the component (b 4) are contacted is usually from 100 ° C to 40 ° C, preferably from 20 ° C to 20 ° C, and most preferably from 1 ° C to 40 ° C. 10 ° C to 10 ° C.
- both of the above nonpolar solvents and polar solvents are used.
- Can. Preferably, it is a nonpolar solvent. This is because the contact product between component (b 1) and component (b 3) and the contact product between component (b 1) and component (b 2) and component (b 3) are 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 formula (IV).
- the amount of component (b 2) used per mole of component (bl) is preferably 0.01 to 1.99 mol, more preferably 0.1 to 1.8 mol, More preferably, it is 0.2 to 1.5 mol, and most preferably 0.3 to 1 mol.
- Use amount of component (b 1) Preferred use amount, more preferred use amount, more preferred use amount, and most preferred use amount of component (b 3) per mole are the valence of M 3 , the above component (b Use amount of 1) Calculated from the use amount of component (b 2) per mole and the above relational expression (I).
- the amount of component (b 1) and component (b 2) used is that the metal atom derived from component (b 1) contained in promoter component (B) contains metal contained in 1 g of promoter component (B).
- the number of moles of atoms is preferably an amount that becomes 0.5 lmmo 1 or more, more preferably an amount that becomes 0.5 to 20 mmo 1.
- a heating process at a higher temperature may be added after the contact as described above.
- a solvent having a high boiling point it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. You can replace it with
- the cocatalyst component (B) is the raw material component (b 1), component (b 2), component (b 3) and / or component (b4) remaining as unreacted substances.
- a cleaning process to remove unreacted material in advance.
- the solvent at that time may be the same as or different from the solvent at the time of contact.
- Such cleaning treatment is preferably performed in an inert gas atmosphere.
- the contact temperature is usually ⁇ 100 to 300 ° C., preferably 80 to 200 ° C.
- the contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.
- the total amount of the transition metal compound (A1) and the transition metal compound (A2) used is usually 1 to: 10000 / xmol lg, and preferably 10 to: I 00 0 per lg of the promoter component (B). / mo 1 / g, more preferably 20 to 500 / zmo 1 g.
- 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 preferably the number of moles of aluminum atoms of organoaluminum compound (C) per mole of the total number of moles of transition metal compound (A1) and transition metal compound (A2), preferably 0.1 to 1000, more preferably 0.5 to 500, and even more preferably 1 to 100.
- organoaluminum compounds (C) include trimethylanoleminium, triethylalminium, tri_n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum
- trialkylamine chloride dimethylaluminum chloride, jetylminum chloride, di-n-propylaluminum chloride, di-n-butylamine chloride, diisobutylaluminum chloride De
- G-n-hexylal Dialkylaluminum chlorides such as minumum chloride; methylaluminum chloride lid, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride Alkyl aluminum dichlorides
- the organoaluminum compound (C) is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri_n-hexylaluminum, tri-n —Octylaluminum, more preferably triisobutylaluminum, and tri-n-octylaluminum.
- 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 to 100, more preferably 0.1 to 50, and even more preferably 0.2 to 5 to 5.
- Examples of the electron donating compound (D) include triethylamine and trinormaloctylamine.
- the contact temperature is usually from 1100 to 300 ° C, and preferably from 80 to 200 ° 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.
- Examples of the method for producing the ethylene- ⁇ -olefin copolymer of the present invention include a method in which ethylene and ⁇ -olefin are copolymerized by a gas phase polymerization method, a slurry polymerization method, a bulk polymerization method, or the like.
- a gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable.
- 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 it in a solution or slurry state.
- the polymerization temperature usually melts the ethylene-monoolefin copolymer. The temperature is lower, 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 ⁇ -olefins used in the polymerization are propylene, 1-butene, 1-pentene, 1 —hexene, 1_heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene,
- Examples include ⁇ -olefins having 3 to 20 carbon atoms such as 4-methyl-1- 1-hexene. These may be used alone or in combination of two or more. It may be.
- 1-butene, 1-hexene, 4-methyl-1-1-pentene and 1-octene are preferred.
