WO2012111779A1 - Catalyseur de polymérisation d'éthylène et procédé de production de polymère éthylénique - Google Patents

Catalyseur de polymérisation d'éthylène et procédé de production de polymère éthylénique Download PDF

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WO2012111779A1
WO2012111779A1 PCT/JP2012/053730 JP2012053730W WO2012111779A1 WO 2012111779 A1 WO2012111779 A1 WO 2012111779A1 JP 2012053730 W JP2012053730 W JP 2012053730W WO 2012111779 A1 WO2012111779 A1 WO 2012111779A1
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group
carbon atoms
tert
ring
butyl
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PCT/JP2012/053730
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Japanese (ja)
Inventor
正行 長谷川
並河　正明
正人 ▲高▼野
伊藤　和幸
昭彦 石井
憲男 中田
啓太 伊久間
智之 戸田
史彦 河内
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住友化学株式会社
国立大学法人埼玉大学
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Publication of WO2012111779A1 publication Critical patent/WO2012111779A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to a catalyst for copolymerizing ethylene alone or ethylene and ⁇ -olefin using a zirconium complex, and a method for producing an ethylene polymer.
  • Non-Patent Document 1 shows that an ethylene- ⁇ -olefin copolymer containing a long chain branch can be obtained by combining a geometrically constrained single site complex and an organoaluminum oxy compound. It has been shown that melting properties can be improved to some extent by simply introducing long-chain branches.
  • An object of the present invention is to provide a polymerization catalyst containing a post metallocene complex capable of producing an ethylene polymer containing a sufficient amount of long chain branches, and a method for producing an ethylene polymer using this catalyst.
  • the inventor of the present invention has found that the present invention can solve the above-mentioned problems through intensive studies.
  • the present invention relates to an ethylene homopolymerization catalyst or a copolymerization catalyst of ethylene and ⁇ -olefin, which is obtained by bringing a complex represented by the following formula (1) into contact with an activating cocatalyst component. .
  • 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 12 are each independently a 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, Substituted silyl groups, Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
  • the 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 9 And R 10 , and R 11 and R 12 may be independently connected to each other to form a ring, and these rings may have a substituent.
  • Each X independently represents a 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 may have a substituent. 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 ethylene polymer or an ethylene- ⁇ -olefin copolymer using the polymerization catalyst.
  • the present invention relates to a complex represented by the following formula (1 ′).
  • 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 not simultaneously a tert-butyl group.
  • R 2 ′ to R 4 ′ and R 6 ′ to R 12 ′ 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, Substituted silyl groups, Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
  • R 1 ′ to R 12 ′ 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 ring
  • the formula compound residue may have a substituent.
  • R 1 ' ⁇ R 12', R 1 ' and R 2', R 2 'and R 3', R 3 'and R 4', 'a R 6' R 5, and R 6 ' R 7 ′, R 7 ′ and R 8 ′, R 9 ′ and R 10 ′, and R 11 ′ and R 12 ′ may be independently connected to each other to form a ring. May have a substituent.
  • X ′ each independently represents a 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 ′ have a substituent. Also good. Adjacent X ′ 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. )
  • a long-chain branched-containing ethylene polymer can be produced.
  • N is 1 or 2, preferably 2.
  • R 1 and R 5 are preferably each independently a 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, A substituted silyl group, More preferably, each independently an alkyl group having 4 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having
  • R 1 and R 5 are the same, An alkyl group having 5 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 it is a substituted silyl group.
  • R 2 to R 4 and R 6 to R 8 are preferably each independently a 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, A substituted silyl group, More preferably, each independently a hydrogen 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 it is a substituted silyl group.
  • R 2 , R 4 , R 6 and R 8 are more preferably a hydrogen atom. More preferably as R 3 and R 7 , 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 it is 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.
  • R 9 to R 12 are preferably each independently a hydrogen 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, A substituted silyl group, More preferably, each independently a hydrogen 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, More preferably, each independently a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring
  • alkyl group, cycloalkyl group, aralkyl group, aryl group, alkoxy group, and aryloxy group may have a substituent.
  • Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 1 to R 12 include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, and a perfluoro group.
  • a tertiary amine having 4 to 8 carbon atoms such as a tert-butyl group, a tert-pentyl group or a texyl group.
  • a kill group Most preferably, it is a tertiary alkyl group having 5 to 8 carbon atoms such as a tert-pentyl group or a texyl group.
  • the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 2 to R 4 and R 6 to R 12 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 and an n-decyl group, more preferably a perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, a ter
  • Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring in R 1 to R 12 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 12 include vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, a decenyl group and the like can be mentioned.
  • An alkenyl group having 3 to 6 carbon atoms is preferable, and an allyl group and a homoallyl group are more preferable.
  • Examples of the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms in R 1 to R 8 include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, and 3-methyl-1-butynyl group.
  • Examples of the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms in R 1 to R 12 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 12 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 12 include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, 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; Methylsilyl) silyl group, dimethyl (trimethylsilyl) silyl group, and a silyl group having as a substituent a hydrocarbyl silyl group having 3 to 20 carbon atoms, such as tris (trimethylsilyl) silyl group.
  • Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms in R 1 to R 12 include 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, ethoxy group,
  • Examples of the substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms in R 1 to R 12 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-tetra Methylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, 2,6-diisopropylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pentafluoro Phenoxy group, 2-trifluoromethylphenoxy group, 3-trifluoromethylphenoxy group, 4-trifluoro Methylphenoxy group, 2,3-difluorophenoxy group, 2,4-fluorophenoxy group, 2,5-difluorophenoxy group
  • Examples of the substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms in R 1 to R 12 include, for example, 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) Ny
  • 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 12 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, Preferred are thienyl group, furyl group, 1-pyrrolyl group, pyridyl group, pyrimidinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, and dibenzo-1H-pyrrol-1-yl 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 , and R 7 and R 8 are Each independently may be linked to each other to form a ring, and the ring may have a substituent, and is preferably a 4- to 10-membered hydrocyclic hydrocarbon containing two carbon atoms on the benzene ring. It is a carbyl ring or a heterocyclic ring, and this 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 preferred are cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, and more preferred are R 1 and R 2 and / or R A cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a benzene ring, and a naphthalene ring in which 5 and
  • R 9 and R 10 , and R 11 and R 12 may be independently connected to each other to form a ring, and the ring has a substituent. You may do it.
  • 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 are represented by R 2 to R 4. And the same groups as those described above for R 6 to R 8 .
  • Examples of the substituted amino group in X include 2 to 14 carbon atoms such as dimethylamino group, diethylamino group, di-n-butylamino group, di-n-propylamino group, diisopropylamino group, dibenzylamino group, or diphenylamino group. And a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, or a dibenzylamino group.
  • 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, -Difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothiophenoxy group, 2-chloro
  • 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.
  • Preferred are hydrocarbyl carboxylate groups having 2 to 10 carbon atoms, and more preferred are acetate groups, propionate groups, 2-ethylhexanoate groups or trifluoroacetate groups.
  • X is preferably a fluorine atom, a chlorine atom, a bromine 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, or 6 to 6 carbon atoms.
  • An amino group particularly preferably a chlorine atom, a methyl group, a benzyl group, an isopropoxy group, a phenoxy group, a dimethylamino group, and most preferably, a chlorine atom, a benzyl group.
  • R 1 to R 12 and X may each independently have a substituent containing a halogen atom, an oxygen atom, a silicon atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.
  • 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.
  • L examples include ethers, amines or thioethers, and specific examples include tetrahydrofuran, diethyl ether, 1,4-dioxane, and pyridine. L is preferably tetrahydrofuran.
  • L is preferably 1 or 0, more preferably 0.
  • the compound which changed the group corresponding to R ⁇ 3 > and R ⁇ 7 > in each said compound into the hydrogen atom, the fluorine atom, the chlorine atom, the bromine atom, the iodine atom, or the methyl group can also be mentioned.
  • Examples thereof also include compounds in which the groups corresponding to R 9 to R 12 in each of the above compounds are substituted with a methyl group or an ethyl group.
  • Preferred examples of the complex (1) include the following compounds.
  • More preferable examples of the complex (1) include the following compounds.
  • the following compounds are particularly preferable.
  • n ′ is 1 or 2, preferably 2.
  • R 1 ′ and R 5 ′ are preferably each independently a 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 wherein R 1 ′ and R 5 ′ are not simultaneously tert-butyl groups, More preferably, each independently a halogen atom, An alkyl group having 5 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, A substituted silyl group, More preferably, each independently an alkyl group having 5 to 20 carbon atoms, A cyclo
  • R 1 and R 5 are the same, An alkyl group having 5 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 it is a substituted silyl group.
  • R 2 ′ to R 4 ′ and R 6 ′ to R 8 ′ are preferably each independently a 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, A substituted silyl group, More preferably, each independently a hydrogen 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
  • R 3 ′ and R 7 ′ are each independently 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 it is 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.
  • R 9 ′ to R 12 ′ are preferably each independently a hydrogen 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, A substituted silyl group, More preferably, each independently a hydrogen 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, More preferably, each independently a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constitu
  • alkyl group, cycloalkyl group, aralkyl group, aryl group, alkoxy group, and aryloxy group may have a substituent.
  • the groups are the same as the groups described above for R 1 to R 12 in the general formula (1).
  • the aryl group having 6 to 30 carbon atoms in R 2 ′ to R 4 ′ and R 6 ′ to R 12 ′ and the heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring are represented by the general formula (1 And the same groups as those described above for R 2 to R 4 and R 6 to R 8 .
  • R 1 ′ to R 8 ′ may be independently connected to each other to form a ring, which ring may have a substituent, preferably on the benzene ring
  • 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 are mentioned, and preferred are cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, and more preferred are R 1 ′ and R 2 ′, and A cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a benzene ring, and a naphthalene ring in which at least
  • R 9 ′ to R 12 ′, R 9 ′ and R 10 ′, and R 11 ′ and R 12 ′ may be independently connected to each other to form a ring,
  • the ring may have a substituent.
  • the thiolate group and the carboxylate group having 1 to 20 carbon atoms are the same as those described above for X in the general formula (1).
  • X ′ is preferably a fluorine atom, a chlorine atom, a bromine 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, or 6 to 6 carbon atoms.
  • An arylamino group particularly preferably a chlorine atom, a methyl group, a benzyl group, an isopropoxy group, a phenoxy group, a dimethylamino group, and most preferably, a chlorine atom, a benzyl group.
  • R 1 ′ to R 12 ′ and X ′ may each independently have a substituent containing a halogen atom, an oxygen atom, a silicon atom, a nitrogen atom, a phosphorus atom or a sulfur atom.
