WO2013022108A1 - Catalyseur de polymérisation oléfinique et procédé pour la préparation de polymère oléfinique - Google Patents

Catalyseur de polymérisation oléfinique et procédé pour la préparation de polymère oléfinique Download PDF

Info

Publication number
WO2013022108A1
WO2013022108A1 PCT/JP2012/070574 JP2012070574W WO2013022108A1 WO 2013022108 A1 WO2013022108 A1 WO 2013022108A1 JP 2012070574 W JP2012070574 W JP 2012070574W WO 2013022108 A1 WO2013022108 A1 WO 2013022108A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
ring
atom
tert
Prior art date
Application number
PCT/JP2012/070574
Other languages
English (en)
Japanese (ja)
Inventor
正人 ▲高▼野
高沖　和夫
健二 十河
伊藤　和幸
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2013022108A1 publication Critical patent/WO2013022108A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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 a catalyst for olefin polymerization using a titanium, zirconium or hafnium complex and a method for producing an olefin polymer.
  • metallocene catalysts is one of the topics in recent years in the chemistry of olefin polymerization that has been greatly developed by Ziegler-Natta type magnesium-supported highly active titanium catalysts. Further, recently, development of so-called post metallocene catalysts has attracted attention as a catalyst for constructing a more precise polymerization process.
  • Patent Document 1 reports propylene polymerization using a diphenoxy titanium complex, a zirconium complex or a hafnium complex derived from ethane-1,2-dithiol.
  • Non-patent Document 1 diphenoxy titanium complex, zirconium complex and hafnium complex derived from trans-cyclooctane-1,2-dithiol have been reported. Furthermore, of these complexes, 1-hexene polymerization using a zirconium complex as a catalyst has been reported (Non-patent Document 2).
  • the problems to be solved by the present invention include an olefin polymerization catalyst capable of producing an olefin polymer with high activity in the presence of a catalyst obtained by contacting a transition metal complex, an activation promoter component and a support, and
  • An object of the present invention is to provide a method for producing an olefin polymer in which an olefin is polymerized in the presence of an olefin polymerization catalyst.
  • the present invention relates to an olefin polymerization catalyst obtained by contacting a complex represented by the general formula (1-1) or (1-2), an activation promoter component and a carrier.
  • a complex represented by the general formula (1-1) or (1-2) an activation promoter component and a carrier.
  • M represents a zirconium atom or a hafnium atom.
  • R 1 and R 5 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms or a substituted silyl group is represented.
  • R 2 to R 4 and R 6 to R 10 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic compound in R 1 to R 10 Each residue may have a substituent.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 2 And R 9 and R 6 and R 10 may be independently connected to each other to form a ring, and these rings may have a substituent.
  • Each X is independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, Substituted silyl groups, A substituted amino group, It represents a substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the carboxylate group in X each have a substituent. Also good. Adjacent Xs may be connected to each other to form a ring.
  • L represents a neutral Lewis base. When there are a plurality of L, the plurality of L may be the same or different. l is 0, 1, or 2. )
  • the present invention also relates to a method for producing an olefin polymer in which an olefin is polymerized in the presence of the catalyst.
  • the present invention relates to an ethylene- ⁇ having a polymer particle content of not more than 2% by volume, a 50% volume particle size of not less than 500 ⁇ m, and a particle bulk density of not less than 400 kg / m 3. -Relating to olefin copolymer particles.
  • an olefin polymer can be produced with high productivity.
  • an ⁇ -olefin polymer having high stereoregularity can be produced with high productivity.
  • the olefin polymerization catalyst according to the present invention is obtained by contacting a complex represented by the following general formula (1-1) or (1-2), an activation promoter component and a carrier.
  • a complex represented by the following general formula (1-1) or (1-2) an activation promoter component and a carrier.
  • the complexes represented by the following general formulas (1-1) and (1-2) will be described.
  • M represents a zirconium atom or a hafnium atom. From the viewpoint of producing a high molecular weight polyolefin, hafnium atoms are preferred.
  • N is 1 or 2, preferably 2.
  • R 1 and R 5 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms or a substituted silyl group is represented.
  • R 1 and R 5 are preferably each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, or a substituted silyl group, More preferably, each independently A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, or a substituted silyl group, R 1 and R 5 are particularly preferably when R 1 and R 5 are the same, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms
  • R 9 and R 10 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
  • R 9 and R 10 are preferably each independently A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, A substituted silyl group, or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, More preferably, each independently an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, Or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, R 9 and R 10 are particularly preferably R 9 and R 10 are the same, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atom
  • R 2 to R 4 and R 6 to R 8 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
  • R 2 to R 4 and R 6 to R 8 are preferably each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, or a substituted silyl group, More preferably, each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms or a substituted silyl group.
  • R 2 , R 4 , R 6 and R 8 are more preferably a hydrogen atom. More preferably, R 3 and R 7 are each independently A halogen atom, A cycloalkyl group having 3 to 10 carbon atoms constituting an alkyl group ring having 1 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms or a substituted silyl group.
  • R 3 and R 7 are the same, A cycloalkyl group having 3 to 10 carbon atoms constituting an alkyl group ring having 1 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, or a substituted silyl group, Most preferably, An alkyl group having 1 to 20 carbon atoms.
  • Each compound residue may have a substituent.
  • Examples of the halogen atom in R 1 to R 10 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 1 to R 10 include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, and a perfluoro group.
  • the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 1 , R 5 , R 9 and R 10 is preferably an n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n- Alkyl groups having 4 to 10 carbon atoms such as pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n-octyl group and n-decyl group And More preferably, it is a tertiary alkyl group having 4 to 10 carbon atoms such as a tert-butyl group, a tert-pentyl group, or a texyl group, Most preferred is a tertiary alkyl group having 5 to 10 carbon atoms
  • the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 2 to R 4 and R 6 to R 8 is preferably a perfluoromethyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n
  • An alkyl group having 4 to 10 carbon atoms such as an octyl group or an n-decyl group, More preferably, it is an alkyl group having 1 to 8 carbon atoms such as perfluoromethyl group, methyl group, isopropyl group
  • Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring in R 1 to R 10 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms in R 1 to R 10 include a vinyl group, an allyl group, a propenyl group, a 2-methyl-2-propenyl group, a homoallyl group, a pentenyl group, and a hexenyl. Group, heptenyl group, octenyl group, nonenyl group, decenyl group, etc., An alkenyl group having 3 to 6 carbon atoms is preferable, and an allyl group or a homoallyl group is more preferable.
  • Examples of the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms in R 1 to R 10 include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, and 3-methyl-1-butynyl.
  • Examples of the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms in R 1 to R 10 include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methyl Phenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, ( 3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) 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-te Lamethylphenyl) methyl group,
  • Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms in R 2 to R 4 and R 6 to R 10 include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 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, 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-tetra Methylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropy
  • Examples of the substituted silyl group in R 1 to R 10 include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a triisobutylsilyl group, and a tert-butyldimethyl group.