- the combination of ethylene and ⁇ -olefin is ethylene Z l -butene, ethylene 1-hexene, ethylene / 4-methylolene 1_pentene, ethylene / 1-otaten, ethylene Z 1-butene 1-hexene, Ethylene / —butene Z 4—methizole 1-pentene, ethylene 1-butene / 1-octene, ethylene 1-hexene Z 1-octene, etc., preferably ethylene 1-hexene, ethylene / 4-methyl 1 —Pentene, ethylene 1-butene Z 1 —Hexene, ethylene 1-butene
- the method for producing the ethylene- ⁇ -year-old olefin copolymer of the present invention includes a transition metal compound (A 1), a transition metal compound ( ⁇ 2), a promoter component ( ⁇ ), and, if necessary, an organic material.
- a prepolymerized solid component obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) using an aluminum compound (C) and an electron donating compound (D) is used as a catalyst component for polymerization.
- a method of copolymerizing ethylene and ⁇ -olefin is preferred as a polymerization catalyst.
- the olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1 pentene, 1-hexene, 1-octene, 4-methinole 1-pentene, and cyclopente. 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 from 0.01 to I 100 g, more preferably 0.0, per promoter component (B) lg. It is 5 to 500 g, more preferably 0.1 to 200 g.
- the prepolymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method.
- transition metal compound (A 1), transition metal compound (A 2), promoter component (B), and, if necessary, organoaluminum compound (C) and electron donating property As a method for adding compound (D), usually, an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is used without water, or each component is dissolved or diluted in a solvent. Then, a method of charging in a solution or slurry state is used.
- 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, more preferably 90 ° C. or lower at normal pressure.> Propane, normal butane, isobutane, normal Pentane, isopentane, nonolemanolehexane, and cyclohexane are more preferable.
- the slurry concentration is such that the amount of the promoter component (B) per liter of solvent is usually 0.1 to 600 g, preferably 0.5. ⁇ 3 0 0 g.
- the prepolymerization temperature is usually ⁇ 20 to 100 ° C., preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed. Further, 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 IMP a.
- the prepolymerization time is usually 2 minutes to 15 hours.
- an inert gas such as nitrogen or argon, hydrogen, ethylene, or the like is used, and there is no moisture.
- a method of dissolving or diluting the components in a solvent and supplying them in a solution or slurry state is used.
- the ethylene ct-olefin copolymer of the present invention may contain a known additive as required.
- 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, for example, 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, or a compression molding method. 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 neck-in when forming a die film can be lowered. In addition, the high-speed take-up property at the time of extrusion molding is also good, and the transparency of the molded product can be excellent.
- the present invention will be described with reference to Examples and Comparative Examples.
- JI S K 7 1 1 2— 1 9 8 it was measured according to the method specified in the ⁇ method. The sample was annealed as described in JISK 6 7 6 0— 1 9 9 5.
- the z-average molecular weight (Mz :), the weight-average molecular weight (Mw), and the number-average molecular weight (Mn) are determined according to the following conditions (1) to (8). Measured to obtain Mw / Mn and Mz / Mw.
- the baseline on the chromatogram consists of a point in the stable horizontal region 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.
- the carbon nuclear magnetic resonance spectrum ( 13 C-NMR) was measured by the carbon nuclear magnetic resonance method under the following measurement conditions, and obtained by the following calculation method.
- AVANCE 600 manufactured by Bruker Measuring solvent: 1, 2-dichlorobenzene / 1, 2-dichlorobenzene d 4
- Pulse repetition time 4 seconds
- the peak area of a peak having a peak top in the vicinity of 38.22 to 38.27 ppm was determined with the sum of all peaks observed at 5 to 50 ppm being 1000.
- 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.
- melt complex viscosity measured at a temperature of 190 ° C and an angular frequency of 100 rad / sec was obtained.
- melt tension tester manufactured by Toyo Seiki Seisakusho, melting ethylene ⁇ -olefin copolymer from an orifice of 2.095 mm in diameter and 8 mm in length at a temperature of 190 ° C and an extrusion speed of 0.32 gZ
- the extruded melted ethylene monoolefin copolymer was taken up into a filament by a take-up roll at a take-up rate of 6.3 (mZ).
- the take-up speed when the filamentous ethylene- ⁇ -olefin copolymer was cut was defined as the maximum take-up speed. The higher this value, the better the take-up property at the time of extrusion molding.
- the number of short chain branches in the ethylene- ⁇ -olefin copolymer was determined from an infrared absorption spectrum. Measurement and calculation were carried out using characteristic absorption derived from ⁇ -olefins 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).
- [7)] is the relative viscosity (J? Re 1) of ethylene- ⁇ -olefin copolymer, and 0.5 weight of ptylhydroxytoluene (BHT) as a thermal degradation inhibitor.
- BHT ptylhydroxytoluene
- Tetralin 100 m 1 containing 0, ethylene one alpha - a Orefuin copolymer 10 Omg dissolved in 135 ° C to prepare a sample solution, and the sample solution and a heat deterioration inhibitor by using an Ubbelohde viscometer Descent time with a blank solution consisting of tetralin containing only 0.5% by weight of BHT GPC is calculated from the molecular weight distribution of the ethylene- ⁇ -olefin copolymer in (4) by the formula (II ⁇ _ ⁇ I), and gscB * Was determined by the formula (III-III) from the measurement of the number of short-chain branches of the ethylene-based one-year-old le
- Example 2 The physical properties of the obtained copolymer are shown in Table 1.
- Example 2 28 g of ethylene was charged, and after the system was stabilized, 10.4 g of the solid catalyst component obtained in Example 1 (1) was added, and then the triisobutylaluminum concentration was lmmo 1 / Polymerization was initiated by adding 4. l mL of mL of a heptane solution of triisobutylaluminum. While continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%, prepolymerization was carried out at 50 ° C. for 100 minutes. After completion of the polymerization, ethylene, butane, hydrogen and the like were purged, and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 18.7 g of polyethylene per 1 g of the solid catalyst component.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Density kg / m 3 925 927 927 923 923
- an ethylene ⁇ -olefin copolymer excellent in extrusion load, swell ratio, high-speed take-up property and melt tension, and excellent mechanical strength, and a molded product formed by extruding the copolymer. can do.
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CN2008801184611A CN101878235B (zh) | 2007-11-30 | 2008-11-27 | 乙烯-α-烯烃共聚物及成型体 |
US12/745,178 US8501891B2 (en) | 2007-11-30 | 2008-11-27 | Ethylene-α-olefin copolymer and molded article |
DE112008003297T DE112008003297T5 (de) | 2007-11-30 | 2008-11-27 | Ethylen-α-Olefin-Copolymer und Formgegenstand |
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Cited By (4)
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WO2010137734A1 (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、成形体、共重合用触媒およびエチレン-α-オレフィン共重合体の製造方法 |
JP2010275446A (ja) * | 2009-05-29 | 2010-12-09 | Sumitomo Chemical Co Ltd | カレンダー成形用エチレン−α−オレフィン共重合体およびカレンダー成形体 |
JP2012116867A (ja) * | 2010-11-14 | 2012-06-21 | Nihon Tetra Pak Kk | 包装材料用組成物 |
US20120316310A1 (en) * | 2009-12-15 | 2012-12-13 | Sumitomo Chemical Company, Limited | ETHYLENE-alpha-OLEFIN COPOLYMER |
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CN101878237B (zh) * | 2007-11-30 | 2013-04-24 | 住友化学株式会社 | 乙烯-α-烯烃共聚物和成型体 |
DE112010002188T5 (de) | 2009-05-29 | 2012-08-30 | Sumitomo Chemical Company, Ltd. | Ethylen-α-Olefin-Copolymer und Formgegenstand |
EP2316864A1 (en) * | 2009-10-29 | 2011-05-04 | Total Petrochemicals Research Feluy | Polyethylene prepared with supported late transition metal catalyst system. |
CN102791750B (zh) | 2010-03-15 | 2014-10-29 | 住友化学株式会社 | 乙烯-α-烯烃共聚物及成型体 |
DE102010056519A1 (de) * | 2010-12-27 | 2012-06-28 | Heliatek Gmbh | Optoelektronisches Bauelement mit dotierten Schichten |
CN103709297B (zh) * | 2012-10-02 | 2018-01-09 | 住友化学株式会社 | 乙烯‑α‑烯烃共聚物 |
WO2019083151A1 (ko) * | 2017-10-26 | 2019-05-02 | 한화케미칼 주식회사 | 혼성 담지 메탈로센 촉매를 이용한 고밀도 에틸렌계 중합체 및 이를 이용한파이프 |
US10703838B2 (en) | 2017-10-31 | 2020-07-07 | Exxonmobil Chemical Patents Inc. | Mixed catalyst systems with four metallocenes on a single support |
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US20110040059A1 (en) | 2011-02-17 |
JP2009149871A (ja) | 2009-07-09 |
JP5407299B2 (ja) | 2014-02-05 |
CN101878235B (zh) | 2012-08-15 |
US8501891B2 (en) | 2013-08-06 |
DE112008003297T5 (de) | 2010-10-07 |
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