  • L ′ and l ′ are the same as L and l in the general formula (1).
  • Examples also include compounds in which the groups corresponding to R 9 ′ to R 12 ′ in each of the above compounds are substituted with a methyl group or an ethyl group.
  • Preferred examples of the complex (1 ′) include the following compounds.
  • More preferable examples of the complex (1 ′) include the following compounds.
  • a compound obtained by changing the group corresponding to R 3 ′ and R 7 ′ of each of the above compounds to a methyl group can also be mentioned.
  • the complex represented by the general formula (1) and the complex represented by the general formula (1 ′) are synthesized according to the method described in, for example, Journal of American Chemical Society, 2009, Volume131,13566-13567 Can do.
  • the complex (1) it can be produced by the following scheme 1 using the compounds represented by the general formulas (2) and (3) as starting materials, but should not be limited to this method.
  • ZrX 4 examples include 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 .
  • the compound (2) and the compound (3) may be reacted as they are, or the compound (3) may be reacted after reacting the compound (2) with a base as necessary.
  • the base to be used include an organic lithium reagent, a Grignard reagent, and a metal hydride.
  • methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyl examples thereof include disilazane, potassium hexamethyldisilazane, sodium hydride and potassium hydride, and preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride.
  • the reaction can be carried out under dehydration and deoxygenation. preferable. Specifically, it is under dry nitrogen and dry argon.
  • the amount of the compound (2) used may be 1 molar equivalent or more with respect to the compound (3), and preferably 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 temperature range of ⁇ 100 ° C. to 150 ° C., preferably in the temperature 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 temperature range of ⁇ 100 ° C. to 150 ° C., preferably in the temperature 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 carried out until the product yield becomes the highest, and is 5 minutes to 24 hours, preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.
  • the reaction time of the compound produced by reacting the compound (2) with the base and the compound (3) may be the time until the yield of the product becomes the highest, and is 5 minutes to 48 hours. Preferably, it is 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 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.
  • R 1 to R 12 and n in the compounds (4) to (7) are the same as in the complex (1).
  • Z represents an anionic leaving group, for example, 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 group Preferred are chlorine atom, bromine atom, iodine atom, CF 3 SO 3 group, CH 3 SO 3 group, 4-MeC 6 H 4 SO 3 group or PhSO 3 group.
  • Trans-cyclooctane-1,2-dithiol (4) is reacted with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (5) in the presence of a base to give compound (6) Can be synthesized.
  • the base is not particularly limited, and examples thereof include inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium 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 can be increased by a purification operation 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 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 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 can be increased by a purification operation 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
  • 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 combination of R 9 and R 10 is R
  • the compound (5) and the compound (7) are combined in an amount of 2.0 to 8.0 equivalents with respect to trans-cyclooctane-1,2-dithiol (4).
  • the compound (2) can also be synthesized by reacting preferably 2.0 to 4.0 equivalents in the presence of a base.
  • Specific examples of the compound (2) include the following compounds.
  • Examples thereof also include compounds in which groups corresponding to R 3 and R 7 of these compounds are substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.
  • Examples thereof also include compounds in which the groups corresponding to R 9 to R 12 in each of the above compounds are substituted with a methyl group or an ethyl group.
  • Examples thereof also include compounds in which a group corresponding to R 3 or R 7 of these compounds is substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.
  • Examples thereof also include compounds in which the groups corresponding to R 9 to R 12 in each of the above compounds are substituted with a methyl group or an ethyl group.
  • the complex represented by the general formula (1) of the present invention described above is preferably used as a polymerization catalyst component for producing an ethylene polymer by homopolymerization of ethylene or copolymerization of ethylene and ⁇ -olefin. Is a catalyst component for homopolymerization.
  • the polymerization catalyst a polymerization catalyst obtained by bringing the complex represented by the general formula (1) of the present invention and the promoter component (A) into contact with each other is used.
  • the promoter component (A) include an activation promoter component containing a group 13 element in the periodic table, for example, (A-1) Organoaluminum compound (A-2) There may be mentioned at least one compound selected from the group consisting of boron compounds. [Organic aluminum compound (A-1)]
  • the organoaluminum compound (A-1) used in the present invention a known organoaluminum compound can be used.
  • (A-1-1) an organoaluminum compound represented by the general formula E 1 a AlY 1 3-a , (A-1-2) a general formula ⁇ —Al (E 2 ) —O— ⁇ b
  • Y 1 represents a hydrogen atom or a halogen atom, and all Y 1 may be the same or different, a is an integer of 0 ⁇ a ⁇ 3, b is an integer of 2 or more, and c is 1 or more. Any one of them, or a mixture of 2 to 3 thereof.
  • organoaluminum compound (A-1-1) represented by the general formula E 1 a AlY 1 3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and the like.
  • Dialkylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, etc.
  • Alkyl aluminum dichloride dimethyl aluminum Um hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
  • Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.
  • E 2 and E 3 in the linear aluminoxane (A-1-3) having the structure represented by 2 are methyl group, ethyl group, n-propyl group, isopropyl group, normal butyl group, Examples thereof include alkyl groups such as isobutyl group, n-pentyl group and neopentyl group.
  • b is an integer of 2 or more
  • c is an integer of 1 or more.
  • E 2 and E 3 are a methyl group and an isobutyl group, b is 2 to 40, and c is 1 to 40.
  • aluminoxane can be made by various methods. There is no restriction
  • an aluminoxane is prepared by bringing a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) into contact with water.