  • Examples include silyl group, methyldiphenylsilyl group, dimethyl (phenyl) silyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, methylbis (trimethylsilyl) silyl group, dimethyl (trimethylsilyl) silyl group, and tris (trimethylsilyl) silyl group.
  • a trialkylsilyl group having 3 to 20 carbon atoms such as trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group; methylbis (trimethylsilyl) silyl group, dimethyl group
  • Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms in R 1 to R 10 include, for example, a perfluoromethoxy group, a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoroisopropoxy group, a perfluoro group, Fluoro-n-butoxy group, perfluoro-sec-butoxy group, perfluoroisobutoxy group, perfluoro-n-pentyloxy group, perfluoronepentyloxy group, perfluoro-n-hexyloxy group, perfluoro-n -Heptyloxy group, perfluoro-n-octyloxy group, perfluoro-n-decyloxy group, perfluoro-n-dodecyloxy group, perfluoro-n-pentadecyloxy group, perfluoro-n-eicosyloxy group Methoxy group, e
  • Examples of the aryloxy group having 6 to 30 carbon atoms in R 1 to R 10 include, for example, phenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6- 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, 2,6-diisopropylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pentafluorophenoxy group, 2 -Trifluoromethylphenoxy group, 3-trifluoromethylphenoxy group, 4-trifluoromethylphenoxy group Group, 2,3-difluorophenoxy group, 2,4-fluorophenoxy group, 2,5-difluorophenoxy group, 2-chlorophenoxy group, 2,3-d
  • Examples of the substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms in R 1 to R 10 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) Nyl) meth
  • Examples of the substituted or unsubstituted heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring in R 2 to R 4 and R 6 to R 10 include a thienyl group, a furyl group, and a 1-pyrrolyl group.
  • 1-imidazolyl group 1-pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, N-carbazolyl Groups, Preferred are thienyl group, furyl group, 1-pyrrolyl group, pyridyl group, pyrimidinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, or N-carbazolyl group. .
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 2 And R 9 and R 6 and R 10 may be independently connected to each other to form a ring, and these rings may have a substituent, preferably 2 on the benzene ring. It is a 4- to 10-membered hydrocarbyl ring or heterocyclic ring containing one carbon atom, and the ring may have a substituent.
  • the ring include cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, benzene ring or naphthalene ring, furan ring, 2,5-dimethylfuran ring, thiophene ring, 2, 5-dimethylthiophene ring, pyridine ring and the like can be mentioned, and preferably a cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, more preferably R 1 and R 2 , R 5 and R 6 , A cyclopentene ring, a cyclohexene ring, a benzene ring or a naphthalene ring in which R 2 and R 9 and / or R 6 and R 10 are linked.
  • Each X is independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, Substituted silyl groups, A substituted amino group, It represents a substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the carboxylate group in X each have a substituent. Also good. Adjacent Xs may be connected to each other to form a ring, and the ring may have a substituent.
  • a halogen atom in X an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms
  • An aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a substituted silyl group, , R 2 to R 4 and R 6 to R 8 are the same as described above.
  • Examples of the substituted amino group in X include, for example, a dimethylamino group, a diethylamino group, a di-n-butylamino group, a di-n-propylamino group, a diisopropylamino group, a dibenzylamino group, or a diphenylamino group.
  • hydrocarbylamino groups A dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group or a dibenzylamino group is preferable.
  • Examples of the substituted thiolate group in X include a thiophenoxy group, 2,3,4-trimethylthiophenoxy group, 2,3,5-trimethylthiophenoxy group, 2,3,6-trimethylthiophenoxy group, 2,4 , 6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group, 2,3,4,5-tetramethylthiophenoxy group, 2,3,4,6-tetramethylthiophenoxy group, 2,3,5 , 6-tetramethylphenoxy group, pentamethylphenoxy group, 2-fluorothiophenoxy group, 3-fluorothiophenoxy group, 4-fluorophenoxy group, pentafluorothiophenoxy group, 2-trifluoromethylthiophenoxy group, 3-tri Fluoromethylthiophenoxy group, 4-trifluoromethylthiophenoxy group, 2,3 Difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothiophenoxy group, 2-chlorothioph
  • Examples of the substituted or unsubstituted carboxylate group having 1 to 20 carbon atoms in X include an acetate group, propionate group, butyrate group, pentanate group, hexanoate group, 2-ethylhexanoate group or trifluoroacetate group. Named, A hydrocarbyl carboxylate group having 2 to 10 carbon atoms is preferred, and an acetate group, propionate group, 2-ethylhexanoate group or trifluoroacetate group is more preferred.
  • X is preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, or a substituted amino group, more preferably a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
  • L represents a neutral Lewis base.
  • L include ethers, amines or thioethers, and specific examples include tetrahydrofuran, diethyl ether, 1,4-dioxane, and pyridine.
  • L is preferably tetrahydrofuran.
  • l is 0, 1, or 2, preferably 0 or 1, and more preferably 0. When there are a plurality of L, the plurality of L may be the same or different.
  • the alkoxy group, the aralkyloxy group, the aryloxy group, the substituent that the carboxylate group may have, and the ring formed by linking X to each other.
  • substituent for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a silicon atom, a nitrogen atom, and a substituted group containing a phosphorus atom or a sulfur atom.
  • two benzyl groups directly bonded to the zirconium atom of each of the above compounds can be replaced with a chlorine atom, a methyl group, a dimethylamino group, an isopropoxy group, a tert-butoxy group, or a phenoxy group. Also included are modified compounds.
  • the group corresponding to R 3 and R 7 in the general formula (1-1) is changed to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.
  • the compound which was made is also mentioned.
  • Preferred examples of the complex represented by the formula (1-1) include the following compounds.
  • the group corresponding to R 3 and R 7 in the general formula (1-1) is changed to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.
  • the compound which was made is also mentioned.
  • More preferable examples of the complex represented by the formula (1-1) include the following compounds.
  • two benzyl groups directly bonded to the titanium atom of each of the above compounds can be replaced with a chlorine atom, a methyl group, a dimethylamino group, an isopropoxy group, a tert-butoxy group, or a phenoxy group. Also included are modified compounds.
  • the group corresponding to R 3 and R 7 in the general formula (1-2) is changed to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group. Also included are the compounds.
  • Preferred examples of the complex represented by the formula (1-2) include the following compounds.
  • the group corresponding to R 3 and R 7 in the general formula (1-2) is changed to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group. Also included are the compounds.
  • More preferable examples of the complex represented by the formula (1-2) include the following compounds.
  • Particularly preferable examples of the complex represented by the formula (1-2) include the following compounds.
  • complex (1) The complex represented by the general formula (1-1) and the complex represented by the general formula (1-2) (hereinafter collectively referred to as “complex (1)”) are described in, for example, the method described in Non-Patent Document 2.
  • the compound represented by the following general formula (2-1) or (2-2) hereinafter collectively referred to as “compound (2)”
  • compound (3) the following general formula (3-1) or (3 -2)
  • R 1 ⁇ R 8 and n in the general formula (2-1) is the same as the R 1 ⁇ R 8 and n in the general formula (1-1) in.
  • R 2 ⁇ R 4 in the general formula (2-2) R 6 ⁇ R 10 and n are the same as the general formula (1-2) in the R 2 ⁇ R 4, R 6 ⁇ R 10 and n is there.
  • M and X in the general formula (3-1) are the same as M and X in the general formula (1-1).
  • MX 4 includes, for example, Zr (CH 2 Ph) 4 , ZrCl 2 (CH 2 Ph) 2 , Zr (CH 2 SiMe 3 ) 4 , ZrF 4 , ZrCl 4 , ZrBr 4 , ZrI 4 , Zr (OMe) 4 , Zr (OEt) 4 , Zr (Oi-Pr) 4 , ZrCl 2 (Oi-Pr) 2 , Zr (On-Bu) 4 , Zr (Oi-Bu) 4 , Zr ( Ot-Bu) 4 , Zr (OPh) 4 , Zr (NMe 2 ) 4 , ZrCl 2 (NMe 2 ) 2 , Zr (NEt 2 ) 4 , Hf (CH 2 Ph) 4 , HfCl 2 (CH 2 Ph ) 2, Hf (CH 2 SiMe 3) 4,
  • TiX 4 examples include Ti (CH 2 Ph) 4 , TiCl 2 (CH 2 Ph) 2 , Ti (CH 2 SiMe 3 ) 4 , TiF 4 , TiCl 4 , TiBr 4 , TiI 4 , and Ti (OMe) 4. , Ti (OEt) 4 , Ti (Oi-Pr) 4 , TiCl 2 (Oi-Pr) 2 , Ti (On-Bu) 4 , Ti (Oi-Bu) 4 , Ti ( O-t-Bu) 4, Ti (OPh) 4, Ti (NMe 2) 4, TiCl 2 (NMe 2) 2, Ti (NEt 2) 4 and the like.
  • the complex (1) may be formed by reacting the compound (2) and the compound (3) as they are. If necessary, the compound (2) is reacted with a base and then the compound (3) is reacted. It may be formed. These reactions are usually performed in a solvent. Examples of the base to be used include organic lithium reagents, Grignard reagents and metal hydrides.