  • a trialkylaluminum for example, trimethylaluminum
  • an appropriate organic solvent benzene, toluene, aliphatic hydrocarbon, etc.
  • the method of making aluminoxane by making trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.
  • (A-1-2) the general formula ⁇ -Al (E 2 ) -O— ⁇ b obtained by the above method and a cyclic aluminoxane having a structure represented by the formula (A-1-3)
  • the linear aluminoxane having a structure represented by E 3 ⁇ —Al (E 3 ) —O— ⁇ c AlE 3 2 may be used after distilling off the volatile components if necessary.
  • 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 for use.
  • the boron compound (A-2) includes (A-2-1) a boron compound represented by the general formula BR 13 R 14 R 15 , (A-2-2) a general formula W + (BR 13 R 14 R 15 R 16 ) — or a boron compound represented by (A-2-3) general formula (VH) + (BR 13 R 14 R 15 R 16 ) — Use.
  • B is a trivalent boron atom
  • R 13 to R 15 are halogen atoms, 1 to 20 Hydrocarbyl group containing 1 to 20 carbon atoms, halogenated hydrocarbyl group containing 1 to 20 carbon atoms, substituted silyl group containing 1 to 20 carbon atoms, alkoxy group containing 1 to 20 carbon atoms Or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different.
  • Preferred R 13 to R 15 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
  • boron compound (A-2-1) examples include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, 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. Most preferred are triphenylborane and tris (pentafluorophenyl) borane.
  • W + is an inorganic or organic cation
  • B is a trivalent valence state.
  • R 13 to R 16 are the same as R 13 to R 15 in the boron compound (A-2-1). That is, R 13 to R 16 include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
  • a substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms which may be the same or different.
  • Preferred R 13 to R 16 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
  • W + that is an inorganic cation examples include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation.
  • W + that is an organic cation examples include a triphenylcarbenium cation. (BR 13 R 14 R 15 R 16 ) — includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro).
  • Phenyl) borate tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistri) Fluoromethylphenyl) borate and the like.
  • Specific examples of the compound represented by the general formula W + (BR 13 R 14 R 15 R 16 ) — include ferrocenium tetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium tetrakis (pentafluoro).
  • Phenyl) borate silver tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, etc.
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate is preferable.
  • R 13 to R 16 are the same as R 13 to R 15 in the boron compound (A-2-3). is there. That is, R 13 to R 16 include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
  • a substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms which may be the same or different.
  • Preferred R 13 to R 16 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
  • Examples of (VH) + that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like (BR 13 R 14 R 15 R 16 ) ⁇ Is the same as described above.
  • the contact between the complex (1) and the cocatalyst component is as follows.
  • any means may be used.
  • the complex (1) and the co-catalyst component (A) may be mixed in advance with dilution with or without dilution.
  • a method of contacting them, or a method of separately supplying the complex (1) and the promoter component (A) to the polymerization tank and bringing them into contact in the polymerization tank can be taken.
  • the co-catalyst component (A) may be used in combination of a plurality of types, but some of them may be mixed in advance or used separately by supplying them to the polymerization tank. May be.
  • the complex (1) an isolated one may be used, or a compound obtained by contacting the compound (2) and the compound (3) may be used as it is.
  • each component used is usually such that the molar ratio of the organoaluminum compound (A-1) to the complex represented by the general formula (1) is in the range of 0.01 to 10,000, preferably in the range of 1 to 5000.
  • each component is adjusted so that the molar ratio of the boron compound (A-2) to the complex represented by the general formula (1) is in the range of 0.01 to 100, preferably 1.0 to 50. It is desirable to use it.
  • the concentration when each component is supplied in a solution state or suspended or slurried in a solvent is determined depending on the performance of the apparatus for supplying each component to the polymerization reactor, etc.
  • the complex represented by the general formula (1) is usually 0.0001 to 10000 mmol / L, more preferably 0.001 to 1000 mmol / L, and still more preferably, 0.01 to 100 mmol / L
  • the organoaluminum compound (A-1) is usually 0.01 to 10000 mmol / L, more preferably 0.05 to 5000 mmol / L, still more preferably 0, in terms of Al atom.
  • the boron compound (A-2) is usually from 0.001 to 500 mmol / L, more preferably from 0.01 to 2000 mmol / L. 50 mmol / L, more preferably, it is desirable to use each component to be in the range of 0.05 ⁇ 100mmol / L.
  • the olefin polymerization catalyst is an olefin polymerization obtained by contacting the complex represented by the general formula (1) with the organoaluminum compound (A-1) and / or the boron compound (A-2).
  • the organoaluminum compound (A-1) is used as an organoaluminum compound (A-1) Is preferably the above-mentioned cyclic aluminoxane (A-1-2) and / or linear aluminoxane (A-1-3).
  • the olefin polymerization catalyst is an olefin polymerization catalyst obtained by contacting the complex represented by the general formula (1), the organoaluminum compound (A-1) and the boron compound (A-2).
  • the organoaluminum compound (A-1) can be easily used as the organoaluminum compound (A-1)
  • the boron compound (A-2) can be a boron compound (A-). 2-1) or a boron compound (A-2-2) is preferred.
  • the method for producing an ethylene polymer of the present invention is a method comprising polymerizing ethylene alone in the presence of the catalyst or copolymerizing ethylene and an ⁇ -olefin.