  • n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazane, Potassium hexamethyldisilazane, sodium hydride or potassium hydride can be mentioned, and preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride.
  • the reaction is preferably carried out under dehydration and deoxygenation. Specifically, it is under dry nitrogen or dry argon.
  • the amount of compound (2) used may be 1 molar equivalent or more with respect to compound (3), and is preferably in the range of 1.0 to 1.5 molar equivalents. Moreover, when the compound (2) remains in the course of the reaction, the compound (3) may be added during the reaction.
  • the temperature at which compound (2) and compound (3) are reacted is in the range of ⁇ 100 ° C. to 150 ° C., preferably in the range of ⁇ 80 ° C. to 50 ° C. However, it is not intended to be limited to this range.
  • the reaction of the compound (2) and the compound (3) may be carried out until the time when the yield of the product becomes the highest, preferably 5 minutes to 48 hours, more preferably 10 minutes to 24 hours.
  • the temperature at which the compound (2) reacts with the base is in the range of ⁇ 100 ° C. to 150 ° C., preferably in the range of ⁇ 80 ° C. to 50 ° C. However, it is not intended to be limited to this range.
  • the reaction time of the compound (2) and the base may be performed until the product yield becomes the highest, for example, 5 minutes to 24 hours, preferably 10 minutes to 12 hours, more preferably 30 minutes. ⁇ 3 hours.
  • the temperature at which the compound (2) and the compound produced by reacting the base and the compound (3) are reacted is in the range of ⁇ 100 ° C. to 150 ° C., preferably in the range of ⁇ 80 ° C. to 50 ° C. However, it is not intended to be limited to this range.
  • the reaction time of the compound produced by reacting the compound (2) with the base and the compound (3) may be up to the time when the yield of the product is the highest, for example, 5 minutes to 48 hours. It is preferably 10 minutes to 24 hours.
  • the solvent to be used is not particularly limited as long as it is a solvent generally used in similar reactions, and examples thereof include a hydrocarbon solvent or an ether solvent.
  • Preferred is toluene, benzene, o-xylene, m-xylene, p-xylene, hexane, pentane, heptane, cyclohexane, diethyl ether or tetrahydrofuran, and more preferred is diethyl ether, toluene, tetrahydrofuran, hexane, pentane, heptane. Or cyclohexane.
  • Compound (2) can be synthesized, for example, according to the method described in Reference: Journal of American Chemical Society, 2009, Volume 131, 13566-13567. Specifically, although it can manufacture by the following scheme 2, it should not be limited to this method. Hereinafter, each process will be described in detail.
  • a compound represented by the following general formula (4), (5-1), (5-2), (6-1), (6-2), (7-1), or (7-2) are represented by “compound (4)”, “compound (5-1)”, “compound (5-2)”, “compound (6-1)”, “compound (6-2)”, “compound (7- 1) "or” Compound (7-2) ".
  • compound (5-1) and “compound (5-2)” are collectively referred to as “compound (5)”
  • compound (6-1) and “compound (6-2)” are referred to as “compound (6-1)”.
  • compound (6) and “compound (7-1)” and “compound (7-2)” are collectively referred to as “compound (7)”.
  • R 1 ⁇ R 10 and n in each compound in scheme2 the general formula (1-1) and (1-2) is the same as R 1 ⁇ R 10 and n in.
  • X ′ represents an anionic leaving group such as a halogen atom, acetate group, trifluoroacetate group, benzoate group, CF 3 SO 3 group, CH 3 SO 3 group, 4-MeC 6 H 4 SO 3 group or PhSO 3 groups, etc. are mentioned, and preferred are a chlorine atom, a bromine atom, an iodine atom, a CF 3 SO 3 group, a CH 3 SO 3 group, a 4-MeC 6 H 4 SO 3 group or a PhSO 3 group.
  • Compound (6) can be synthesized by reacting compound (4) with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (5) in the presence of a base.
  • the base is not particularly limited, but includes inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium hydrogen carbonate, and amine bases such as triethylamine and triisobutylamine. Preferably, it is an amine base.
  • This reaction can be performed in an atmosphere of air, helium, argon, or nitrogen.
  • it is under a helium, argon or nitrogen atmosphere, more preferably under a nitrogen or argon atmosphere.
  • the compound (6) may be purified as necessary.
  • a purification method for example, an ammonium chloride aqueous solution, a hydrochloric acid aqueous solution or a sodium chloride aqueous solution is added to the reaction solution, followed by addition of ethyl acetate or diethyl ether, and an extraction operation is performed to remove excess base or salt.
  • the purity of the compound (6) can be increased by purification operations such as distillation, recrystallization or silica gel chromatography.
  • Compound (2) can be synthesized by reacting compound (6) with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (7) in the presence of a base.
  • the base examples include inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium hydrogen carbonate, and amine bases such as triethylamine and triisobutylamine, with amine bases being preferred.
  • inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium hydrogen carbonate
  • amine bases such as triethylamine and triisobutylamine, with amine bases being preferred.
  • This reaction can be performed in an atmosphere of air, helium, argon, or nitrogen.
  • it is under a helium, argon or nitrogen atmosphere, more preferably under a nitrogen or argon atmosphere.
  • the compound (2) may be purified as necessary.
  • a purification method for example, an ammonium chloride aqueous solution, a hydrochloric acid aqueous solution or a sodium chloride aqueous solution is added to the reaction solution, followed by addition of ethyl acetate or diethyl ether, and an extraction operation is performed to remove excess base or salt.
  • the purity of the compound (2) can be increased by purification operations such as distillation, recrystallization or silica gel chromatography.
  • the compound (2) can also be obtained by reacting the compound (6) and the compound (7) produced in the reactor by controlling the reaction conditions of [step 1].
  • R 1 is the same as R 5 (or R 9 is R 10 )
  • R 2 is the same as R 6
  • R 3 is the same as R 7
  • R 4 is the same as R 8
  • the compound (5) and the compound (7) are combined, and the compound (4) is reacted with 2.0 to 8.0 equivalents, preferably 2.0 to 4.0 equivalents in the presence of a base. (2) can also be synthesized.
  • the groups corresponding to R 3 and R 7 in the general formula (2-1) in each of the above compounds are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, Or the compound substituted with the methyl group is also mentioned.
  • Specific examples of the compound (2-2) include, in addition to the specific examples of the compound (2-1), the following compounds and R 3 and R 7 in the general formula (2-2) in these compounds. And a compound in which a group corresponding to is substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.
  • the general formula (5-1) or (7-1) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom. , An iodine atom, or a compound substituted with a methyl group.
  • Specific examples of the compound (5-2) and the compound (7-2) include, in addition to the specific examples of the compound (5-1) and the compound (7-1), the following compounds and the above compounds in these compounds. And compounds in which the groups corresponding to R 3 and R 7 in formula (5-2) or (7-2) are substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group. .
  • the complex (1) described above is used as a polymerization catalyst component in the production of a polymer by homopolymerization of olefins or copolymerization of two or more polymerizable olefins.
  • the catalyst component for homopolymerization is used. It is.
  • the polymerization catalyst a polymerization catalyst obtained by bringing the complex (1), the activation promoter component and the carrier into contact with each other is used.
  • activation promoter component examples include an activation co-catalyst component containing a Group 13 element of the periodic table.
  • an organoaluminum compound (A), a boron compound (B), and boron described below are used.
  • the at least 1 sort (s) of compound chosen from the group which consists of a compound (C) can be mentioned.
  • the organoaluminum compound (A), the boron compound (B), and the boron compound (C) are respectively referred to as “activation promoter component (A)”, “activation promoter component (B)”, and “ Hereinafter, it may be referred to as “activation promoter component (C)”.
  • organoaluminum compound (A) in the present invention a known organoaluminum compound can be used.
  • any one of the following compounds (A-1), (A-2), and (A-3), or a mixture of 2 to 3 thereof can be exemplified.
  • A-1) Organoaluminum compound represented by general formula E 1 a AlY 1 3-a
  • A-2) General formula ⁇ -Al (E 2 ) —O— ⁇ having a structure represented by b
  • E 1 has 1 to E 2 and E 3 each independently represents a hydrocarbyl group having 1 to 8 carbon atoms, an alkoxy group containing an electron withdrawing group or an electron withdrawing group.
  • An aryloxy group to be contained is represented.
  • a plurality of E 1 s , E 2 s, and E 3 s may be the same or different.
  • Y 1 represents a hydrogen atom or a halogen atom, and a plurality of Y 1 may be the same or different.
  • a represents an integer of 0 ⁇ a ⁇ 3
  • b represents an integer of 2 or more
  • c represents an integer of 1 or more.
  • Examples of the hydrocarbyl group having 1 to 8 carbon atoms in E 1 to E 3 of the compounds (A-1) to (A-3) include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, and a normal butyl group. Group, isobutyl group, normal pentyl group, and neopentyl group.
  • E 2 and E 3 of the compounds (A-2) and (A-3) may be an alkoxy group containing an electron withdrawing group or an aryloxy group containing an electron withdrawing group.
  • Hammett's rule substituent constant ⁇ and the like are known, and a functional group having positive ⁇ can be cited as an electron withdrawing group.
  • the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group.
  • alkoxy group containing an electron withdrawing group in E 2 and E 3 examples include a fluoromethoxy group, a chloromethoxy group, a bromomethoxy group, an iodomethoxy group, a difluoromethoxy group, a dichloromethoxy group, a dibromomethoxy group, Iodomethoxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, triiodomethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, 2,2,2- Tribromoethoxy group, 2,2,2-triiodoethoxy group, pentafluoroethoxy group, pentachloroethoxy group, pentabromoethoxy group, pentaiodoethoxy group, 2,2,3,3,3-pentafluoropropoxy group 2,2,3,3,3-pentachloropropoxy group, 2,2,3,3 3-pen
  • Examples of the aryloxy group containing an electron withdrawing group in E 2 and E 3 include, for example, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 2,3-difluorophenoxy group, 2, 4-difluorophenoxy group, 2,5-difluorophenoxy group, 2,6-difluorophenoxy group, 3,4-difluorophenoxy group, 3,5-difluorophenoxy group, 2,3,4-trifluorophenoxy group, 2 , 3,5-trifluorophenoxy group, 2,3,6-trifluorophenoxy group, 2,4,5-trifluorophenoxy group, 2,4,6-trifluorophenoxy group, 3,4,5-tri Fluorophenoxy group, 2,3,4,5-tetrafluorophenoxy group, 2,3,4,6-tetrafluorophenoxy group, , 3,5,6-tetrafluorophenoxy group, 2,3,4,5,6-pentafluorophenoxy group, 2,3,
  • organoaluminum compound (A-1) represented by the general formula E 1 a AlY 1 3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum.
  • Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkyls such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride Aluminum dichloride; Dimethyla Mini um hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, dialkylaluminum hydride such as dihexyl aluminum hydride; and the like. Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.
  • An aryloxy group containing an electron withdrawing group such as 4-fluorophenoxy group, 3,4,5-trifluorophenoxy group, 2,3,4,5,6-pentaflu
  • aluminoxane can be made by various methods. There is no restriction
  • the compound (A-2) and the compound (A-3) obtained by the above method may be used after removing volatile components by distillation, if necessary. Further, the compound obtained by distilling off the volatile components and drying may be washed with an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) and dried again.
  • an appropriate organic solvent benzene, toluene, aliphatic hydrocarbon, etc.
  • B boron compound (B) in the present invention
  • B-1 Boron compound represented by the general formula BR 11 R 12 R 13
  • B-2 Boron compound represented by the general formula U + (BR 11 R 12 R 13 R 14 ) — 3
  • B 11 to R 14 each independently represents a halogen atom or a carbon atom number of 1
  • R 11 to R 14 may be the same as or different from each other.
  • R 11 to R 14 are preferably each independently a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a halogenated hydrocarbyl group having 1 to 20 carbon atoms.
  • B is a boron atom in a trivalent valence state.
  • U + is an inorganic or organic cation.
  • T is a neutral Lewis base and (TH) + is a Bronsted acid.
  • U + that is an inorganic cation examples include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation.
  • Examples of U + that is an organic cation include a triphenylcarbenium cation.
  • borate represented by (BR 11 R 12 R 13 R 14 ) — include, for example, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis ( 2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate -To, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like.
  • Examples of (TH) + that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium.
  • boron compound (B-1) examples include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5).
  • -Tetrafluorophenyl) borane tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like.
  • boron compound (B-2) examples include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Examples include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate. .
  • boron compound (B-3) examples include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, (N-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N , N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethyl
  • boron compound (C) in the present invention examples include use of any of the following compounds (C-1) and (C-2).
  • C-1) Boron compound represented by the general formula U + (BR 15 R 16 R 17 R 18 ) ⁇
  • C-2) General formula (TH) + (BR 15 R 16 R 17 R 18 ) - boron in the compound formulas, R 15 ⁇ R 18 represented by each independently, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl of 1 to 20 carbon atoms Group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a disubstituted amino group having 2 to 20 carbon atoms.
  • R 15 to R 18 may be the same or different from each other, but at least one of R 15 to R 18 has the general formula (ZH) (wherein Z represents O, S, NR or PR; R represents a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermyl group, or hydrogen.
  • B is a boron atom in a trivalent valence state.
  • U + is an inorganic or organic cation.
  • T is a neutral Lewis base and (TH) + is a Bronsted acid.
  • borate represented by (BR 15 R 16 R 17 R 18 ) — include triphenyl (hydroxyphenyl) borate, diphenyl di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, Tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (Hydroxyphenyl) borate, tris (3,5-bis (trifluoromethyl) phenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxy The Borate, tris (pentafluorophenyl) (2-hydroxycyclohexyl) borate, tris
  • boron compound (C-1) examples include ferrocenium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, silver tris (pentafluorophenyl) (4-hydroxyphenyl) borate, triphenylcarbenium tris. (Pentafluorophenyl) (4-hydroxyphenyl) borate and the like.
  • boron compound (C-2) examples include triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tripropylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri (n- Butyl) ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri (n-butyl) ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, N, N-dimethylanilinium tris (pentafluorophenyl) ) (4-hydroxyphenyl) borate, N, N-diethylanilinium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, N, N-2,4,6-pentamethylanilinium tris Tafluorophenyl) (4-hydroxyphenyl) borate, N, N-dimethylanilinium tri
  • Carrier As the carrier, a porous material is preferably used, an inorganic material or an organic polymer is preferable, and an inorganic material is more preferable.
  • inorganic substance examples include inorganic oxides, magnesium compounds, clays, clay minerals, and combinations thereof. Among these, inorganic oxides are preferable.
  • Examples of the inorganic oxide SiO 2, Al 2 O 3 , MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO 2, V 2 O 5, Cr 2 O 3 , and mixtures thereof (For example, SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 , and SiO 2 —TiO 2 —MgO). . Of these, SiO 2 and / or Al 2 O 3 are preferable, and SiO 2 is particularly preferable.
  • the inorganic oxide includes a small amount of Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg (NO 3 ) 2. Carbonates, sulfates, nitrates or oxides such as Al (NO 3 ) 3 , Na 2 O, K 2 O, and Li 2 O may be included.
  • magnesium compound examples include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride.
  • Alkoxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, and 2-ethylhexoxymagnesium; phenoxymagnesium And allilo such as dimethylphenoxymagnesium Shi magnesium; and carboxylic acid salts of magnesium such as magnesium laurate and magnesium stearate.
  • magnesium halide or alkoxymagnesium and more preferred is magnesium chloride or butoxymagnesium.
  • Examples of the clay or the clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophilite, talc, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, Dickite, and halloysite.
  • preferred is smectite, montmorillonite, hectorite, laponite or saponite, and more preferred is montmorillonite or hectorite.
  • the inorganic substance is preferably dried to substantially remove moisture, and is preferably dried by heat treatment.
  • the heat treatment is usually carried out at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for inorganic substances whose moisture cannot be visually confirmed.