  • ethylene is polymerized alone, a long chain branched polyethylene is obtained.
  • ethylene and ⁇ -olefin are copolymerized, a copolymer of ethylene and ⁇ -olefin containing a long chain branch is obtained.
  • the content of ⁇ -olefin in the copolymer of ethylene and ⁇ -olefin is less than 50 mol%, preferably 35 mol% or less, more preferably 15 mol% or less, and further preferably 10 mol% or less.
  • One or more ⁇ -olefins may be used.
  • ethylene and a single ⁇ -olefin are polymerized, a copolymer of ethylene and a single ⁇ -olefin is obtained.
  • ethylene and a plurality of ⁇ -olefins are polymerized, ethylene and a plurality of ⁇ -olefins are obtained. The copolymer is obtained.
  • the ⁇ -olefin can be a monoolefin or a diolefin.
  • monoolefins examples include carbons such as 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 atoms (which may be branched), cyclopentene, cyclohexene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetra Cyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5 -Methoxycarboni Norbornene, 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 are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane and styrene.
  • propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, and styrene and more preferably propylene, 1-pentene, Preferred are butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and vinylcyclohexane, and most preferred are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and vinylcyclohexane.
  • 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, and ethylene and 4 -Methyl-1-pentene, ethylene and vinylcyclohexane, ethylene and styrene, ethylene and 4-methyl-1-pentene, ethylene and butadiene, ethylene and 1,5-hexadiene, and the like.
  • ethylene and propylene ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, ethylene and styrene, ethylene and 4-methyl-1-pentene More preferably ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, ethylene and styrene, and still more preferably ethylene and propylene, ethylene and 1 -Butene, ethylene and 1-hexene, ethylene and vinylcyclohexane.
  • the polymerization method is not particularly limited.
  • aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane
  • aromatic hydrocarbons such as benzene and toluene
  • halogenated hydrocarbons such as methylene dichloride.
  • Solvent polymerization using carbon as a solvent, slurry polymerization, or the like is possible, and either continuous polymerization or batch polymerization is possible.
  • the temperature and time of the polymerization reaction can be determined in consideration of the desired polymerization average molecular weight, and the activity and usage of the catalyst.
  • the polymerization temperature can usually be in the range of ⁇ 50 ° C. to 200 ° C., but the range of ⁇ 20 ° C. to 100 ° C. is particularly preferable.
  • the polymerization pressure is usually preferably from normal pressure to 50 MPa.
  • the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can usually be in the range of 1 minute to 20 hours, preferably in the range of 5 minutes to 18 hours. However, it is not intended to be limited to these ranges.
  • a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.
  • the concentration of each compound in the solvent is not particularly limited.
  • the concentration of the zirconium complex in the solvent can be selected, for example, in the range of 1 ⁇ 10 ⁇ 8 mmol / L to 10 mol / L, and the concentration of the promoter component is, for example, 1 ⁇ 10 ⁇ 8 mmol / L to 10 mol / L.
  • a range can be selected.
  • the volume ratio of olefin: solvent can be selected from 100: 0 to 1: 1000.
  • these ranges are examples and are not intended to be limited to them. Even when no solvent is used, the concentration can be appropriately set with reference to the above range.
  • the ethylene polymer obtained by the present invention contains a sufficient amount of long-chain branches, has improved melt characteristics, and is excellent in workability.
  • the extrusion torque at the time of melt processing of the blend can be reduced and the fluidity can be increased.
  • a known molding method such as an inflation film molding method, a T-die film molding method, an extrusion molding method such as a lamination film molding method, an injection molding method, etc.
  • a compression molding method or the like is used for the molding of the ethylene polymer obtained by the present invention.
  • the ethylene polymer obtained by the present invention 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 and the like; surface protection materials.
  • a calibration curve was prepared using standard polystyrene. 41.3 was used as the Q factor of polystyrene.
  • Measurement conditions 1 (Examples 1 to 5, Examples 15 to 20, Comparative Example 1) Equipment: TSK HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H (20) 2 Measurement temperature: 152 ° C Solvent: o-dichlorobenzene (0.05% BHT added) Solvent flow rate: 1 ml / min Sample concentration: 0.05% Sample for column / equipment calibration: TSK standard polystyrene F-2000 to A-1000 (manufactured by Tosoh) Measurement conditions 2 (Examples 6 to 14) Equipment: Waters 150C (Waters) Solvent: o-dichlorobenzene (0.05% BHT added) Column: 3 TSKgel GMH6-HT (made by Tosoh) Measurement temperature: 140 ° C Solvent flow rate: 1 ml
  • the Q factor was calculated from the following formula, assuming 17.7.
  • Molecular weight (Mw, Mn) molecular chain length (Aw, An) ⁇ Q factor (3) long chain branching (LCB) number calculation method Peak top at 5-50 ppm in 13 C-NMR spectrum measured under the following conditions The area of the peak derived from methine carbon to which a branch having 7 or more carbon atoms is bonded when the sum of the areas of all the peaks is 1000 is the number of long chain branches per 1000 carbons (a branch having 7 or more carbon atoms) Number). Under the present measurement conditions, the number of long chain branches (the number of branches having 7 or more carbon atoms) was determined from the peak area having a peak top in the vicinity of 38.22 to 38.27 ppm.
  • the peak area was in the range from the chemical shift of the valley with the peak adjacent on the high magnetic field side to the chemical shift of the valley with the peak adjacent on the low magnetic field side.