  • the heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Examples of the drying method include a method of circulating an inert gas (for example, nitrogen or argon) dried under heating at a constant flow rate, and a method of depressurizing under heating.
  • the average particle size of the inorganic substance is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, and still more preferably 10 to 100 ⁇ m.
  • the pore volume of the inorganic substance is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g.
  • the specific surface area of the inorganic substance is preferably 10 to 1000 m 2 / g, more preferably 100 to 500 m 2 / g.
  • organic polymer for the carrier a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group is preferred.
  • Examples of the functional group having active hydrogen include primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid Groups, sulfinic acid groups, sulfenic acid groups, thiol groups, thioformyl groups, pyrrolyl groups, imidazolyl groups, piperidyl groups, indazolyl groups, and carbazolyl groups.
  • a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group particularly preferably a primary amino group, Secondary amino group, amide group or hydroxy group.
  • These functional groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • non-proton-donating Lewis basic functional group examples include pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, N , N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted Examples include a carbamoyl group, a thioalkoxy group, a substituted sulfinyl group, a substituted sulfonyl group, and a substituted sulfonic acid group.
  • heterocyclic group preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring, and particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group. And most preferably a pyridyl group.
  • These functional groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • the amount of the functional group having active hydrogen or the non-proton-donating Lewis basic functional group is preferably 0.01 to 50 mmol / g as the molar amount of the functional group per gram of polymer unit, more preferably 0.8. 1 to 20 mmol / g.
  • a method for producing the polymer having the functional group a method of homopolymerizing a monomer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group and one or more polymerizable unsaturated groups, And a method of copolymerizing the monomer and another monomer having a polymerizable unsaturated group.
  • the monomer is preferably combined with a crosslinking polymerizable monomer having two or more polymerizable unsaturated groups.
  • the monomer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups include (1) a functional group having active hydrogen and one or more polymerizations. And a monomer having an unsaturated proton group and (2) a monomer having a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated 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 amide compounds, and vinyl group-containing hydroxy compounds. Can be mentioned. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine, 1- And ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, and 3-buten-1-ol.
  • Monomers having a non-proton donating Lewis basic functional group and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole.
  • Examples of the other monomer having a polymerizable unsaturated group include ethylene, ⁇ -olefin, and aromatic vinyl compounds. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 4- And methyl-1-pentene, styrene, and combinations of two or more thereof. Among these, ethylene or styrene is preferable.
  • Examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.
  • the average particle size of the organic polymer is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m.
  • the pore volume of the organic polymer is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g.
  • the specific surface area of the organic polymer is preferably 10 to 1000 m 2 / g, more preferably 50 to 500 m 2 / g.
  • the organic polymer is preferably dried to substantially remove moisture, and is preferably dried by heat treatment.
  • the heat treatment is usually carried out at a temperature of 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 not particularly limited, but is preferably 30 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Examples of the drying method include a method of circulating an inert gas (for example, nitrogen or argon) dried under heating at a constant flow rate, and a method of depressurizing under heating.
  • the volume standard geometric standard deviation of the particle size of the support is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less, from the viewpoint of the particle size distribution of the obtained polymer.
  • the carrier, inorganic material is preferred, the inorganic oxide is more preferably, SiO 2 is more preferred.
  • the olefin polymerization catalyst of the present invention can be obtained by contacting the complex represented by the general formula (1-1) or (1-2), the co-catalyst component for activation, and the support.
  • the activation promoter component is at least one compound selected from the group consisting of an organoaluminum compound (A), a boron compound (B), or a boron compound (C). Further, as the activation promoter component (A), a plurality of components among the organoaluminum compounds (A-1) to (A-3) may be used.
  • Method 1 A method in which a support is brought into contact with a contact product obtained by bringing the complex (1) into contact with an activation promoter component.
  • Method 2 A method in which the complex (1) is brought into contact with a contact product obtained by bringing the support into contact with the activating cocatalyst component.
  • Method 3 A method of bringing an activating co-catalyst component into contact with a contact product obtained by bringing the carrier into contact with the complex (1).
  • Method 4 A method in which the complex (1), the activating co-catalyst component and the support are simultaneously contacted.
  • the complex (1) may be an isolated one, or may be used as it is by contacting the compound (2) with the compound (3).
  • the contact product in contact with the support and the activation promoter component is brought into contact with the contact product in contact with the complex (1) and the activation promoter component.
  • the method is preferred.
  • the reaction it is preferable to carry out the reaction in the presence of a solvent.
  • the solvent include aromatic hydrocarbyl solvents such as benzene, toluene and xylene, aliphatic hydrocarbyl solvents such as hexane, heptane and octane, and halogenated hydrocarbyl solvents such as dichloromethane.
  • aromatic hydrocarbyl solvents such as benzene, toluene and xylene
  • aliphatic hydrocarbyl solvents such as hexane, heptane and octane
  • halogenated hydrocarbyl solvents such as dichloromethane.
  • the solvent which does not dissolve is preferable, and the solvent which dissolves the complex (1) and the promoter component for activation is more preferable.
  • the temperature and time for contact are not particularly limited.
  • the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 120 ° C.
  • the contact time is usually about 30 minutes to 12 hours, preferably about 30 minutes to 8 hours, more preferably about 30 minutes to 6 hours.
  • the ratio of each component when contacting the carrier, the complex (1) and the activating cocatalyst component (A) is 0.05 to 20 parts by weight of the complex (1) per 1 part by weight of the carrier.
  • Component (A) is 10 to 300 parts by weight, preferably 0.1 to 10 parts by weight of complex (1) and 20 to 200 parts by weight of activation promoter component (A) per part by weight of the support.
  • the ratio of each component when contacting the carrier, the complex (1) and the activating co-catalyst component (B) is 0.05 to 20 parts by weight of the complex (1) per 1 part by weight of the carrier.
  • Component (B) is 0.1 to 60 parts by weight, preferably 0.1 to 10 parts by weight of complex (1) and 0.2 to 30 parts by weight of activation promoter component (B) per part by weight of the support. It is.
  • the olefin polymerization catalyst of the present invention can also be obtained by bringing the complex (1), the carrier and the activation promoter component (C) into contact with each other, but the activation promoter component (A) can be used in combination. preferable.
  • These contact methods are not particularly limited, and a plurality of components among the compounds (A-1) to (A-3) may be used as the activation promoter component (A).
  • the order of contacting the support, the complex (1) and the activating cocatalyst components (C) and (A) is not particularly limited, and examples thereof include the following methods. Preferably, it is Method 6, Method 7 or Method 8, and more preferably Method 6 or Method 8.
  • the order of charging in each contact of each method is not particularly limited, and some or all of these contacts may be performed in a polymerization tank or a reactor.
  • Method 5 A method of bringing the co-catalyst component for activation (C) into contact with the contact product obtained by bringing the co-catalyst component for activation (A) into contact with the carrier, and further bringing the complex (1) into contact therewith.
  • Method 6 A method in which the support is brought into contact with the contact product obtained by bringing the activating cocatalyst component (A) and the activating cocatalyst component (C) into contact, and the complex (1) is further brought into contact.
  • Method 7 A method in which the complex (1) is brought into contact with the contact product obtained by bringing the activating cocatalyst component (A) and the carrier into contact, and the activating cocatalyst component (C) is further brought into contact.
  • Method 8 A method of bringing the co-catalyst component for activation (C) into contact with the contact product obtained by bringing the co-catalyst component for activation (A) into contact with the carrier, and further bringing the complex (1) into contact therewith.
  • the complex (1) may be an isolated one, or may be used as it is by contacting the compound (2) with the compound (3).
  • the reaction it is preferable to carry out the reaction in the presence of a solvent.
  • the solvent include aromatic hydrocarbyl solvents such as benzene, toluene and xylene, aliphatic hydrocarbyl solvents such as hexane, heptane and octane, and halogenated hydrocarbyl solvents such as dichloromethane.
  • aromatic hydrocarbyl solvents such as benzene, toluene and xylene
  • aliphatic hydrocarbyl solvents such as hexane, heptane and octane
  • halogenated hydrocarbyl solvents such as dichloromethane.
  • the solvent which does not dissolve is preferable, and the solvent which dissolves the complex (1) and the promoter component for activation is more preferable.
  • the temperature and time for contact are not particularly limited.
  • the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 120 ° C.
  • the contact time is usually about 30 minutes to 12 hours, preferably about 30 minutes to 8 hours, more preferably about 30 minutes to 6 hours.
  • the ratio of each component when contacting the support, the complex (1), the activating co-catalyst component (A) and the activating co-catalyst component (C) is 0.05% of complex (1) per 1 part by weight of the support.
  • the catalyst according to the present invention produced by the above-described method can be used for homopolymerization of olefins or for copolymerization of two or more olefins.
  • the catalyst according to the present invention can be particularly preferably used for homopolymerization of olefins having 2 to 6 carbon atoms or copolymerization of two or more olefins having 2 to 6 carbon atoms.
  • the method for producing an olefin polymer in the present invention is a method including polymerizing an olefin alone in the presence of the catalyst or copolymerizing two or more olefins.
  • the olefin can be a monoolefin or a diolefin.
  • the monoolefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, etc.
  • 1-alkene having 3 to 10 carbon atoms which may be branched), or cyclopentene, cyclohexene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene , Tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene , 5-Met Sicarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetra
  • diolefin examples include 1,5-hexadiene, 1,4-hexadiene, 1,6-heptadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5 -Methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-hexadiene, 1,3-octadiene, 1,3 -Cyclooctadiene, 1,3-cyclohexadiene, butad
  • Preferred monoolefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, and the like.
  • Olefin having 2 to 10 carbon atoms more preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, vinylcyclohexane and the like.
  • isotactic pentad fraction [mmmm] (%) is used.
  • the isotactic pentad fraction referred to here is A.I. Isotactic linkage at the pentad unit in a crystalline polypropylene molecular chain measured using the method published by Macrobells, 1973, No. 6, pp. 925-926, ie, using 13 C-NMR. In other words, it is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded.
  • the monomer constituting the copolymer examples include ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 1-decene, ethylene and 4 -Methyl-1-pentene, ethylene and vinylcyclohexane, ethylene and 4-methyl-1-pentene, ethylene and butadiene, ethylene and 1,5-hexadiene.
  • ethylene and carbon such as ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, ethylene and 4-methyl-1-pentene Copolymerization with olefins having 3 to 10 atoms, more preferably ethylene and carbon atoms such as ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, etc. Copolymerization with olefins of 3 to 8.
  • the particle property is very high by the method of bringing the contact product in contact with the support and the activation promoter component into contact with the contact product in contact with the complex (1) and the activation promoter component.
  • the following ethylene- ⁇ -olefin copolymer excellent in the above can be obtained.
  • the following copolymer particles are not particles obtained by granulating copolymer particles obtained by copolymerization of ethylene and ⁇ -olefin, but directly by copolymerizing ethylene and ⁇ -olefin in a polymerization reactor. Means the resulting particles.
  • the ethylene- ⁇ -olefin copolymer having a volume particle size of 300 ⁇ m or less and a polymer particle content of 2% by volume or less, a 50% volume reference particle size (D50) of 500 ⁇ m or more, and a particle bulk density of 400 kg / m 3 or more. Polymer particles.
  • the amount of particles having a volume standard particle size of 300 ⁇ m or less is preferably smaller from the viewpoint of operational stability, preferably 2% by volume or less, more preferably 1% by volume or less, More preferably, it is 0.5 volume% or less.
  • the ethylene- ⁇ -olefin copolymer particles have a 50% volume standard particle diameter (D50) of 500 ⁇ m or more, and are preferably higher from the viewpoint of productivity, preferably 750 ⁇ m or more, more preferably 1000 ⁇ m or more. From the viewpoint of the fluidity of the particles, it is preferably not too large, preferably 4000 ⁇ m or less, more preferably 3500 ⁇ m or less, and still more preferably 3000 ⁇ m or less.
  • D50 50% volume standard particle diameter
  • the ethylene- ⁇ -olefin copolymer particles have a particle bulk density of 400 kg / m 3 or more, and preferably have a high particle bulk density from the viewpoint of enhancing production, preferably 425 kg / m 3 or more, and more preferably Is 450 kg / m 3 or more.
  • the particle bulk density (BD) can be determined by filling a 10 cc graduated cylinder from 10 cm above the powder and dividing the mass of the powder by the volume including the voids between the particles.
  • the particle size measurement on the volume basis of the polymer particles can be calculated, for example, by measuring the particle size distribution by dispersing the polymer particles in a dry state using a laser diffraction particle size distribution analyzer HELOS & RODOS system manufactured by SYMPATEC. Can do.
  • the content derived from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer particles obtained by the production method of the present invention is preferably smaller from the viewpoint of the tackiness of the copolymer, and the number of short chain branches (N SCB ) Is less than 30 / 1000C, more preferably less than 25 / 1000C, and even more preferably less than 20 / 1000C.
  • the melt flow rate (MFR) of the ethylene- ⁇ -olefin copolymer obtained by the production method of the present invention is the method defined in JIS K7210-1995 under the conditions of a temperature of 190 ° C. and a load of 21.18 N. Is a value measured by.
  • the MFR of the ethylene- ⁇ -olefin copolymer obtained by the production method of the present invention is 0.1 to 100 g / 10 min.
  • the MFR is preferably 0.2 g / 10 min or more from the viewpoint of improving molding processability, particularly from the viewpoint of reducing the extrusion load. Further, from the viewpoint of increasing the melt tension and the mechanical strength of the resulting molded article, it is preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and further preferably 20 g / 10 min or less.
  • H-MFR is a value of MFR measured under the conditions of a load of 211.82 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995.
  • the MFRR is a value obtained by dividing H-MFR by the MFR measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. in the method specified in JIS K7210-1995. is there.
  • the MFRR of the ethylene- ⁇ -olefin copolymer obtained by the production method of the present invention is preferably 70 or more, more preferably 100 or more, and still more preferably, from the viewpoint of further reducing the extrusion load during the molding process. Is 130 or more, particularly preferably 170 or more. Moreover, from a viewpoint which raises the mechanical strength of the molded object obtained more, Preferably it is 300 or less, More preferably, it is 250 or less.
  • the density of the ethylene- ⁇ -olefin copolymer obtained by the production method of the present invention is 850 to 940 kg / m 3 , and preferably 930 kg / m 3 from the viewpoint of increasing the impact strength of the mechanical strength of the obtained molded product. 3 or less. From the viewpoint of enhancing among tensile strength of mechanical strength of the resulting molded product, it is preferably 870 kg / m 3 or more, more preferably 880 kg / m 3 or more, more preferably 890 kg / m 3 or more, particularly preferably Is 900 kg / m 3 or more