  • Triethylamine 1.1 mL (7.9 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and also at room temperature for 2 hours. 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 then saturated brine, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 0.17 mL (1.2 mmol) was added here, and it stirred at room temperature for 2 hours. After evaporating volatile components under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 24 mL (172 mmol) was added here, and it heated and refluxed for 2.5 hours.
  • the reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate was added to the residue, followed by washing with 1M HCl and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 19.2 g of a mixture containing 3- (1-adamantyl) -5-methylsalicylaldehyde.
  • reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure.
  • Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order.
  • the organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure.
  • Triethylamine 0.70 mL (5.1 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and room temperature for 1 hour. Furthermore, 90 mg (0.50 mmol) of trans-cyclooctane-1,2-dithiol was added and stirred at room temperature for 1 hour. Volatile components were distilled off under reduced pressure, and ethyl acetate and an 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.
  • Triethylamine 0.70 mL (5.1 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. Volatile components were distilled off under reduced pressure, and ethyl acetate and an 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.
  • Triethylamine 0.90 mL (6.5 mmol) was added here, and it stirred at room temperature for 22.5 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 obtained 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.
  • Triethylamine 1.0 mL (7.2 mmol) was added here, and it stirred at room temperature for 22 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.
  • 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.
  • the reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure.
  • Example 1 The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C.
  • Example 2 Synthesis in Reference Example 3 instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium with an input amount of d-MAO of 102 mg [Cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorozirconium (0.45 mmol / L, toluene solution) 0.22 mL (0.1 ⁇ mol) ) was carried out in the same manner as in Example 1 except that. The results are shown in Table 1.
  • Example 3 The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, 0.5 mL (0.5 mmol) of triisobutylaluminum (1.0 mol / L, toluene solution) was added, and then synthesized in Reference Example 5.
  • Example 4 The input amount of d-MAO was 129 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 8
  • Example 1 was used except that the synthesized [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium was used. Carried out. The results are shown in Table 1.
  • Example 5 The input amount of d-MAO was 121 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 10 Except for using the synthesized ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2-oxoylbenzylsulfanyl] ⁇ dibenzylzirconium, The same operation as in Example 1 was performed. The results are shown in Table 1.
  • Example 6 The input amount of d-MAO was 122 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 12
  • Example 1 was used except that the synthesized ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl] ⁇ dibenzylzirconium was used. It carried out similarly. The results are shown in Table 1.
  • Example 7 The input amount of d-MAO was 149 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 14
  • Example 1 except that the synthesized ⁇ cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl] ⁇ dibenzylzirconium was used. Was carried out. The results are shown in Table 1.
  • Example 8 The polymerization temperature was 0 ° C., the amount of d-MAO charged was 119 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (Cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-) synthesized in Reference Example 14 instead of 0.10 mL (0.050 ⁇ mol) (0.5 mmol / L, toluene solution) Methyl-2-oxoylbenzylsulfanyl] ⁇ dibenzylzirconium (1.0 mmol / L, toluene solution) was used in the same manner as in Example 1 except that 1.0 mL (1.0 ⁇ mol) was used. The results are shown in Table 1.
  • Example 9 The amount of d-MAO was 125 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 16 The procedure was carried out in the same manner as in Example 1 except that the synthesized [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl)] dichlorozirconium was used. The results are shown in Table 1.
  • Example 10 Synthesis in Reference Example 18 instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium with a d-MAO input of 122 mg Except that ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium was used, The same operation as in Example 1 was performed. The results are shown in Table 1.
  • Example 12 The polymerization temperature was set to 70 ° C., and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene solution) ⁇ Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) ⁇ synthesized in Reference Example 18 instead of 0.10 mL (0.05 ⁇ mol) ⁇ 2-Hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.50 ⁇ mol / mL, toluene solution), except that 0.20 mL (0.10 ⁇ mol) was used. The results are shown in Table 1.
  • Example 13 Feeding while adjusting the polymerization temperature to 70 ° C. and adjusting the ethylene pressure to 1.2, [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl) [Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-] synthesized in Reference Example 18 instead of 0.10 mL (0.05 ⁇ mol) of dibenzylzirconium (0.50 ⁇ mol / mL, toluene solution)
  • Example 3 except that 0.10 mL (0.01 ⁇ mol) of 3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.10 ⁇ mol / mL, toluene solution) was used. It implemented like. The results are shown in Table 1.
  • Example 14 Feeding while adjusting the polymerization temperature to 70 ° C. and adjusting the ethylene pressure to 1.8, [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl) [Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-] synthesized in Reference Example 18 instead of 0.10 mL (0.05 ⁇ mol) of dibenzylzirconium (0.50 ⁇ mol / mL, toluene solution)
  • Example 3 except that 0.10 mL (0.01 ⁇ mol) of 3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.10 ⁇ mol / mL, toluene solution) was used. It implemented like. The results are shown in Table 1.
  • Example 15 The polymerization temperature was set to 70 ° C., and 200 mL of hexane was used instead of 200 mL of toluene as a solvent, [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl) [Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-] synthesized in Reference Example 18 instead of 0.10 mL (0.05 ⁇ mol) of dibenzylzirconium (0.50 ⁇ mol / mL, toluene solution)
  • Example 3 except that 0.20 mL (0.10 ⁇ mol) of 3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.50 ⁇ mol / mL, toluene solution) was used. It implemented like.
  • Example 16 The polymerization time was 15 minutes, the d-MAO charge was 117 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium ( 0.50 ⁇ mol / mL, toluene solution) [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3- (2- Phenyl-2-butyl) -2-hydroxybenzylsulfanyl)] dichlorozirconium (0.05 mmol / L, toluene solution) 0.2 mL (0.01 ⁇ mol) was used, and the same procedure as in Example 1 was performed. did. The results are shown in Table 1.
  • Example 17 The amount of d-MAO was 123 mg, and synthesized in Reference Example 22 instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Except for using ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] ⁇ dichlorozirconium Performed as in Example 1. The results are shown in Table 1.
  • Example 18 [Cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene solution) 0.10 mL (0.05 ⁇ mol) ) ⁇ Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] ⁇ dichloro synthesized in Reference Example 22 instead of The same operation as in Example 3 was carried out except that 0.10 mL (0.01 ⁇ mol) of zirconium (0.10 ⁇ mol / mL, toluene solution) was used. The results are shown in Table 1.
  • Example 19 The d-MAO input was 142 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene Solution) ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) synthesized in Reference Example 24 instead of 0.10 mL (0.05 ⁇ mol) Benzylsulfanyl] ⁇ dichlorozirconium (0.05 mmol / L, toluene solution) was used in the same manner as in Example 1 except that 0.2 mL (0.01 ⁇ mol) was used. The results are shown in Table 1.
  • Example 20 The amount of d-MAO charged was 130 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene Solution) ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2,3-dimethyl-2-butyl) synthesized in Reference Example 26 instead of 0.10 mL (0.05 ⁇ mol) ) -2-Hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.05 mmol / L, toluene solution) 0.2 mL (0.01 ⁇ mol) was used, and the same procedure as in Example 1 was performed. The results are shown in Table 1.
  • Example 21 The amount of d-MAO charged was 134 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene Solution) ⁇ cyclooctanediyl-trans-1,2-bis [5-bromo-3- (1-adamantyl) -2-hydroxybenzylsulfanyl] synthesized in Reference Example 28 instead of 0.10 mL (0.05 ⁇ mol) ⁇ It carried out like Example 1 except having used 0.2 mL (0.01 micromol) of dichloro zirconium (0.05 mmol / L, toluene solution). The results are shown in Table 1.
  • Example 22 The amount of d-MAO charged was 114 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene Solution) [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) synthesized in Reference Example 30 instead of 0.10 mL (0.05 ⁇ mol) It carried out like Example 1 except having used 0.2 mL (0.01 micromol) of dichloro zirconium (0.05 mmol / L, toluene solution). The results are shown in Table 1.
  • Example 23 The amount of d-MAO charged was 136 mg, and [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (0.50 ⁇ mol / mL, toluene Solution) ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3-triisopropylsilyl-2-hydroxybenzylsulfanyl] synthesized in Reference Example 32 instead of 0.10 mL (0.05 ⁇ mol) ⁇ Implemented in the same manner as in Example 1 except that 0.20 mL (0.10 ⁇ mol) of dibenzylzirconium (0.50 mmol / L, toluene solution) was used. The results are shown in Table 1.
  • Table 1 shows the polymerization results obtained in Examples 1 to 23 and Comparative Example 1.
  • Example 24 An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 185 mL of toluene as a solvent and 15 mL of 1-hexene as a comonomer were charged, and the temperature of the reactor was raised to 40 ° C.
  • Example 25 The input amount of d-MAO was 113 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 3 Synthesized [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorozirconium (0.45 mmol / L, toluene solution) 0.22 mL (0. The same procedure as in Example 24 was performed except that 1 ⁇ mol) was used. The results are shown in Table 2.
  • Example 26 An autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon. Then, 198 mL of hexane was charged as a solvent, 2 mL of 1-hexene was charged as a comonomer, and the reactor was heated to 40 ° C.
  • Example 27 The input amount of d-MAO was 120 mg, and instead of [cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium in Reference Example 5 Synthesized [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1.0 mmol / L, toluene solution) 0.050 mL (0 .050 ⁇ mol) was carried out in the same manner as in Example 24. The results are shown in Table 2.
  • Example 28 The same procedure as in Example 27 was performed except that the amount of toluene was 198 mL, the amount of 1-hexene was 2 mL, and the amount of d-MAO input was 110 mg. The results are shown in Table 2.
  • Example 29 The same operation as in Example 27 was performed except that vinylcyclohexane was used instead of 1-hexene and the amount of d-MAO input was 118 mg. The results are shown in Table 2.
  • Example 30 An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 190 mL of toluene was charged as a solvent, 10 mL of 1-hexene was charged as a comonomer, and the reactor was heated to 40 ° C. After raising the temperature, the ethylene pressure was fed while adjusting to 0.6 MPa, 0.25 mL (0.25 mmol) of triisobutylaluminum (1.0 mol / L, toluene solution) was added, and then synthesized in Reference Example 18.
  • Example 31 The same operation as in Example 30 was carried out except that the amount of toluene was 195 mL and the amount of 1-hexene was 5 mL. The results are shown in Table 2.
  • Example 32 The polymerization temperature was 70 ° C., the amount of toluene was 160 mL, the amount of 1-hexene was 40 mL, and synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, Example 5 except that the amount of 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium was 0.50 ⁇ mol / mL (toluene solution) 0.20 mL (0.10 ⁇ mol) Implemented. The results are shown in Table 2.
  • Example 33 The polymerization temperature was 70 ° C., the amount of toluene was 185 mL, the amount of 1-hexene was 15 mL, and synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, Example 5 except that the amount of 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium was 0.50 ⁇ mol / mL (toluene solution) 0.20 mL (0.10 ⁇ mol) Implemented. The results are shown in Table 2.
  • Example 34 The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the amount of 1-hexene was 5 mL, and synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, Example 5 except that the amount of 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium was 0.50 ⁇ mol / mL (toluene solution) 0.20 mL (0.10 ⁇ mol) Implemented. The results are shown in Table 2.
  • Example 35 The polymerization temperature was 70 ° C., the amount of toluene was 198 mL, the amount of 1-hexene was 2 mL, and synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, Example 5 except that the amount of 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium was changed to 0.20 mL (0.020 ⁇ mol) (0.10 ⁇ mol / mL, toluene solution) Implemented. The results are shown in Table 2.
  • Example 36 The same procedure as in Example 30 was performed except that 5 g of 1-butene was used as a comonomer instead of 10 mL of 1-hexene. The results are shown in Table 2.
  • Example 37 The same procedure as in Example 30 was performed except that 195 mL of toluene was used and 2.6 g of 1-butene was used instead of 10 mL of 1-hexene as a comonomer. The results are shown in Table 2.
  • Example 38 The polymerization temperature was 70 ° C., the amount of toluene was 160 mL, and the amount of vinylcyclohexane was 40 mL instead of 10 mL of 1-hexene as a comonomer, which was synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [ The amount of 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.50 ⁇ mol / mL, toluene solution) was 0.20 mL (0.10 ⁇ mol). The procedure was the same as in Example 30 except that. The results are shown in Table 2.
  • Example 39 The polymerization temperature was 70 ° C., the amount of toluene was 185 mL, the amount of vinylcyclohexane was 15 mL instead of 10 mL of 1-hexene as a comonomer, and synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [ The amount of 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.10 ⁇ mol / mL, toluene solution) was 0.20 mL (0.020 ⁇ mol). The procedure was the same as in Example 30 except that. The results are shown in Table 2.
  • Example 40 The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the amount of vinylcyclohexane was 5 mL instead of 1 mL of 1-hexene as a comonomer, and synthesized in Reference Example 18 ⁇ cyclooctanediyl-trans-1,2-bis [ The amount of 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium (0.10 ⁇ mol / mL, toluene solution) was 0.20 mL (0.020 ⁇ mol). The procedure was the same as in Example 30 except that. The results are shown in Table 2.
  • Example 41 To a 200 mL four-necked flask, 60 mL of toluene and 30 mL of a butadiene solution (manufactured by Aldrich, toluene solution, 20 w%) were added, and the temperature was raised to 40 ° C.
  • a butadiene solution manufactured by Aldrich, toluene solution, 20 w%
  • Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. As a result of the polymerization, 1.4 g of ethylene / butadiene copolymer was obtained. About the obtained polymer, melting
  • the present invention is useful in the field relating to the production of polyolefins.

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Abstract

La présente invention concerne un catalyseur de polymère comprenant un complexe post-métallocène permettant de produire, avec une grande activité, un polymère éthylénique qui présente une ramification à chaîne longue suffisante. L'invention concerne également un procédé de production d'un polymère éthylénique au moyen dudit catalyseur. L'invention concerne un catalyseur d'homopolymérisation d'éthylène ou un catalyseur de copolymérisation d'éthylène/α-oléfine comprenant un complexe représenté par la formule (1). L'invention concerne également un procédé de production d'un polymère éthylénique selon lequel de l'éthylène est soumis à une homopolymérisation ou de l'éthylène ou une α-oléfine est soumis à une copolymérisation en présence dudit catalyseur.
PCT/JP2012/053730 2011-02-18 2012-02-16 Catalyseur de polymérisation d'éthylène et procédé de production de polymère éthylénique WO2012111779A1 (fr)

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WO2018022279A1 (fr) * 2016-07-29 2018-02-01 Exxonmobil Chemical Patents Inc. Ligands phénolate, complexes de métaux de transition, leur production et leur utilisation
US10221260B2 (en) 2016-07-29 2019-03-05 Exxonmobil Chemical Patents Inc. Phenolate transition metal complexes, production and use thereof
CN109476683A (zh) * 2016-07-29 2019-03-15 埃克森美孚化学专利公司 酚基过渡金属络合物，其生产和用途
US10358397B2 (en) 2017-06-29 2019-07-23 Exxonmobil Chemical Patents Inc. Production of olefin dimers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018022279A1 (fr) * 2016-07-29 2018-02-01 Exxonmobil Chemical Patents Inc. Ligands phénolate, complexes de métaux de transition, leur production et leur utilisation
US10221260B2 (en) 2016-07-29 2019-03-05 Exxonmobil Chemical Patents Inc. Phenolate transition metal complexes, production and use thereof
CN109476683A (zh) * 2016-07-29 2019-03-15 埃克森美孚化学专利公司 酚基过渡金属络合物，其生产和用途
CN109476683B (zh) * 2016-07-29 2022-07-22 埃克森美孚化学专利公司 酚基过渡金属络合物，其生产和用途
US10358397B2 (en) 2017-06-29 2019-07-23 Exxonmobil Chemical Patents Inc. Production of olefin dimers

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