  • the weight average molecular chain length (hereinafter sometimes referred to as “Aw”) and the number average molecular chain length (hereinafter referred to as “An”) of the ethylene- ⁇ -olefin copolymer obtained by the production method of the present invention is 2 to 10. If Aw / An is too small, the extrusion load at the time of molding may increase. Aw / An is preferably 2.5 or more. When Aw / An is too large, the mechanical strength of the obtained molded product may be lowered. Aw / An is preferably 6.5 or less, more preferably 6 or less, and even more preferably 5 or less.
  • N LCB has a carbon atom number of 5 or more, with the total area of all peaks observed at 5 to 50 ppm as 1000 from the 13 C-NMR spectrum measured by the carbon nuclear magnetic resonance ( 13 C-NMR) method. It is obtained by determining the area of the peak derived from the methine carbon to which the branch is bonded.
  • the peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded is around 38.2 ppm (Reference: Scientific literature “Macromolecules”, (USA), American Chemical Society, 1999, Vol. 32, p.3817-3818) ).
  • the N LCB of the ethylene- ⁇ -olefin copolymer obtained by the production method of the present invention is preferably at least 0.05, more preferably at least 0.10, per 1000 carbons from the viewpoint of processability. Especially preferably, it is 0.15 or more. From the viewpoint of the mechanical strength of the obtained polymer, it is preferably not too much, preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.
  • the olefin polymer obtained by the method for producing an olefin polymer of the present invention has an extrusion load at the time of molding, bubble stability at the time of forming an inflation film, neck-in at the time of T-die film molding, and a shape retention of the parison at the time of hollow molding. Excellent moldability such as properties, and excellent mechanical strength. Moreover, the transparency of the molded product is also excellent.
  • the olefin polymer is molded by a known molding method, for example, an extrusion molding method such as an inflation film molding method and a T-die film molding method, a hollow molding method, an injection molding method, a compression molding method, or the like.
  • an extrusion molding method and a hollow molding method are preferably used, and an inflation film molding method, a T-die film molding method, and a hollow molding method are particularly preferably used.
  • the olefin polymer is used after being molded into various forms.
  • the form of a molded article is not specifically limited, it is used for a film, a sheet, a container (tray, bottle, etc.), etc.
  • the molded article is also suitably used for applications such as food packaging materials; pharmaceutical packaging materials; electronic component packaging materials used for packaging semiconductor products, etc .; surface protection materials.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of each polymer are based on the weight average molecular chain length (Aw) in terms of polystyrene and the number average molecular chain length (An) in terms of polystyrene. Factors were calculated from the following formulas with 17.7 and 26.4, respectively.
  • Molecular weight (Mw, Mn) molecular chain length (Aw, An) ⁇ Q factor
  • Density (d, unit: Kg / m 3 ) Measured according to the method defined in Method A of JIS K7112-1980. The sample was annealed according to JIS K6760-1995.
  • N SCB Number of short chain branches (N SCB , unit: 1 / 1000C)
  • FT-IR7300 infrared spectrophotometer
  • This N SCB value represents the content of monomer units derived from ⁇ -olefin in a copolymer of ethylene and ⁇ -olefin.
  • Melt flow rate (MFR, unit: g / 10 min) In the method defined in JIS K7210-1995, measurement was performed by the method A under the conditions of a load of 21.18 N and a temperature of 190 ° C.
  • H-MFR Melt flow rate ratio
  • Particle bulk density (10) Particle bulk density (BD)
  • the particle bulk density (BD) is a value obtained by dividing the mass of the powder by the volume including 10 cm of powder in a 10 cc graduated cylinder and including the voids between the particles.
  • Elemental analysis Aluminum and hafnium A metal component was extracted by irradiating an ultrasonic wave after throwing the sample into a sulfuric acid aqueous solution (1M). The obtained liquid portion was quantified by ICP emission spectrometry.
  • the formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure.
  • Ether and saturated aqueous ammonium chloride solution were added to the resulting residue, and the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (developing solvent hexane-dichloromethane 1: 1) to obtain 6.74 g (yield 89%) of the title compound as colorless crystals.
  • Triethylamine 6.5 mL (47 mmol) was added here, and it heated and refluxed for 3 hours.
  • the reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue.
  • the organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate.
  • the solvent was distilled off under reduced pressure to obtain 8.05 g of a mixture containing 5-tert-butyl-3-cumylsalicylaldehyde (purity 79.9%, yield 93%).
  • Triethylamine 1.1 mL (7.9 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. After the volatile components were distilled off from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 0.7 mL (5.0 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. Further, 0.05 g (0.013 mmol) of 5-tert-butyl-2-hydroxy-3- (3,5-dimethyl-1-adamantyl) benzyl bromide was added, and the mixture was stirred at room temperature for 1 hour. After the volatile components were distilled off from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate and 2% HCl were added to the residue. The organic layer was washed with water and saturated brine in that order and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 2.2 g of a mixture containing 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] salicylaldehyde (yield> 99%). Obtained.
  • Triethylamine 1.0 mL (7.2 mmol) was added here, and it stirred at room temperature for 15.5 hours.
  • the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure.
  • Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue.
  • the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • Example 1 The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, 200 mL of hexane was charged as a solvent, and the reactor was heated to 70 ° C. After the temperature rise, the ethylene pressure was adjusted to 0.6 MPa and then fed, and 0.5 mL (0.5 mmol) of triisobutylaluminum (1.0 mol / L, toluene solution) was synthesized in Reference Example 7 [cyclooctane.
  • Example 2 [Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] synthesized in Reference Example 8 instead of dibenzylzirconium Example 1, except that 1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium was used and the amount of MAO / SiO 2 was 17.1 mg. It carried out similarly. The results are shown in Table 1.
  • Example 3 An autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon, 185 mL of hexane was charged as a solvent, 15 mL of 1-hexene was charged as a comonomer, and the reactor was heated to 70 ° C. After raising the temperature, the ethylene pressure was adjusted to 0.6 MPa and then fed, and triisobutylaluminum (1.0 mol / L, toluene solution) 0.5 mL (0.5 mmol) was synthesized in Reference Example 5 [cyclooctanediyl.
  • Example 4 An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of hexane as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was raised to 70 ° C.
  • Example 5 [Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] synthesized in Reference Example 8 instead of dibenzylzirconium 1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium (1.0 mmol / L, toluene solution) 0.2 mL (0.2 ⁇ mol) was used, The same operation as in Example 4 was carried out except that the amount of MAO / SiO 2 input was 20.4 mg. The results are shown in Table 2.
  • Table 2 shows the polymerization results obtained in Examples 4 and 5 and Comparative Examples 3 and 4.
  • Example 6 to 32 In Examples 6 to 19, the complex-supported catalyst 2 was used to examine ethylene-butene or ethylene-hexene copolymerization. During the polymerization, the temperature was kept constant, and the pressure was kept constant with ethylene gas to carry out the polymerization. The polymerization conditions and results are summarized in Tables 3 and 4.
  • Examples 20 to 28 the ethylene-butene or ethylene-hexene copolymerization was examined using the complex-supported catalysts 1, 3 to 9. During the polymerization, the temperature was kept constant, and the pressure was kept constant with ethylene gas to carry out the polymerization. The polymerization conditions and results are summarized in Table 5. In Examples 29 to 32, propylene was polymerized using complex-supported catalysts 1 to 4. The polymerization conditions and results are summarized in Table 6.
  • Example 13 The polymer particles obtained in Example 13 were observed with a scanning microscope (manufactured by KEYENCE, VE-8800). An SEM photograph taken at that time is shown in FIG. In addition, (a) and (b) of FIG. 1 image
  • the present invention is useful in the field relating to the production of polyolefins.

Abstract

L'invention concerne un catalyseur de polymérisation oléfinique obtenu en faisant entrer en contact l'un avec l'autre un complexe représenté par la formule générale (1-1) ou (1-2), un composant cocatalyseur d'activation et un support.
PCT/JP2012/070574 2011-08-11 2012-08-10 Catalyseur de polymérisation oléfinique et procédé pour la préparation de polymère oléfinique WO2013022108A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-175679 2011-08-11
JP2011175679A JP2014198744A (ja) 2011-08-11 2011-08-11 オレフィン重合用触媒及びオレフィン重合体の製造方法

Publications (1)

Publication Number Publication Date
WO2013022108A1 true WO2013022108A1 (fr) 2013-02-14

Family

ID=47668610

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/070574 WO2013022108A1 (fr) 2011-08-11 2012-08-10 Catalyseur de polymérisation oléfinique et procédé pour la préparation de polymère oléfinique

Country Status (2)

Country Link
JP (1) JP2014198744A (fr)
WO (1) WO2013022108A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014133005A1 (fr) * 2013-02-27 2014-09-04 三井化学株式会社 Catalyseur de multimérisation d'oléfines et procédé de production d'un multimère oléfinique en présence d'un catalyseur de multimérisation d'oléfines
US10358397B2 (en) 2017-06-29 2019-07-23 Exxonmobil Chemical Patents Inc. Production of olefin dimers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001829A (ja) * 2001-02-13 2009-01-08 Fina Technol Inc メタロセン触媒の調製法
WO2011099583A1 (fr) * 2010-02-12 2011-08-18 国立大学法人埼玉大学 Catalyseur de polymérisation d'oléfine stéréosélective, et procédé de production de polyoléfine stéréosélective

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001829A (ja) * 2001-02-13 2009-01-08 Fina Technol Inc メタロセン触媒の調製法
WO2011099583A1 (fr) * 2010-02-12 2011-08-18 国立大学法人埼玉大学 Catalyseur de polymérisation d'oléfine stéréosélective, et procédé de production de polyoléfine stéréosélective
WO2011099584A1 (fr) * 2010-02-12 2011-08-18 国立大学法人埼玉大学 Catalyseur de polymérisation d'éthylène et procédé de production de polymère d'éthylène

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CAPACCHIONE C. ET AL.: "Synthesis of Branched Polyethylene by Ethylene Homopolymerization Using Titanium Catalysts that Contain a Bridged Bis(phenolate) Ligand", JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY, vol. 42, 2004, pages 2815 - 2822 *
ISHII A. ET AL.: "Synthesis of Titanium(IV) and Zirconium(IV) Complexes with an [OSSO]-Type Bis(phenolate) Ligand Bearing a trans- Cyclohexane-1,2-diyl Ring and 1-Hexene", POLYMERIZATION, ORGANOMETALLICS, vol. 30, 11 May 2011 (2011-05-11), pages 2947 - 2956 *
ISHII A. ET AL.: "Zirconium Complex of an [OSSO]-Type Diphenolate Ligand Bearing trans- 1,2-Cyclooctanediylbis(thio) Core: Synthesis, Structure, and Isospecific 1-Hexene Polymerization", JOURNAL OF AMERICAN CHEMICAL SOCIETY, vol. 131, 2009, pages 13566 - 13567 *
NAKATA N. ET AL.: "Recent advances in the chemistry of Group 4 metal complexes incorporating [OSSO]-type bis(phenolato) ligands as post-metallocene catalysts", POLYMER CHEMISTRY, vol. 2, 16 March 2011 (2011-03-16), pages 1597 - 1610 *
TODA T. ET AL.: "Synthesis and structures of dialkyl zirconium complexes with an [OSSO]-type bis(phenolate) ligand bearing a trans-1,2- cyclooctanediylbis(thio) unit", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 696, 15 March 2011 (2011-03-15), pages 1258 - 1261 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014133005A1 (fr) * 2013-02-27 2014-09-04 三井化学株式会社 Catalyseur de multimérisation d'oléfines et procédé de production d'un multimère oléfinique en présence d'un catalyseur de multimérisation d'oléfines
JP2016203173A (ja) * 2013-02-27 2016-12-08 三井化学株式会社 オレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法
JPWO2014133005A1 (ja) * 2013-02-27 2017-02-02 三井化学株式会社 オレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法
US9616421B2 (en) 2013-02-27 2017-04-11 Mitsui Chemicals, Inc. Catalyst for olefin multimerization and method for producing olefin multimer in presence of catalyst for olefin multimerization
US10358397B2 (en) 2017-06-29 2019-07-23 Exxonmobil Chemical Patents Inc. Production of olefin dimers

Also Published As

Publication number Publication date
JP2014198744A (ja) 2014-10-23

Similar Documents

Publication Publication Date Title
US8470947B2 (en) Ethylenic polymer
US6548686B2 (en) Transition metal compound, catalyst for addition polymerization, and process for producing addition polymer
US8383848B2 (en) Transition metal compound and catalyst for olefin polymerization
US8871885B2 (en) Ethylene-a-olefin copolymer and molded article
US20100310799A1 (en) ETHYLENE-a-OLEFIN COPOLYMER AND MOLDED ARTICLE
JPWO2011099584A1 (ja) エチレン系重合用触媒及びエチレン系重合体の製造方法
US20130041119A1 (en) Olefin polymer producing method, ethylene polymer, and mold product
US9695260B2 (en) Method for producing olefin block polymer using plurality of types of transition metal catalysts
US20040039140A1 (en) Catalyst precursor and olefin polymerization processes
WO2012147995A1 (fr) Procédé de production de copolymère séquencé d'oléfine
WO2012111779A1 (fr) Catalyseur de polymérisation d'éthylène et procédé de production de polymère éthylénique
WO2013022108A1 (fr) Catalyseur de polymérisation oléfinique et procédé pour la préparation de polymère oléfinique
WO2002051878A1 (fr) Particule modifiee, support, composant de catalyseur pour polymerisation d'addition, catalyseur pour polymerisation d'addition et processus de production de polymere d'addition
WO2012111780A1 (fr) Catalyseur pour polymérisation d'oléfine et procédé de production de polymère d'oléfine
JP2013166735A (ja) 新規錯体、当該錯体を含む重合用触媒およびオリゴマー化用触媒、ならびにこれらの利用
JP2013166898A (ja) オレフィン重合用触媒およびオレフィン重合体の製造方法
WO2013022103A1 (fr) Procédé de fabrication d'un polymère à blocs d'oléfine à l'aide d'un complexe d'un métal de transition du groupe 4
WO2013022102A1 (fr) Catalyseur de polymérisation d'éthylène et procédé pour la préparation de polymère d'éthylène
WO2012115259A1 (fr) COPOLYMÈRE D'ÉTHYLÈNE ET D'α-OLÉFINE ET ARTICLE MOULÉ
WO2012111777A1 (fr) Catalyseur de polymérisation d'oléfines et procédé de production de polymère oléfinique
WO2012111778A1 (fr) Catalyseur de polymérisation d'oléfines et procédé de production de polymère oléfinique
JP2013166897A (ja) オレフィン重合用触媒およびオレフィン重合体の製造方法
WO2012169641A1 (fr) Complexe, catalyseur pour la polymérisation d'oléfines, et procédé de production de polymères d'oléfines
JP2013053309A (ja) オレフィン重合用触媒、およびオレフィン重合体の製造方法
JP2012031154A (ja) 新規の遷移金属化合物およびこれを用いたオレフィン重合用触媒

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12822550

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12822550

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP