WO2013081080A1 - 複数の種類の遷移金属触媒を用いるオレフィンブロックポリマーの製造方法 - Google Patents
複数の種類の遷移金属触媒を用いるオレフィンブロックポリマーの製造方法 Download PDFInfo
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- WO2013081080A1 WO2013081080A1 PCT/JP2012/081003 JP2012081003W WO2013081080A1 WO 2013081080 A1 WO2013081080 A1 WO 2013081080A1 JP 2012081003 W JP2012081003 W JP 2012081003W WO 2013081080 A1 WO2013081080 A1 WO 2013081080A1
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- 0 Cc1c(*)c(*)c(*)c(C)c1OC1[C@@](**(*II*(I)=Nc2c(*)c(*)c(*)c(*)c2OC)=N)*C1 Chemical compound Cc1c(*)c(*)c(*)c(C)c1OC1[C@@](**(*II*(I)=Nc2c(*)c(*)c(*)c(*)c2OC)=N)*C1 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Definitions
- the present invention relates to a method for producing an olefin block polymer using a plurality of types of transition metal catalysts.
- a block polymer in which two or more types of segments having different properties are chemically linked exhibits excellent physical properties.
- the block polymer acts on the interface between the phases to control the morphology of the dispersed phase. It becomes a compatibilizing agent, and at the same time, functions as a modifier that improves physical properties such as impact resistance of the mixed resin.
- a polymerization catalyst containing a specific transition metal compound and a specific organometallic compound such as organoaluminum, organozinc, or organogallium compound
- a specific transition metal compound such as organoaluminum, organozinc, or organogallium compound
- transition metals that are catalytically active species
- Non-Patent Document 1 and Patent Document 1 in solution polymerization using a transition metal compound and an organoaluminum compound or an organozinc compound, a method for obtaining an olefin block polymer by connecting in series polymerization tanks having different olefin compositions.
- Patent Document 2 discloses a method for obtaining an olefin block polymer by sequentially adding two kinds of transition metal compounds having different copolymerization properties under the same polymerization conditions.
- the problem to be solved by the present invention is to provide a method for producing an olefin block polymer with less by-products and high production efficiency of the olefin block polymer in the synthesis of the olefin block polymer by reversible chain transfer polymerization. is there.
- the present invention comprises a polymerization catalyst (X), a polymerization catalyst (Y), Olefin block polymer that polymerizes olefin using organometallic compound (C) (excluding co-catalyst component for activation (B)) containing an atom selected from Group 2, 12 and 13 of Periodic Table of Elements
- a manufacturing method of The polymerization catalyst (X) includes a transition metal compound (AX) represented by the following general formula (1-X), an organoaluminum oxy compound (B-1), an organoboron compound (B-2), a zinc assistant Formed by contacting a catalyst component (B-3) and an activating co-catalyst component (B) selected from ion-exchanged layered silicate (B-4),
- the polymerization catalyst (Y) includes a transition metal compound (AY) selected from the following general formula (1-Y) (excluding the transition metal compound represented by the following general formula (1-X)), an organic An activation promoter component (B) selected from an aluminum oxy
- R X1 ⁇ R X8 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.
- Each compound residue may have a substituent.
- R X1 and R X2 , R X2 and R X3 , R X3 and R X4 , R X5 and R X6 , R X6 and R X7 , R X7 and R X8 are May be linked to each other to form a ring, and these rings may have a substituent.
- X and X 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 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, A substituted silyl group having 1 to 20 carbon atoms, A substituted amino group having 1 to 20 carbon atoms, A substituted thiolate group having 1 to 20 carbon atoms or a carboxylate group having 1 to 20 carbon atoms is represented.
- the alkyl group in X X, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, have the aryloxy group and the carboxylate groups each substituent May be.
- X X together may be linked to each other to form a ring.
- E X represents a neutral Lewis base. If E X there is a plurality, the plurality of E X may be the same or different.
- X subscript that indicates the number of E X is 0, 1 or 2.
- M represents a transition metal atom of Groups 4 to 11 of the periodic table of elements, and when n is 2 or more, M may be the same or different from each other.
- L is a ⁇ -electron conjugated anionic group containing up to 70 atoms excluding hydrogen atoms and bonded to M via a conjugated ⁇ -electron, and when a is 2 or more, L may be the same as each other May be different.
- X is a non-conjugated anionic group containing up to 70 atoms excluding hydrogen atoms. When b is 2 or more, Xs may be the same or different from each other.
- E is a neutral Lewis basic ligand containing up to 70 atoms excluding hydrogen atoms and bonded to M via one or more unshared electron pairs, and when c is 2 or more, E may be the same as or different from each other.
- a is an integer of 0 to 6
- b is an integer of 0 to 8
- c is an integer of 0 to 9
- n is an integer of 1 to 4.
- M, L, valence each m e of X, l e, when the x e, satisfy the relationship of m e l e ⁇ a + x e ⁇ b.
- L, X, and E may be linked to each other by two or more to form a ring.
- an olefin block polymer having high production efficiency of an olefin block polymer can be obtained in the synthesis of an olefin block polymer by reversible chain transfer polymerization. Furthermore, such an olefin block polymer with high production efficiency of the olefin block polymer can improve rigidity and impact resistance when mixed with a polypropylene resin composition, for example.
- Transition metal compound (AX) The transition metal compound (AX) used in the present invention is represented by the following general formula (1-X). Hereinafter, the transition metal compound (AX) represented by the formula (1-X) will be described.
- R X1 ⁇ R X8 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.
- Each compound residue may have a substituent.
- R X1 and R X2 , R X2 and R X3 , R X3 and R X4 , R X5 and R X6 , R X6 and R X7 , R X7 and R X8 are May be linked to each other to form a ring, and these rings may have a substituent.
- X and X 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 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, A substituted silyl group having 1 to 20 carbon atoms, A substituted amino group having 1 to 20 carbon atoms, A substituted thiolate group having 1 to 20 carbon atoms or a carboxylate group having 1 to 20 carbon atoms is represented.
- the alkyl group in X X, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, have the aryloxy group and the carboxylate groups each substituent May be.
- X X together may be linked to each other to form a ring.
- E X represents a neutral Lewis base. If E X there is a plurality, the plurality of E X may be the same or different.
- X subscript that indicates the number of E X is 0, 1 or 2.
- M X represents a titanium atom, a zirconium atom or a hafnium atom, preferably a hafnium atom.
- N is 1, 2 or 3, preferably 2 or 3, more preferably 3.
- R X1 and R X5 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 aralkyloxy group having 7 to 30 carbon atoms, An aryloxy 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,
- R X2 to R X4 and R X6 to R X8 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 aralkyloxy group having 7 to 30 carbon atoms, An aryloxy 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 Hydrogen atom, An alkyl group having 1 to 20 halogen 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
- R X2 , R X4 , R X6 and R X8 are more preferably a hydrogen atom.
- R X3 and R X7 are more preferably 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 X3 and R X7 particularly preferably are the same and R X3 and R X7, 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, R X3 and R X7 are the same and are an alkyl group having 1 to 20 carbon atoms.
- Each compound residue may have a substituent.
- halogen atom in R X1 ⁇ R X8 for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
- alkyl group having 1 to 20 carbon atoms which may have a substituent in R X1 to R X8 include, for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, and perfluoroisopropyl.
- the alkyl group having 1 to 20 carbon atoms which may have a substituent in R X1 and R X5 is preferably an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, or an n-pentyl group.
- Alkyl groups having 4 to 10 carbon atoms such as isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n-octyl group, n-decyl group, etc.
- More preferred are tertiary alkyl groups having 4 to 6 carbon atoms such as tert-butyl group, tert-pentyl group and texyl group.
- the alkyl group having 1 to 20 carbon atoms which may have a substituent in R X2 to R X4 and R X6 to R X8 is preferably a perfluoromethyl group, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, texyl, neohexyl, n-
- Examples of the cycloalkyl group having 3 to 10 carbon atoms constituting the ring which may have a substituent in R X1 to R X8 include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, Cycloheptyl group, cyclooctyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-phenylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1-adamantyl group, 2-adamantyl group, Preferably, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-indanyl, 2-indanyl, norbornyl, borny
- these cycloalkyl groups may have a hydrocarbyl group having 1 to 10 carbon atoms as a substituent.
- the group constituting the ring is a 1-adamantyl group, 3,5-dimethyladamantyl group, 3,5,7-trimethyladamantyl group, 3,5-diethyladamantyl group, 3,5,7-triethyladamantyl group Group, 3,5-diisopropyladamantyl group, 3,5,7-triisopropyladamantyl group, 3,5-diisobutyladamantyl group, 3,5,7-triisobutyladamantyl group, 3,5-diphenyladamantyl group, 3, 5,7-triphenyladamantyl group, 3,5-di (p-toluyl) adamantyl group, 3,5,7-tri (p-toluyl) adamantyl group, 3,5-di (3,5-xylyl) adam
- alkenyl group having 2 to 20 carbon atoms which may have a substituent in R X1 to R X8 include a vinyl group, an allyl group, a propenyl group, a 2-methyl-2-propenyl group, a homoallyl group, Examples thereof include a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, and the like, preferably an alkenyl group having 3 to 6 carbon atoms, and more preferably an allyl group or a homoallyl group.
- alkynyl group having 2 to 20 carbon atoms which may have a substituent in R X1 to R X8 include, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 3-methyl -1-butynyl group, 3,3-dimethyl-1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 4-methyl-1-pentynyl group, 2-pentynyl group, 3-pentynyl group 4-pentynyl group, 4-methyl-1-pentenyl group, 1-hexynyl group, 1-octynyl group and phenylethynyl group, preferably an alkynyl group having 3 to 8 carbon atoms, more preferably 3 -Methyl-1-butynyl group, 3,3-dimethyl-1-butynyl group, 4-
- Examples of the aralkyl group having 7 to 30 carbon atoms which may have a substituent in R X1 to R X8 include, for example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) 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-tetramethyl
- Examples of the aryl group having 6 to 30 carbon atoms which may have a substituent in R X1 to R X8 include a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3 -Xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2 , 3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl Group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-buty
- Examples of the substituted silyl group in R X1 to R X8 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
- alkoxy group having 1 to 20 carbon atoms which may have a substituent in R X1 to R X8 include, for example, a perfluoromethoxy group, a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoroiso group.
- Examples of the aryloxy group having 6 to 30 carbon atoms which may have a substituent in R X1 to R X8 include, for example, phenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethyl.
- Examples of the aralkyloxy group having 7 to 30 carbon atoms which may have a substituent in R X1 to R X8 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-dimethyl) Phenyl) 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-trimethyl) (T
- heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring which may have a substituent in R X1 to R X8 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 X1 and R X2 , R X2 and R X3 , R X3 and R X4 , R X5 and R X6 , R X6 and R X7 , R X7 and R X8 are respectively They may be linked to each other to form a ring, which may have a substituent, and preferably contains two carbon atoms on the benzene ring shown in formula (1-X) It is a 4- to 10-membered hydrocarbyl ring or 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, 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 cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, and more preferred are R X1 and R X2 and / or R X5 and R.
- X6 is a cyclopentene ring, cyclohexene ring, benzene ring or naphthalene ring linked to each other.
- Two XXs 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, or an alkyl group having 2 to 20 carbon atoms.
- X X Halogen atom in X, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms constituting the ring, alkenyl group having 2 to 20 carbon atoms, aralkyl having 7 to 30 carbon atoms Groups, aryl groups having 6 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyloxy groups having 7 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, and 1 to 20 carbon atoms
- the substituted silyl groups are the same as those having 1 to 20 carbon atoms among those described as the substituted silyl groups in R X2 to R X4 and R X6 to R X8 .
- the substituted amino group having 1 to 20 carbon atoms in X X for example, dimethylamino group, diethylamino group, di-n- butylamino group, di-n- propylamino group, diisopropylamino group, dibenzylamino group, or diphenylamino
- hydrocarbylamino groups having 2 to 14 carbon atoms such as A dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group or a dibenzylamino group is preferable.
- the substituted thiolate group having 1 to 20 carbon atoms in X X for example, thiophenoxy group, 2,3,4-methylthiophenoxy group, 2,3,5-methylthiophenoxy 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-tetramethylthio Phenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, 2-fluorothiophenoxy group, 3-fluorothiophenoxy group, 4-fluorophenoxy group, pentafluorothiophenoxy group, 2-trithio group Fluoromethylthiophenoxy group, 3-trifluoromethylthiophenoxy group, 4-trifluoromethylthio group Ofenoxy group, 2,3-difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothi
- the carboxylate group having 1 to 20 carbon atoms in X X for example, an acetate group, propionate group, butyrate group, pentanate group, hexanoate group, 2-ethylhexanoate group, or trifluoroacetate group and the like,
- 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 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 carbon atoms.
- the alkyl group in X X, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, have the aryloxy group and the carboxylate groups each substituent May be.
- X X together may be linked to each other to form a ring, the ring may have a substituent.
- R X1 to R X8 and X X may each independently have a substituent containing a halogen atom, oxygen atom, silicon atom, nitrogen atom, phosphorus atom or sulfur atom.
- E X represents a neutral Lewis base.
- EX include ethers, amines or thioethers, and specific examples thereof include tetrahydrofuran, diethyl ether, 1,4-dioxane, and pyridine.
- the preferred E X tetrahydrofuran.
- the x subscript represents the number of E X, 0, 1, or 2, preferably 0 or 1, more preferably 0. If E X there is a plurality, the plurality of E X may be the same or different.
- Substituents that the compound residue may have, R X1 and R X2 , R X2 and R X3 , R X3 and R X4 , R X5 and R X6 , R X6 and R X7 , or R X7 and R X8 are linked to the ring formed has optionally may substituent, the alkyl group in X X, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the The aryloxy group and the substituent that the carboxylate group may have, and a
- transition metal compound (AX) represented by the formula (1-X) include the following compounds.
- the two benzyl groups directly bonded to the titanium atoms of the above compounds are changed to chlorine atoms, methyl groups, dimethylamino groups, isopropoxy groups, tert-butoxy groups or phenoxy groups.
- the compound obtained is also exemplified as an example of the transition metal compound (AX).
- the transition metal compound (AX) preferably includes the following compounds.
- transition metal compound (AX) More preferable examples include the following compounds.
- transition metal compound (AX) include the following compounds.
- the transition metal compound (AX) can be synthesized, for example, by the method described in Reference: Journal of American Chemical Society, 2009, Volume 131, 13566-13567. Specifically, a compound represented by the general formula (2) (hereinafter referred to as “compound (2)”) and a compound represented by the general formula (3) (hereinafter referred to as “compound (3)”).
- the transition metal compound (AX) represented by the general formula (1-X) can be produced by the following scheme 1 as a starting material.
- R X1 ⁇ R X8 and n in the general formula (2) is the same as R X1 ⁇ R X8 and n in the general formula (1-X) in.
- E X in Scheme1 is identical to the E X of the general formula (1-X) in, E X in the reaction system may be present or absent, if not, the E X
- the subscript x indicating the number is zero.
- M X and X X of the general formula (3) is the same as the M X and X X in the general formula (1-X).
- M X X X 4 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 , Ti ( OMe) 4, Ti (OEt) 4, Ti (O-i-Pr) 4, TiCl 2 (O-i-Pr) 2, Ti (O-n-Bu) 4, Ti (O-i-Bu) 4 , Ti (Ot-Bu) 4 , Ti (OPh) 4 , Ti (NMe 2 ) 4 , TiCl 2 (NMe 2 ) 2 , Ti (NEt 2 ) 4 , Zr (CH 2 Ph) 4 , ZrCl 2 ( CH 2 Ph) 2 , Zr (CH 2 SiMe 3 ) 4 , ZrF 4 , ZrC
- the transition metal compound (AX) may be formed by reacting the compound (2) and the compound (3) as they are, and after reacting the compound (2) with a base, reacting the compound (3). It may be formed. These reactions are usually performed in a solvent.
- the base to be used include organolithium reagents, Grignard reagents, and metal hydrides. Specific examples include n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazane.
- Potassium hexamethyldisilazane, sodium hydride or potassium hydride preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride.
- transition metal compound (AX) and compound (3) are usually unstable to air and moisture, the reaction is carried out under dehydration and deoxygenation. It is preferable. Specifically, it is under dry nitrogen or dry argon.
- the amount of the compound (2) used may be 1 molar equivalent or more with respect to the compound (3), preferably 1.0 to 1.5 molar equivalent. 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 the compound (2) and the compound (3) are reacted is usually ⁇ 100 ° C. to 150 ° C., preferably ⁇ 80 ° C. to 50 ° C.
- 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 usually ⁇ 100 ° C. to 150 ° C., preferably ⁇ 80 ° C. to 50 ° C.
- 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 temperature at which the compound (3) is reacted with the compound produced by reacting the compound (2) with a base is usually ⁇ 100 ° C. to 150 ° C., preferably ⁇ 80 ° C. to 50 ° C.
- 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, it can be produced by the method described in scheme 2 below. Hereinafter, each process described in scheme 2 will be described in detail.
- the compounds represented by the following general formulas (4) to (7) are referred to as “compounds (4) to (7)”, respectively.
- R X1 ⁇ R X8 and n in each compound in scheme2 is the same as R X1 ⁇ R X8 and n in the general formula (1-X).
- 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 examples include inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate and sodium 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, potassium hydrogen carbonate, calcium hydrogen carbonate and sodium 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 (6) may be purified.
- 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, potassium hydrogen carbonate, calcium hydrogen carbonate and sodium 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, potassium hydrogen carbonate, calcium hydrogen carbonate and sodium 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.
- 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].
- compound (2) can be synthesized by reacting compound (4) with 2.0 to 8.0 equivalents, preferably 2.0 to 4.0 equivalents in the presence of a base. it can.
- Specific examples of the compound (2) include the following compounds.
- the groups corresponding to R X3 and R X7 in the general formula (2) in each of the above compounds are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a methyl group.
- Examples of the compound (2) are also compounds changed to.
- groups corresponding to R X3 or R X7 in the above general formula (5) or (7) in each of the above compounds are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine
- a compound changed to an atom or a methyl group is also exemplified as the compound (5) and the compound (7).
- Transition metal compound (AY) used in the present invention is selected from one or more transition metal atoms, a ⁇ -electron conjugated anionic group, a non-conjugated anionic group, and a neutral Lewis basic ligand.
- the transition metal compounds represented by the following general formula (1-Y) containing one or more groups / ligands are excluded. Selected from the group of transition metal compounds. Examples include a metallocene, a half metallocene, or a transition metal compound having a multidentate chelate group having a hetero atom as a coordination element.
- the transition metal compound represented by the formula (1-Y) will be described.
- M represents a transition metal atom of Group 4 to 11 of the periodic table, and when n is 2 or more, M may be the same or different from each other. Among them, preferably a transition metal atom selected from Group 4 to 10, more preferably Group 4, 5, 6, 8, 9, 10, further preferably Group 4, 6, 8, 10 and most preferably Group 4. is there.
- L is a ⁇ -electron conjugated anionic group containing up to 70 atoms excluding hydrogen atoms and bonded to M via a conjugated ⁇ -electron, and when a is 2 or more, L may be the same as each other May be different.
- X is a non-conjugated anionic group containing up to 70 atoms excluding hydrogen atoms.
- Xs may be the same or different from each other.
- E is a neutral Lewis basic ligand containing up to 70 atoms excluding hydrogen atoms and bonded to M via one or more unshared electron pairs, and when c is 2 or more, E may be the same as or different from each other.
- a is an integer of 0 to 6
- b is an integer of 0 to 8
- c is an integer of 0 to 9
- n is an integer of 1 to 4.
- M, L, valence each m e of X, l e, when the x e, satisfy the relationship of m e l e ⁇ a + x e ⁇ b.
- L, X, and E may be linked to each other by two or more to form a ring.
- L's are together
- b is 2 or more
- X's are together.
- Es may be connected to each other
- n is 2 or more
- Ls, Xs, and Es may be connected to each other to form a ring.
- the ⁇ -electron conjugated anionic group may be any anionic group that binds to M via a conjugated ⁇ -electron, for example, a cyclopentadienyl group, an indenyl group, a fluorenyl group, Tetrahydroindenyl group, tetrahydrofluorenyl group, octahydrofluorenyl group, pentadienyl group, cyclohexadienyl group, dihydroanthracenyl group, hexahydroanthracenyl group, decahydroanthracenyl group, phosphole
- their derivatives in particular their C 1-10 hydrocarbyl substituted or tris (C 1-10 hydrocarbyl) silyl substituted derivatives are included.
- a cyclopentadienyl group a pentamethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a tetramethyltrimethylsilylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and 2,3-dimethyl are preferable.
- non-conjugated anionic groups include hydrogen atom, oxygen atom, sulfur atom, halogen atom, boron-containing group, aluminum-containing group, gallium-containing group, carbon-containing group, silicon-containing group, germanium-containing group, tin-containing group , Nitrogen-containing groups, phosphorus-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, halogen-containing groups, and heterocyclic compound residues.
- the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.
- the boron-containing group is a group containing 1 to 5 boron atoms, and preferably a hydroboryl group or a part or all of the hydrogen atoms of the hydroboryl group are halogen atoms, nitrogen-containing groups, oxygen-containing groups, hydro A carbyl group, or a part or all of hydrogen atoms of the hydrocarbyl group is substituted by a halogen atom, a nitrogen-containing group, an oxygen-containing group, or a group substituted by a plurality, or a plurality Things.
- the aluminum-containing group is preferably a group in which the boron atom of the boron-containing group is substituted with an aluminum atom
- the gallium-containing group is preferably a group in which the boron atom of the boron-containing group is substituted with a gallium atom.
- a hydrocarbyl group, or a part or all of the hydrogen atoms of the hydrocarbyl group are halogen atoms, boron-containing groups, aluminum-containing groups, gallium-containing groups, silicon-containing groups, germanium-containing groups, tin And a group substituted by any one or more of a containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a halogen-containing group, and a heterocyclic compound residue.
- hydrocarbyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, a linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms such as an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc.
- C3-C30 preferably C3-C20 cyclic alkyl group, phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group, etc.
- C6-C30 preferably 6-20 2 to 8 carbon atoms such as aryl, vinyl, allyl, isopropenyl 0, preferably 2-20 linear or branched alkenyl groups, ethynyl groups, propargyl groups, etc.
- hydrocarbyl group part or all of the hydrogen atoms may be substituted with other hydrocarbyl groups, such as aralkyl groups such as benzyl and cumyl, tolyl groups, isopropylphenyl groups, and tert-butylphenyl groups.
- aralkyl groups such as benzyl and cumyl
- tolyl groups isopropylphenyl groups
- tert-butylphenyl groups alkyl-substituted aryl groups such as dimethylphenyl group and di-tert-butylphenyl group.
- the silicon-containing group is a group containing 1 to 5 silicon atoms, preferably a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group.
- Hydrocarbyl-substituted silyl groups such as dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group, hydrocarbyl-substituted silyloxy groups such as trimethylsilyloxy group, hydrocarbyl such as trimethylsilylmethyl group It is a hydrocarbyl-substituted silylaryl group such as a building-substituted silylalkyl group or a trimethylsilylphenyl group.
- the germanium-containing group is preferably a group in which the silicon atom of the silicon-containing group is substituted with a germanium atom
- the tin-containing group is a group in which the silicon atom of the silicon-containing group is substituted with a tin atom.
- the nitrogen-containing group is a group containing 1 to 5 nitrogen atoms, preferably an alkylamino group such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dicyclohexylamino group, a benzylamino group, or a cumylamino group.
- an alkylamino group such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dicyclohexylamino group, a benzylamino group, or a cumylamino group.
- Phenylamino group diphenylamino group, ditolylamino group, dinaphthylamino group, arylamino group such as methylphenylamino group, aralkylamino group such as benzylamino group, cumylamino group, imino group, amide group, imide group, hydrazino group Hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group and the like.
- the phosphorus-containing group is a group containing 1 to 5 phosphorus atoms, and preferably a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group, or the like.
- the oxygen-containing group is a group containing 1 to 5 oxygen atoms, preferably an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, a phenylmethoxy group, a phenylethoxy group, a phenoxy group, a methylphenoxy group, a dimethyl group.
- alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, a phenylmethoxy group, a phenylethoxy group, a phenoxy group, a methylphenoxy group, a dimethyl group.
- aryloxy groups such as phenoxy group and naphthoxy group, acyl groups, ester groups, carboxyl groups, carboxylic acid groups, carbonate groups, carboxylic anhydride groups, and peroxy groups.
- the sulfur-containing group is a group containing 1 to 5 sulfur atoms, preferably a mercapto group, an alkylthio group, an arylthio group, a thioacyl group, a thioester group, a dithioester group, a thioether group, a thiocyanate group, or an isothiocyanic acid group.
- Examples thereof include an ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group.
- the selenium-containing group is preferably a group obtained by substituting the sulfur atom of the sulfur-containing group with a selenium atom.
- Preferred halogen-containing groups are fluorine-containing groups such as PF 6 and BF 4 , chlorine-containing groups such as ClO 4 and SbCl 6, and iodine-containing groups such as IO 4 .
- the heterocyclic compound residue is a residue such as a nitrogen-containing compound such as pyrrole, pyridine, pyrimidine, quinoline or triazine, an oxygen-containing compound such as furan or pyran, a sulfur-containing compound such as thiophene, or a heterocyclic ring thereof.
- the neutral Lewis basic ligand may be any neutral ligand that binds to M via one or more unshared electron pairs.
- dimethyl ether, diethyl Linear or cyclic saturated or unsaturated ethers such as ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, furan, dioxane, dimethylfuran, anisole, diphenyl ether, methyl-t-butyl ether, acetaldehyde, propionaldehyde, n-butyl Chain or cyclic saturated or unsaturated aldehydes such as aldehyde, benzaldehyde, p-tolylaldehyde, p-nitrobenzaldehyde, phenylacetaldehyde, acetone, methyl ethyl ketone, methyl-n-propyl ketone, acetophenone, benzopheno Linear or cyclic saturated or unsaturated
- Linear or cyclic saturated or unsaturated esters linear or cyclic saturated or unsaturated acid anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, formamide, acetamide, benzamide, n-barrelamide, stearylamide , N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylpropionamide, N, N-dimethyl-n-butyramide and other linear or cyclic saturated or unsaturated amides, succinimide, phthalimide, etc.
- acid anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, formamide, acetamide, benzamide, n-barrelamide, stearylamide , N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylpropionamide, N, N-dimethyl-n-butyramide and
- Chain or cyclic saturated or unsaturated Chain or cyclic saturation such as trimethylamine, triethylamine, triphenylamine, dimethylamine, N, N, N ′, N′-tetramethylethylenediamine, aniline, N, N-dimethylaniline, pyrrolidine, piperidine, morpholine Or chained or cyclic saturated or unsaturated imines such as unsaturated amines, methanimine, etanimine, phenylmethanimine, N-methylmethanimine, pyridine, ⁇ -picoline, ⁇ -picoline, quinoline, isoquinoline, 2-methyl Nitrogen-containing heterocyclic compounds such as pyridine, pyrrole, oxazole, imidazole, pyrazole, and indole, thioethers such as dimethyl sulfide, methylphenyl sulfide, and diphenyl sulfide, dimethyl sulfoxide, and
- the transition metal compound (AY) forming the polymerization catalyst (Y) used in the present invention is preferably the following general formulas (1-Y-1), (1-Y-2), (1-Y-3) ), (1-Y-4), (1-Y-5), (1-Y-6), (1-Y-7) and (1-Y-8) It is.
- the formulas (1-Y-1), (1-Y-2), (1-Y-3), (1-Y-4), (1-Y-5), (1-Y-6) The transition metal compounds represented by (1-Y-7) and (1-Y-8) will be described.
- M, X, and b are the same as those in the above formula (1-Y), and M is preferably a group 4 transition metal atom, specifically titanium.
- R 1 represents a hydrocarbyl group containing 1 to 30 atoms in addition to a hydrogen atom. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, Cycloalkyl groups having 3 to 30 carbon atoms such as alkyl groups such as dodecyl group and eicosyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert
- T 1 represents a divalent bridging group containing 1 to 40 atoms other than hydrogen atoms, preferably a bridging group containing 1 to 20 atoms other than hydrogen, more preferably 1 carbon atom.
- Is an aralkyl group such as a cycloalkyl group of 3 to 20, benzyl group, phenylethyl group, phenylpropyl group, phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, Aryl groups such as diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl 1 connected to include two substituted methylene group or a silylene group.
- aralkyl group such as a cycloalkyl group of 3 to 20, benzyl group, phenylethyl group, phenylpropy
- a methylene group or silylene group substituted with one aryl group having 6 to 20 carbon atoms is preferred, and a methylene group or silylene group substituted with one substituted phenyl group or one condensed polycyclic aryl group is more preferred.
- E 1 represents a heterocyclic compound residue having 5 to 40 carbon atoms having Lewis basicity.
- the transition metal compound represented by the general formula (1-Y-1) is preferably a compound represented by the following general formula (1-Y-1a).
- R 1 is preferably a phenyl group, Tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, diisopropylphenyl group, triisopropylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, tri-tert- An aryl group having 6 to 20 carbon atoms such as a butylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, or a phenanthryl group.
- R 2 to R 4 represent a hydrogen atom, a halogen atom, a silyl group, a hydrocarbyl group having 1 to 20 carbon atoms, or a group in which the hydrogen atom of the hydrocarbyl group is substituted with a heteroatom-containing group.
- a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 5 represents a silyl group, a hydrocarbyl group having 1 to 20 carbon atoms, or a group in which a hydrogen atom of the hydrocarbyl group is substituted with a heteroatom-containing group, preferably 6 to 20 carbon atoms.
- the groups R 2 to R 5 can also form a condensed ring derivative by bonding adjacent groups to each other.
- transition metal compound represented by the general formula (1-Y-1a) is more preferably a compound represented by the following general formula (1-Y-1b).
- M, X, R 2 to R 5 , T 1 and b each represents the same as the general formula (1-Y-1a), and R 5 is preferably Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri An aryl group having 6 to 20 carbon atoms such as tert-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group;
- the divalent bridging group T 1 is preferably —CR 6 R 7 — or —SiR 6 R 7 —, more preferably —CR 6 R 7 —.
- R 6 and R 7 are each independently a hydrogen atom, a halogen atom, or an alkyl group or aryl group having 1 to 20 carbon atoms, preferably one of R 6 and R 7 is a hydrogen atom, and the other Is an aryl group having 6 to 20 carbon atoms.
- Each R a is independently an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, d is 1-5.
- the aryl group substituted by R a is preferably a 2,4,6-trimethylphenyl group, a 2,4,6-triethylphenyl group, a 2,4,6-triisopropylphenyl group, a 2,4,6-triethyl group. and t-butylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-diisopropylphenyl group, and 2,6-dit-butylphenyl group.
- transition metal compound represented by the general formula (1-Y-1b) is more preferably a compound represented by the following general formula (1-Y-1c).
- X represents the same as in the general formula (1-Y-1b), preferably a halogen atom, an N, N-dimethylamide group or a carbon atom number of 1 to 4. And more preferably a methyl group.
- R b and R c represents a hydrogen atom, a halogen atom, an aryl group an alkyl group or a carbon atom number of 6 to 20 carbon atoms having 1 to 6, in some cases is R b together and R c together two adjacent They may combine to form a condensed ring derivative, and e is 1 to 4, and f is 1 to 5.
- the phenylene group substituted by R b is preferably a 5-methylphenylene group, a 5-ethylphenylene group, a 5-isopropylphenylene group, a 5-cyclohexylphenylene group, or a condensed ring formed by bonding of R b to each other.
- the derivative is preferably a naphthalenyl group, an anthryl group, or a phenanthryl group.
- the phenyl group substituted by R c is preferably 2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-triisopropylphenyl group, 2,4,6-triphenyl.
- An isopropylphenyl group, a 2-cyclohexylphenyl group, and a condensed ring derivative formed by bonding of R c is preferably a naphthalenyl group, an anthryl group, or a phenanthryl group.
- transition metal compound represented by the general formula (1-Y-1c) compounds represented by the following general formulas (1-Y-1d) and (1-Y-1e) are more preferable.
- X represents the same as in the general formula (1-Y-1c), preferably a halogen atom, N, N-dimethylamide Group or an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
- R 8 is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, and is preferably a methyl group, an isopropyl group, a t-butyl group, or a cyclohexyl group.
- transition metal compound (AY) represented by the general formula (1-Y-1) is shown below, but is not limited thereto.
- the modified compounds are similarly mentioned.
- the transition metal compound (AY) represented by the general formula (1-Y-1) can be produced by the method described in US Patent Application Publication No. 2004/0220050.
- M is preferably a group 4 or group 5 transition metal atom of the periodic table, more preferably a group 4 transition metal atom, specifically a titanium atom, a zirconium atom, or a hafnium atom, Zirconium atoms and hafnium atoms are preferred.
- G is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen-containing group (—NR d —) having a substituent R d , preferably an oxygen atom and a sulfur atom, more preferably an oxygen atom.
- R d a nitrogen-containing group
- Gs may be the same as or different from each other.
- T 2 is a nitrogen atom or a carbon-containing group (—CR e ⁇ ) having a substituent R e , preferably a carbon-containing group.
- R e a substituent
- T 2 may be the same or different from each other.
- R 9 to R 11 , R d contained in G, and R e contained in T 2 are the same as those in X in the general formula (1-Y).
- R 9 to R 11 , R d , and R e may be the same or different from each other.
- R 9 , R 10 , R 11 , R d , and R e are mutually It may be the same or different.
- Two or more of R 10 , R 11 , R d , and R e may be connected to each other to form a ring.
- R 9 to R 11 , R d , R e may be linked to one group of R 9 to R 11 , R d , R e contained in another ligand.
- R 9 to R 11 , R d , and R e are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, or a heterocyclic compound residue, and more preferably methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- drocalbyl and perhalocarbyl groups include drocalbyl and perhalocarbyl groups, and hydrocarbyl-substituted silyl groups such as trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl groups.
- transition metal compound represented by the general formula (1-Y-2) a compound represented by the following general formula (1-Y-2a) is preferably used.
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, a trialkylsilylmethyl group, an alkoxo group, an aryloxo group, or an N, N-dialkylamide group.
- R 12 to R 15 are the same as those in X in the general formula (1-Y).
- R e included in R 9 , R 12 to R 15 , and T 2 may be the same or different from each other, and R 9 , R 12 , R 13 , R 14 , R 15 , and R e May be the same as or different from each other.
- Two or more of R 12 to R 15 and R e may be connected to each other to form a ring, and one group of R 9 , R 12 to R 15 , and R e And one group of R 9 , R 12 to R 15 , and R e contained in another ligand may be linked.
- R 9 , R 12 to R 15 , and R e are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, or a heterocyclic compound residue, and more preferably methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- transition metal compound represented by the general formula (1-Y-2) a compound represented by the following general formula (1-Y-2b) is preferably used.
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, a trialkylsilylmethyl group, an alkoxo group, an aryloxo group, or an N, N-dialkylamide group.
- T 3 g represents a divalent bridging group R 9 together in the general formula (1-Y-2a) are linked to each other, T 3 is, -CR f 2 -, - SiR f 2 -, - NR f - , —PR f —, —P (O) R f —, —O—, —S—, —S (O) — or —SO 2 —, preferably —CR f 2 —, —SiR f 2 —. More preferably, it is —CR f 2 —.
- T 3 contains a hetero atom, the hetero atom of T 3 may be directly coordinated to M.
- g is an integer of 1 to 7, and preferably 2 to 5.
- T 3 each other may be the same or different from each other.
- R f contained in T 3 are the same as those in X in the general formula (1-Y). If R f is a plurality, R f each other may be the same or different from each other, may form a ring R f together with each other.
- R 12 to R 15 are the same as those in the general formula (1-Y-2a).
- R e contained in R 12 to R 15 , T 2, and R f contained in T 3 may be the same or different from each other, and R 12 , R 13 , R 14 , R 15 , R e May be the same as or different from each other, and two or more of R 12 to R 15 , R e and R f may be connected to each other to form a ring.
- R 12 to R 15 , R e and R f are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group or a heterocyclic compound residue, more preferably methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- transition metal compound (AY) represented by the general formula (1-Y-2) examples of the specific structure of the transition metal compound (AY) represented by the general formula (1-Y-2) are shown below, but are not limited thereto.
- the modified compounds are similarly mentioned.
- the transition metal compound (AY) represented by the general formula (1-Y-2) is “J. Am. Chem. Soc.” Vol. 123, 6847 (2001).
- M is preferably a group 4 or group 5 transition metal atom of the periodic table, more preferably a group 4 transition metal atom, specifically a titanium atom, a zirconium atom, or a hafnium atom, Zirconium atoms and hafnium atoms are preferred.
- T 4 is —CR g 2 —, —C 6 R g 4 —, —SiR g 2 —, —NR g —, —PR g —, —P (O) R g —, —S—, —S ( O) — or —SO 2 —, preferably —CR g 2 —, —C 6 R g 4 —, —SiR g 2 —, more preferably —CR g 2 —.
- T 4 contains a hetero atom, the hetero atom of T 4 may be directly coordinated to M.
- R d contained in R 10 , R 11 , R 16 and G, and R g contained in T 4 may be the same as X in the general formula (1-Y).
- R 10, R 11, R 16 , R d, R g may be the same or different from each other, each other R 16 may be the same or different, when a is 2 or more, R 10 s, R 11 , R d , and R g may be the same or different from each other.
- Two or more of R 10 , R 11 , R d , and R g may be connected to each other to form a ring.
- R 10 , R 11 , R 16 , R d , R g and one group out of R 10 , R 11 , R 16 , R d , R g contained in the other ligand are linked together. Also good.
- R 10 , R 11 , R 16 , R d , R g are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a heterocyclic compound residue,
- carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- Hydrocarbyl groups such as 6-20 aryl groups, and some or all of the hydrogen atoms in these hydrocarbyl groups are substituted with halogen atoms.
- transition metal compound represented by the general formula (1-Y-3) a compound represented by the following general formula (1-Y-3a) is preferably used.
- M, X, T 4 and R 16 are the same as those in the general formula (1-Y-3).
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, a trialkylsilylmethyl group, an alkoxo group, an aryloxo group, or an N, N-dialkylamide group.
- R 12 to R 15 are the same as those in the general formula (1-Y-2a).
- R g contained in R 12 to R 15 , R 16 and T 4 may be the same or different from each other, and R 12 to each other, R 13 to each other, R 14 to each other, R 15 to each other, R 16 to each other, R g to each other May be the same as or different from each other.
- two or more of R 12 to R 15 and R g may be connected to each other to form a ring, and one group of R 12 to R 15 , R 16 and R g And one group of R 12 to R 15 , R 16 and R g contained in another ligand may be linked.
- R 12 to R 15 , R 16 and R g are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group or a heterocyclic compound residue, more preferably methyl.
- Idorokarubiru groups and perhalocarbyl group and a trimethylsilyl group, triethylsilyl group, triphenylsilyl group, a hydrocarbyl-substituted silyl groups such as dimethylphenylsilyl group.
- transition metal compound represented by the general formula (1-Y-3) a compound represented by the following general formula (1-Y-3b) is preferably used.
- M, X, T 4 and R 16 are the same as those in the general formula (1-Y-3), respectively, and T 3 and g are Y-2b) is the same.
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, a trialkylsilylmethyl group, an alkoxo group, an aryloxo group, or an N, N-dialkylamide group.
- R 12 to R 15 are the same as those in the general formula (1-Y-3a).
- R f contained in R 12 to R 15 , R 16 , T 3, and R g contained in T 4 may be the same or different from each other, and R 12 , R 13 , R 14 , R 15 , R 16 together, R g together, may be the same or different, when R f is a plurality, R f each other may be the same or different from each other.
- R 12 to R 15 , R 16 , R f , R g may be connected to each other to form a ring, and when there are a plurality of R f , two or more R f may be connected to each other to form a ring.
- R 12 to R 15 , R 16 , R f , R g are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a heterocyclic compound residue,
- carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- Hydrocarbyl groups such as 6-20 aryl groups, and some or all of the hydrogen atoms in these hydrocarbyl groups are substituted with halogen atoms.
- transition metal compound (AY) represented by the general formula (1-Y-3) examples of the specific structure of the transition metal compound (AY) represented by the general formula (1-Y-3) are shown below, but are not limited thereto.
- the modified compounds are similarly mentioned.
- transition metal compound (AY) represented by the general formula (1-Y-3) is described in “Organometallics”, Vol. 28, 1391 (2009), “Macromolecules”, Vol. 43, 1689 (2010).
- M, X, and R 12 to R 15 are the same as those in the general formula (1-Y-2a), and T 3 and g are the same as in the general formula (1).
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom.
- T 3 each other may be the same or different from each other.
- T 5 is —CR h 2 —, —C 6 R h 4 —, —SiR h 2 —, —NR h —, —PR h —, —P (O) R h —, —S—, —S ( O) — or —SO 2 —, preferably —CR h 2 —, —C 6 R h 4 —, —SiR h 2 —, more preferably —C 6 R h 4 —.
- T 5 contains a hetero atom
- the hetero atom of T 5 may be directly coordinated to M. Further, T 5 together may be the same or different from each other.
- R h contained in T 5 include the same as X in the general formula (1-Y).
- R 12 to R 15 are the same as those in the general formula (1-Y-2a).
- R 12 to R 15 , R f contained in T 3, and R h contained in T 5 may be the same or different from each other, and R 12 to each other, R 13 to each other, R 14 to each other, R 15 to each other, R h to each other or different are identical to one another, when R f is a plurality, R f each other may be the same or different from each other.
- Two or more of R 12 to R 15 , R f , and R h may be connected to each other to form a ring.
- R 12 to R 15 , R f and R h are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group or a heterocyclic compound residue, more preferably methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- Idrocarbyl and perhalocarbyl groups and hydrocarbyl-substituted silyl groups such as trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl groups, and pyrrolidyl, pyrrolyl, piperidyl, pyrazolyl, imidazolyl, and indolyl groups , 2 to 30, preferably 2 to 20, heterocyclic compound residues such as carbazolyl groups, etc., and groups in which some or all of the hydrogen atoms in these heterocyclic compound residues have been substituted with hydrocarbyl groups It is.
- transition metal compound represented by the general formula (1-Y-4) a compound represented by the following general formula (1-Y-4a) is preferably used.
- M, X, T 3 and g are the same as those in the general formula (1-Y-4).
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom. If g is 2 or more, T 3 each other may be the same or different from each other.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, a trialkylsilylmethyl group, an alkoxo group, an aryloxo group, or an N, N-dialkylamide group.
- R 12 to R 15 are the same as those in the general formula (1-Y-4), and R 17 to R 20 are also the same as R 12 to R 15 in the general formula (1-Y-4).
- R f contained in R 12 to R 15 , R 17 to R 20 , and T 3 may be the same as or different from each other, and R 12 to each other, R 13 to each other, R 14 to each other, R 15 to each other, R 17 to each other, R 18 , R 19 , and R 20 may be the same or different from each other.
- R f may be the same or different from each other.
- Two or more of R 12 to R 15 , R 17 to R 20 , and R f may be connected to each other to form a ring.
- two or more R f may be connected to each other to form a ring.
- R 12 to R 15 , R 17 to R 20 , and R f are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a heterocyclic compound residue,
- carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- Hydrocarbyl groups such as 6 to 20 aryl groups, and some or all of hydrogen atoms in these hydrocarbyl groups are substituted with halogen atoms.
- halohydrocarbyl group and perhalocarbyl group, and hydrocarbyl-substituted silyl groups such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, and pyrrolidyl group, pyrrolyl group, piperidyl group, pyrazolyl group, 2-30, preferably 2-20 heterocyclic compound residues such as imidazolyl, indolyl, carbazolyl, etc., and some or all of the hydrogen atoms in these heterocyclic compound residues are hydrocarbyl groups Is a group substituted by.
- transition metal compound represented by the general formula (1-Y-4a) a compound represented by the following general formula (1-Y-4b) is preferably used.
- M, X, T 3 and g are the same as those in the general formula (1-Y-4a).
- M is preferably a group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a zirconium atom or a hafnium atom. If g is 2 or more, T 3 each other may be the same or different from each other.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, a trialkylsilylmethyl group, an alkoxo group, an aryloxo group, or an N, N-dialkylamide group.
- R 13 , R 15 and R 18 represent the same as those in the general formula (1-Y-4a).
- R f contained in R 13 , R 15 , R 18 , and T 3 may be the same or different, and R 13 , R 15 , and R 18 may be the same or different, and g is 2 In the above case, R f may be the same or different from each other.
- R 13 , R 15 , R 18 , and R f may be connected to each other to form a ring.
- g is 2 or more, two or more R f may be bonded to each other. They may be connected to each other to form a ring.
- R 13 , R 15 , R 18 and R f are preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, or a heterocyclic compound residue, more preferably methyl.
- Hydrocarbyl group and perhalocarbyl group, and hydrocarbyl-substituted silyl groups such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, and pyrrolidyl group, pyrrolyl group, piperidyl group, pyrazolyl group, imidazolyl group, 2-30, preferably 2-20 heterocyclic compound residues such as indolyl group, carbazolyl group, etc., and some or all of the hydrogen atoms in these heterocyclic compound residues are substituted with hydrocarbyl groups. It is a group.
- transition metal compound represented by the general formula (1-Y-4b) a compound represented by the following general formula (1-Y-4c) is preferably used.
- each X represents the same as in the general formula (1-Y-4b), and X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, or a trialkyl.
- X is preferably a halogen atom, a methyl group, a neopentyl group, a benzyl group, or a trialkyl.
- R 21 may be the same as X in the general formula (1-Y). R 21 may be the same as or different from each other, and R 21 may be linked to each other to form a ring.
- R 21 is preferably a hydrogen atom, a halogen atom, a carbon-containing group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, or a heterocyclic compound residue, more preferably a methyl group, an ethyl group, or an n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc.
- Hydrocarbyl groups such as chain groups or branched alkyl groups, phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, phenanthryl groups, anthracenyl groups and the like, and aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.
- aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.
- some or all of the hydrogen atoms in these hydrocarbyl groups are substituted with halogen atoms.
- -Halocarbyl groups, and hydrocarbyl-substituted silyl groups such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group.
- transition metal compound (AY) represented by the general formula (1-Y-4) examples of the specific structure of the transition metal compound (AY) represented by the general formula (1-Y-4) are shown below, but are not limited thereto.
- the modified compounds are similarly mentioned.
- the transition metal compound (AY) represented by the general formula (1-Y-4) can be produced by the method described in US Pat. No. 7,241,714.
- M and X are the same as those in the general formula (1-Y), and R 22 is the same as X in the general formula (1-Y). Is mentioned.
- M is preferably a transition metal atom of Group 4 or 5 of the periodic table, more preferably a transition metal atom of Group 4, specifically a titanium atom, a zirconium atom, or a hafnium atom, Titanium atoms and zirconium atoms are preferred.
- X is preferably a hydrogen atom, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrocarbyl group, or a silicon-containing group, and these groups are up to 20 other than hydrogen. It is a group containing an atom, and a part or all of the hydrogen atoms of the hydrocarbyl group may be substituted with one or more of a halogen atom, an oxygen-containing group and a nitrogen-containing group.
- b is an integer of 1 to 4. When b is 2 or more, Xs may be the same or different from each other, and two or more Xs may be connected to each other to form a ring.
- R 22 is preferably a hydrogen atom, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrocarbyl group, or a silicon-containing group, and up to 20 of these groups other than hydrogen. And a part or all of the hydrogen atoms of the hydrocarbyl group may be substituted with any one or more of a halogen atom, an oxygen-containing group and a nitrogen-containing group.
- R 22 may be the same as or different from each other, and two adjacent R 22s may be connected to each other to form a ring.
- the ring formed by the bond between the substituents R 22 on the cyclopentadienyl ring may include any ring such as an aromatic ring, an aliphatic ring or a heterocyclic ring, but preferably an indenyl ring, a fluorenyl ring, Such as an azulenyl ring, and some or all of the hydrogen atoms on these rings may be further substituted with R 22 .
- M is preferably a transition metal atom of Group 4 or 5 of the periodic table, more preferably a transition metal atom of Group 4, specifically a titanium atom, a zirconium atom, or a hafnium atom. Particularly preferred are a zirconium atom and a hafnium atom.
- X is preferably a hydrogen atom, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrocarbyl group, or a silicon-containing group, and these groups are up to 20 other than hydrogen. It is a group containing an atom, and a part or all of the hydrogen atoms of the hydrocarbyl group may be substituted with one or more of a halogen atom, an oxygen-containing group and a nitrogen-containing group.
- b is an integer of 1 to 3. When b is 2 or more, Xs may be the same or different from each other, and two or more Xs may be connected to each other to form a ring.
- R 22 is preferably a hydrogen atom, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a hydrocarbyl group, or a silicon-containing group, and these groups are groups containing up to 20 atoms other than hydrogen.
- some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with one or more of halogen atoms, oxygen-containing groups, nitrogen-containing groups.
- R 22 may be the same as or different from each other, and two adjacent R 22s may be connected to each other to form a ring.
- the ring formed by the bond between the substituents R 22 on the cyclopentadienyl ring may include any ring such as an aromatic ring, an aliphatic ring or a heterocyclic ring, but preferably an indenyl ring, a fluorenyl ring, Such as an azulenyl ring, and some or all of the hydrogen atoms on these rings may be further substituted with R 22 .
- Examples of the general formula (1-Y-6) are given below.
- Bis (cyclopentadienyl) zirconium dichloride bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (penta Methylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride,
- transition metal compounds (AY) represented by the general formulas (1-Y-5) and (1-Y-6) are disclosed in JP-A-3-163088, JP-A-3-188092, 4-268307, JP-A-6-206890, and JP-A-9-87313.
- M, X, and b are the same as those in the general formula (1-Y).
- M is preferably a transition metal atom of Group 8 or Group 9 of the periodic table, more preferably an iron atom and a cobalt atom, and still more preferably an iron atom.
- Z is a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a nitrogen-containing group having a substituent R m (—NR m —) or a phosphorus-containing group having a substituent R m (—PR m —), preferably Are a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a nitrogen atom.
- R m contained in R 23 to R 25 and Z are the same as those in X in the general formula (1-Y).
- R 23 to R 25 and R m may be the same or different from each other, and R 23 , R 24 , and R 25 may be the same or different from each other.
- Two or more of R 23 , R 24 , R 25 and R m may be connected to each other to form a ring.
- transition metal compound (AY) represented by the general formula (1-Y-7) examples of the specific structure of the transition metal compound (AY) represented by the general formula (1-Y-7) are shown below, but are not limited thereto.
- the compound changed to dimethylamide, diethylamide, sulfonate, hexafluorophosphate is also mentioned similarly.
- the transition metal compound (AY) represented by the general formula (1-Y-7) is small, B. L .; Brookhart, M .; Bennett, A. M. A. J. Am. Chem. Soc. 1998, 120, 4049-4050.
- M, X and b are the same as those in the general formula (1-Y).
- M is preferably a group 10 transition metal atom of the periodic table, more preferably a nickel atom or a palladium atom, and still more preferably a nickel atom.
- R 26 and R 27 are the same as those of X in the general formula (1-Y).
- R 26 and R 27 may be the same as or different from each other.
- Two or more selected from two R 26 and two R 27 may be linked to each other to form a ring.
- transition metal compound (AY) represented by the general formula (1-Y-8) examples of the specific structure of the transition metal compound (AY) represented by the general formula (1-Y-8) are shown below, but are not limited thereto.
- the compound changed into diethylamide, sulfonate, and hexafluorophosphate is also mentioned similarly.
- the transition metal compound (AY) represented by the general formula (1-Y-8) includes Ittel, S. D .; Johnson, L. K .; Brookhart, M. Chem. Rev. 2000, 100, It can be produced by the method described in 1169-1204.
- the active promoter component (B) used in the present invention includes the following organoaluminum oxy compounds (B-1), organoboron compounds (B-2), zinc promoter components (B-3), and ion exchange.
- organoaluminum oxy compounds B-1
- organoboron compounds B-2
- zinc promoter components B-3
- ion exchange One or more kinds of compounds selected from the conductive layered silicate (B-4).
- organoaluminum oxy compound (B-1) examples include one or more compounds selected from the following compounds (B-1-1) and (B-1-2).
- R B1 and R B2 represented by B2 represent hydrocarbyl groups having 1 to 20 carbon atoms, and R B1 and R B2 may be the same or different.
- Subscript B1 and B2 represent an integer of 2 or more.
- R B1 and R B2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and a neopentyl group.
- a linear or branched alkynyl group having 2 to 20, preferably 2 to 10 carbon atoms such as an ethynyl group or a propargyl group The recited, and more preferably, a methyl group or isobutyl group.
- the organoaluminum oxy compound (B-1) can be produced, for example, by the following method and is usually obtained as a solution in a hydrocarbyl solvent.
- Compounds containing adsorbed water or salts containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc.
- a method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbyl suspension.
- the organoaluminum oxy compound (B-1) may contain a small amount of an organoaluminum component.
- the aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.
- Organic boron compound (B-2) examples include one or more compounds selected from the following compounds (B-2-1), (B-2-2), and (B-2-3).
- Q B + represents an inorganic or organic cation
- the inorganic cation is preferably a lithium cation, sodium cation, potassium cation, silver cation, ferrocenium cation or substituted ferrocenium cation, and is preferably an organic cation.
- E B H + represents a Bronsted acid, and preferred examples include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium.
- R B3 , R B4 and R B5 are each a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halohydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbylsilyl group having 1 to 20 carbon atoms.
- R B3 , R B4, and R B5 may be the same or different.
- BR B4 4 - and BR B5 4 - represents a borate anion, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5- Fluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, phenyltris (penta Fluorophenyl) borate and the like.
- borane compound (B-2-1) represented by the general formula BR B3 3 examples include 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, tris (3,5-bistrifluoromethyl) Phenyl) borane, phenylbis (pentafluorophenyl) borane, and the like.
- the organoboron compound (B-2) as described above may be used in combination of two or more, or may be used in combination with the organoaluminum oxy compound (B-1).
- ⁇ Zinc promoter component (B-3)> As the zinc promoter component (B-3), the zinc promoter component (B-3-1) obtained by contacting the following compound (B-3a) and the compound (B-3b) or the following compound (B -3a) to (B-3c) are contacted with a zinc promoter component (B-3-2).
- the compound represented by T B2 H 2 R B6 represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and R B6 may be the same or different.
- R B7 and R B8 each independently represent a hydrocarbyl group, a halogenated hydrocarbyl group, an electron withdrawing group or a group containing an electron withdrawing group, and R B7 and R B8 may be the same or different.
- T B1 and T B2 each independently represent an atom of Group 15 or Group 16 of the Periodic Table.
- B3 represents a valence of T B1
- B4 represents a valence of T B2.
- Examples of the compound (B-3a) include dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc, diisobutyl zinc, dinormal hexyl zinc, diallyl zinc, and bis (cyclopentadienyl) zinc.
- dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc, diisobutyl zinc, dinormal hexyl zinc, diallyl zinc, and bis (cyclopentadienyl) zinc.
- Diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, normal butyl zinc chloride, isobutyl zinc chloride, normal hexyl zinc chloride, methyl zinc bromide, Ethyl zinc bromide, propyl zinc bromide, normal butyl zinc bromide, isobutyl zinc bromide, normal hexyl bromide zinc, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, normal butyl zinc iodide, iodide Isobutyl zinc, normal iodide Halogenated alkyl zinc such as sill zinc; and the like; zinc fluoride, zinc chloride, zinc bromide, zinc halide such as zinc iodide.
- Examples of amines of the compound (B-3b) include di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, and bis (dichloro).
- Methyl) amine bis (dibromomethyl) amine, bis (diiodomethyl) amine, bis (trifluoromethyl) amine, bis (trichloromethyl) amine, bis (tribromomethyl) amine, bis (triiodomethyl) amine, bis ( 2,2,2-trifluoroethyl) amine, bis (2,2,2-trichloroethyl) amine, bis (2,2,2-tribromoethyl) amine, bis (2,2,2-triiodoethyl) ) Amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,3,3,3) Pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2,2- Trifluoro-1-trifluoromethylethyl) amine, bis
- a phosphine compound in which a nitrogen atom in the compound is substituted with a phosphorus atom is also an example of the compound (B-3b).
- These phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples to phosphine.
- Examples of the alcohol of the compound (B-3b) include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodethanol, trifluoromethanol, trichloromethanol, tribromomethanol, Triiodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3 , 3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, , 2,2-trifluoro-1-trifluorome Ethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-trii
- a thiol compound in which an oxygen atom in the above compound is substituted with a sulfur atom is also an example of the compound (B-3b).
- These thiol compounds are compounds represented by rewriting methanol in the above specific examples to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.
- Examples of the phenols of the compound (B-3b) include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3 -Bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol, 3,5-dichloro Phenol, 2,6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol, 2,4,6-trifluorophenol, 3,4,5-trifluoro Phenol, 2,4,6-trichlorophenol, 2,4,6 Tribromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, 2-
- thiophenol compound in which an oxygen atom in the above compound is substituted with a sulfur atom is also an example of the compound (B-3b).
- These thiophenol compounds are compounds represented by rewriting phenols of the specific examples described above with thiophenols.
- Examples of the carboxylic acids of the compound (B-3b) include 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2, 5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4 , 5-trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, Fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoic acid, heptafluorobutanoic acid, 1,1-bis (trifluoromethyl) -2,2,2-tri Such as
- Examples of the sulfonic acids of the compound (B-3b) include fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1-bis (trifluoromethyl). ) -2,2,2-trifluoroethanesulfonic acid and the like.
- the compound (B-3b) is preferably bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, or bis (2,2,3,3,3-penta).
- Fluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, Or bis (pentafluorophenyl) amine, and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2- Trifluoro-1-trifluoromethylethanol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol
- phenols 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-triflu
- the amount of the compounds (B-3a) and (B-3b) used when the compounds (B-3a) and (B-3b) are contacted is preferably based on 1 mol of the compound (B-3a).
- the compound (B-3b) is greater than 0 mole and less than or equal to 100 moles, more preferably the compound (B-3b) is greater than 0 mole and less than or equal to 20 moles, and more preferably, the compound (B-3b) is 0 mole or less. More preferably, the compound (B-3b) is greater than 0 mole and less than 5 moles, and most preferably, the compound (B-3b) is greater than 0 mole and less than 4 moles. .
- the method for producing the zinc promoter component (B-3-1) will be described in more detail below when the compound (B-3a) is diethyl zinc and the compound (B-3b) is a halogenated alcohol.
- a toluene solution of diethylzinc is added to a toluene solvent, cooled to 0 ° C., and 2 to 4 moles of halogenated alcohol are added dropwise to diethylzinc, and then at 90 ° C. to 120 ° C. for 10 minutes to 24 ° C. Stir for hours. After distilling off the volatile substances under reduced pressure, the residue is dried at room temperature under reduced pressure for 1 to 20 hours. Thereby, the component (B-3-1) can be produced.
- the compound (B-3c) is preferably water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) arylamine, more preferably water.
- Hydrogen sulfide methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, amylamine, n-hexylamine, n- Octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-tolylamine, 4-tolylami 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 5-trimethylaniline, 2,3,6
- Component (B-3-2) is a component obtained by bringing compounds (B-3a), (B-3b) and (B-3c) into contact with each other.
- the order in which (B-3a), (B-3b), and (B-3c) are brought into contact with each other is not particularly limited.
- the following orders (1) to (3) can be employed.
- (2) A method of contacting (B-3b) after contacting (B-3a) and (B-3c).
- the contact order is preferably (1) or (2), more preferably (1).
- the component (B-3-2) is preferably a component obtained by bringing (B-3c) into contact with a contact product obtained by bringing (B-3a) and (B-3b) into contact with each other. Or a component obtained by bringing (B-3a) and (B-3c) into contact with (B-3b), and more preferably (B-3a) and (B-3b).
- -3b) is a component obtained by contacting the contact product obtained by contacting (B-3c).
- y is more preferably a number of 0.20 to 1.80, particularly preferably a number of 0.25 to 1.50, most preferably 0.50 to 1. .00 number.
- silicate ion-exchange layered silicate
- Silicate has a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with each other and have a binding force.
- a silicate compound in which the ions to be exchanged are exchangeable Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can.
- Specific examples of the silicate include, for example, the following layered silicate described in Reference: Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
- smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculite such as vermiculite, mica, mica, illite, sericite, sea green stone, attapulgite, sepiolite, palygorskite , Bentonite, pyrophyllite, talc, chlorite group.
- the silicate used as a raw material in the present invention is preferably a silicate having a 2: 1 type structure as a main component silicate, more preferably a smectite group, and particularly preferably montmorillonite.
- the kind of interlayer cation is preferably a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation from the viewpoint that it can be obtained relatively easily and inexpensively as an industrial raw material.
- the silicate used in the present invention can be used as it is without any particular treatment, It is preferable to perform chemical treatment.
- chemical treatment any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay can be used.
- Specific examples of the chemical treatment in the present invention include the following (1) acid treatment, (2) salt treatment, (3) alkali treatment, and (4) organic matter treatment.
- the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. in the crystal structure.
- the acid used in the acid treatment is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or oxalic acid. Two or more acids may be used for the treatment.
- the conditions for treating a silicate with an acid are usually an acid concentration of 0.1 to 50% by weight, a treatment temperature of room temperature to a boiling point, and a treatment time of 5 minutes to 24 hours.
- the acid is generally used in an aqueous solution.
- Salts used in such salt treatment for ion exchange are a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid and an organic acid.
- At least one anion selected from the group consisting of OH, O 2 Cl 2 , OCl 3 , OOCH, OOCCH 2 CH 3 , C 2 H 4 O 4 and C 5 H 5 O 7 Is a compound consisting of
- salts include LiF, LiCl, LiBr, LiI, Li 2 SO 4 , Li (CH 3 COO), LiCO 3 , Li (C 6 H 5 O 7 ), LiCHO 2 , LiC 2 O 4 , LiClO 4.
- Alkali treatment examples include LiOH, NaOH, KOH, Mg (OH) 2 , Ca (OH) 2 , Sr (OH) 2 , and Ba (OH) 2 .
- Organic substance treatment examples include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
- anion constituting the organic treatment agent examples include anions exemplified as anions constituting the salt treatment agent, hexafluorophosphate, tetrafluoroborate, tetraphenylborate and the like.
- silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water before use. Silicate adsorbed water and interlayer water can be removed by heating the silicate, but it is necessary to select heating conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer.
- the moisture content of the silicate obtained by dehydrating silicate for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight
- the moisture content of the silicate is 3% by weight or less, preferably 1 It is preferable to heat the silicate so that it is not more than wt%.
- the ion-exchange layered silicate (B-4) a particularly preferable one is obtained by performing a salt treatment and / or an acid treatment and having a water content of 3% by weight or less.
- Silicate is preferably treated with an organometallic compound (C) described later before being used as a catalyst raw material or catalyst.
- the usage-amount of the organometallic compound (C) with respect to 1g of silicate is 20 mmol or less normally, Preferably it is 0.5 mmol or more and 10 mmol or less.
- the treatment temperature is usually from 0 ° C. to 70 ° C., and the treatment time is from 10 minutes to 3 hours. It is preferred to wash the silicate after treatment.
- the solvent used for the washing is the same hydrocarbon solvent as that used in the prepolymerization or slurry polymerization described later.
- spherical particles having an average particle diameter of 5 ⁇ m or more are preferably used. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a silicate whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used. Examples of the granulation method include a stirring granulation method and a spray granulation method. In granulation, organic substances, inorganic solvents, inorganic salts, and various binders may be used.
- the spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, from the viewpoint of suppressing crushing or generation of fine powder in the polymerization step.
- a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, from the viewpoint of suppressing crushing or generation of fine powder in the polymerization step.
- the organoaluminum oxy compound (B-1), the organoboron compound (B-2), the zinc promoter component (B-3), and the ion-exchange layered silicate (B-4) are used alone. Or you may use in combination of 2 or more types.
- Organometallic compound (C) used in the present invention is not particularly limited as long as it is a compound containing an element selected from Groups 2, 12 and 13 of the Periodic Table (except for the activation promoter component (B)). However, at least one compound selected from the group of compounds represented by the following formula is used. M C RC p (NR C 2 ) q (OR C ) r X C s
- M C represents a periodic table of the elements 2, 12, 13 group atoms, for example, beryllium atom, a magnesium atom, calcium atom, a strontium atom, a barium atom, a zinc atom, cadmium atom, a mercury atom, a boron atom, an aluminum atom Gallium atom, indium atom, thallium atom, etc., preferably magnesium atom, calcium atom, aluminum atom, zinc atom or gallium atom, more preferably aluminum atom or zinc atom.
- R C represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and examples thereof include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group, and these include a halogen atom, a hydrocarbyloxy group, It may have an amino group, a nitro group, a sulfonyl group, a silyl group, or the like as a substituent. Moreover, several RC may mutually be same or different.
- alkyl group examples include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
- Branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, isoamyl group, and 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group
- a cyclic alkyl group such as a cyclooctyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms.
- Examples of the aralkyl group include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 20 carbon atoms is preferable.
- Examples of the aryl group include a phenyl group, a naphthyl group, and a tolyl group, and an aryl group having 6 to 20 carbon atoms is preferable.
- alkenyl group examples include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group, branched alkenyl groups such as isobutenyl group, and 4-methyl-3-pentenyl group, Examples thereof include a cyclic alkenyl group such as a 2-cyclohexenyl group and a 3-cyclohexenyl group, and a linear or branched alkenyl group having 2 to 20 carbon atoms is preferable.
- X C represents a halogen atom, and examples thereof include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and a chlorine atom is preferable. Further, a plurality of X C each other may be the same or different from each other.
- organoaluminum compound used as the organometallic compound (C) in the present invention examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-pentylaluminum, and tri-n-hexylaluminum.
- Tri-n-alkylaluminum such as tri-n-octylaluminum, tri-n-decylaluminum; Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; Triarylaluminum such as triphenylaluminum, Diethyl aluminum bromide, di n-propyl
- organic zinc compound used as the organometallic compound (C) in the present invention examples include dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, di-n-pentyl zinc, and di-n-hexyl zinc.
- Di-n-alkyl zinc such as di-n-octyl zinc and di-n-decyl zinc; Diisopropylzinc, diisobutylzinc, disec-butylzinc, ditert-butylzinc, di2-methylbutylzinc, di3-methylbutylzinc, di2-methylpentylzinc, di3-methylpentylzinc, di4-methylpentylzinc Di-branched alkyl zinc such as di-2-methylhexyl zinc, di-3-methylhexyl zinc, di-2-ethylhexyl zinc, Dicycloalkylzinc such as dicyclohexylzinc and dicyclooctylzinc, Diaryl zinc such as diphenyl zinc; Ethyl zinc bromide, n-propyl zinc bromide, n-butyl zinc bromide, n-pentyl zinc bromide, n-hexyl zinc
- the support (D) is used as needed for the purpose of supporting the transition metal compound (AX) and / or the transition metal compound (AY) and / or the activating cocatalyst component (B). Is done.
- the carrier (D) examples include inorganic oxide particles, inorganic halide particles, and organic polymer particles. Among them, porous particles having a uniform particle diameter are preferable. From the viewpoint of the particle size distribution of the obtained polymer, the carrier (D) having a volume standard geometric standard deviation of the particle size of preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less. Is used.
- any inorganic oxide may be used, and a plurality of inorganic substances may be mixed and used.
- the inorganic oxide include SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, and ThO 2 , and mixtures thereof, SiO 2 —MgO, SiO.
- Examples include 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.
- These inorganic oxides are preferably SiO 2 and / or Al 2 O 3 , and particularly preferably SiO 2 .
- 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 , Carbonic acid salts such as Al (NO 3 ) 3 , Na 2 O, K 2 O, and Li 2 O, sulfates, nitrates, and oxide components may be contained.
- the inorganic oxide is preferably dried to substantially remove moisture, and the drying method is preferably heat drying.
- the drying temperature is usually 100 to 1500 ° C., preferably 100 to 1000 ° C., more preferably 200 to 800 ° C.
- the drying time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
- Examples of the heat drying method include a method in which an inert gas (eg, nitrogen or argon) dried while heating the inorganic oxide is circulated at a constant flow rate, or the inorganic oxide is removed under reduced pressure. The method of heat-drying etc. are mentioned.
- Inorganic oxides usually have hydroxy groups formed on the surface, but modified inorganic oxides in which active hydrogen of surface hydroxy groups are substituted with various substituents can be used as inorganic oxides.
- modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldichlorosilanes such as diphenyldichlorosilane.
- Alkyltrichlorosilanes such as methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane, and dialkyldialkoxysilanes such as dimethyldimethoxysilane , Diaryldialkoxysilanes such as diphenyldimethoxysilane, and alkyltols such as methyltrimethoxysilane Alkoxysilane, aryltrialkoxysilane such as phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, methanol
- dialkylamines such as diethylamine and diphenylamine
- alcohols such as methanol and ethanol
- inorganic oxides contacted with phenol there can be mentioned dialkylamines such as diethylamine and diphenylamine, alcohols such as methanol and ethanol, and inorganic oxides contacted with phenol.
- Inorganic oxides may have increased strength due to hydrogen bonding between hydroxy groups. In that case, if all the active hydrogens of the surface hydroxy group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to replace all active hydrogens on the surface hydroxy group of the inorganic oxide, and the substitution rate of the surface hydroxy group may be determined as appropriate. The substitution rate of the surface hydroxy group can be changed depending on, for example, the amount of the compound used for the contact treatment.
- the average particle size of the inorganic oxide particles is not particularly limited, but is usually 1 to 5000 ⁇ m, 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 oxide particles is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g.
- the specific surface area of the inorganic oxide particles is preferably 10 to 1000 m 2 / g, more preferably 100 to 500 m 2 / g.
- the inorganic halide MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 or the like is used.
- the inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. It is also possible to use an inorganic halide obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating them in a fine particle form with a precipitating agent.
- organic polymer may be used as the organic polymer particles, and a mixture of plural kinds of organic polymers may be used.
- the organic polymer is preferably a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group.
- the functional group having active hydrogen is not particularly limited as long as it has active hydrogen.
- the functional group for example, 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 group, Examples thereof include a sulfinic acid group, a sulfenic acid group, a thiol group, a thioformyl group, a pyrrolyl group, an imidazolyl group, a piperidyl group, an indazolyl group, and a carbazolyl group.
- the non-proton donating Lewis basic functional group is not particularly limited as long as it has no active hydrogen atom and has a Lewis base moiety.
- the functional group include a pyridyl group, an N-substituted imidazolyl group, an N-substituted indazolyl group, a nitrile group, an azide group, an N-substituted imino group, an N, N-substituted amino group, and an N, N-substituted aminooxy group.
- a heterocyclic group is preferable, and an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring is more preferable.
- a pyridyl group an N-substituted imidazolyl group and an N-substituted indazolyl group
- a pyridyl group is particularly preferred. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
- the content of the functional group having active hydrogen or the non-proton donating Lewis basic functional group in the organic polymer is not particularly limited.
- the content thereof is preferably 0.01 to 50 mmol / g, more preferably 0.1 to 20 mmol / g as the molar amount of the functional group per gram of the polymer.
- Examples of the method for producing an organic polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group include a functional group having active hydrogen or a non-proton donating Lewis basic functional group,
- the method of homopolymerizing the monomer which has the above polymerizable unsaturated groups, or the method of copolymerizing the monomer and the other monomer which has a polymerizable unsaturated group is mentioned. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.
- Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group, and alkynyl groups such as ethyne group.
- Examples of the monomer 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. Is mentioned.
- Examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine.
- Monomers having no active hydrogen atom and having a functional group having a Lewis base moiety and one or more polymerizable unsaturated groups include, for example, vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N— Substituted) indazole.
- Examples of the other monomer having a polymerizable unsaturated group include ethylene, ⁇ -olefin, aromatic vinyl compound and cyclic olefin compound.
- Examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Preferred is ethylene or styrene. Two or more of these monomers may be used.
- Examples of the crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.
- the average particle diameter of the organic polymer particles is not particularly limited, but is usually 1 to 5000 ⁇ m, preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m.
- the pore volume of the organic polymer particles is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g.
- the specific surface area of the organic polymer particles is preferably 10 to 1000 m 2 / g, more preferably 50 to 500 m 2 / g.
- These organic polymer particles are preferably dried and substantially free of moisture, and those dried by heat drying are preferred.
- the drying temperature is usually 30 to 400 ° C, preferably 50 to 200 ° C, more preferably 70 to 150 ° C.
- the heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
- a method of heat drying for example, a method of drying by circulating an inert gas (for example, nitrogen or argon) while heating the organic polymer particles at a constant flow rate, or the organic polymer particles under reduced pressure is used. The method of heat-drying etc. are mentioned.
- Examples of the organic polymer particles include granular or fine particle solids having a particle size in the range of 10 to 300 ⁇ m.
- the polymer forming the organic polymer particles is a (co) polymer produced mainly from an ⁇ -olefin having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene. Examples thereof include vinylcyclohexane, (co) polymers mainly composed of styrene, and modified products thereof.
- Organic compound (E) In the present invention, the organic compound (E) is used as necessary for the purpose of improving the polymerization performance and the physical properties of the produced polymer.
- Examples of the organic compound (E) include alcohols, phenols, carboxylic acids, amines, phosphorus compounds, and sulfonic acids and salts thereof.
- Alcohols and phenols are represented by the general formula R E1 OH, R E1 represents a halo hydrocarbyl group hydrocarbyl group or having 1 to 20 carbon atoms having 1 to 20 carbon atoms, preferably carbon atoms It is a halohydrocarbyl group of formula 1-10.
- the carboxylic acids are represented by the general formula R E2 COOH, and R E2 represents a hydrocarbyl group having 1 to 20 carbon atoms or a halohydrocarbyl group having 1 to 20 carbon atoms, preferably 1 to 1 carbon atom. 10 halohydrocarbyl groups.
- the amine is represented by the general formula NR E3 3 , wherein R E3 represents a hydrogen atom, a hydrocarbyl group having 1 to 20 carbon atoms or a halohydrocarbyl group having 1 to 20 carbon atoms, and at least one R E3 is a hydrocarbyl group or a halohydrocarbyl group, preferably a halohydrocarbyl group having 1 to 10 carbon atoms.
- the sulfonic acid and its salt are represented by the general formulas R E5 SO 3 H and (R E6 SO 3 ) t M E u , and M E is an element of Groups 1 to 14 of the periodic table.
- R E5 and R E6 are a hydrocarbyl group having 1 to 20 carbon atoms or a halohydrocarbyl group having 1 to 20 carbon atoms.
- a method for forming the polymerization catalyst (X) is not particularly limited, but includes a transition metal compound (AX), an activation promoter component (B), an organic metal compound (C) as an optional component, And the method of making a support
- the contact is carried out in the presence or absence of a solvent, and these contact mixtures may be added to the polymerization tank, or they may be separately added to the polymerization tank in any order and contacted in the polymerization tank. Alternatively, the optional two-component contact mixture and the remaining components may be added separately to the polymerization vessel.
- the addition method, addition order and addition amount of each component are arbitrarily selected, and the following methods are exemplified.
- a method in which a contact mixture of a catalyst component having a transition metal compound (AX) supported on a carrier (D) and an activating co-catalyst component (B) is added to a polymerization tank.
- a method in which a catalyst component in which a transition metal compound (AX) and an activating co-catalyst component (B) are supported on a carrier (D) is added to a polymerization tank.
- each of the above methods (1) to (9) it is used as a scavenger for a trace amount of water, oxygen and other components that become catalyst poisons in the polymerization tank, or as an alkylating agent for the transition metal compound (AX).
- one or more compounds selected from the organometallic compound (C) can be added to the polymerization tank in any order.
- the organometallic compound (C) is an optional component in the formation of the polymerization catalyst (X), but is an essential component in the production method according to the present invention.
- the supported catalyst component may be prepolymerized with olefin.
- a transition metal compound (AX) may further be supported on the catalyst component thus formed.
- the transition metal compound (AX) supported on the carrier (D) and the transition metal compound (AX) not supported on the carrier (D) may be the same as or different from each other.
- the activation promoter component (B) not supported is added as necessary. They may be added to the polymerization tank in any order. In this case, the activation promoter component (B) supported on the support (D) and the activation promoter component (B) not supported on the support (D) are the same or different from each other. Also good.
- the transition metal compound (AX) is generally used in an amount of 10 ⁇ 12 to 10 ⁇ 2 mol, preferably 10 ⁇ 10 to 10 ⁇ 3 mol per liter of reaction volume.
- the metal compound in the organoaluminum oxy compound (B-1) and the transition metal compound (AX) is usually 10 to 500,000, preferably 20 to 100,000.
- the organic boron compound (B-2) is used, the molar ratio [B / (AX)] between the boron atom in the organic boron compound (B-2) and the transition metal compound (AX) is The amount is usually 1 to 1,000, preferably 1 to 100.
- the method of (5), (6), (7), (8) in which each component is added to the polymerization tank in an arbitrary order is particularly preferable.
- the method (5) is more preferable.
- the above components constituting the polymerization catalyst (X), the transition metal compound (AX), the activation promoter component (B), the organometallic compound (C) and the carrier A plurality of different polymerization catalysts (X) formed such that at least one of (D) is different may be used.
- the method for forming the polymerization catalyst (Y) is not particularly limited, but includes a transition metal compound (AY), an activation promoter component (B), an organic metal compound (C) as an optional component, And the method of making a support
- the contact is carried out in the presence or absence of a solvent, and these contact mixtures may be added to the polymerization tank, or they may be separately added to the polymerization tank in any order and contacted in the polymerization tank. Alternatively, the optional two-component contact mixture and the remaining components may be added separately to the polymerization vessel.
- the addition method, the addition order, and the addition amount of each component are arbitrarily selected, and the following methods are exemplified.
- a method in which a contact mixture of a catalyst component carrying a transition metal compound (AY) on a carrier (D) and an activating co-catalyst component (B) is added to a polymerization tank.
- a method in which the catalyst component having the transition metal compound (AY) supported on the carrier (D) and the activating co-catalyst component (B) are added to the polymerization tank in an arbitrary order.
- each of the above methods (1) to (9) it is used as a scavenger for a trace amount of water, oxygen and other components that become catalyst poisons in the polymerization tank, or as an alkylating agent for the transition metal compound (AY).
- AY transition metal compound
- one or more compounds selected from the organometallic compound (C) can be added to the polymerization tank in any order.
- the organometallic compound (C) is an optional component in the formation of the polymerization catalyst (Y), but is an essential component in the production method according to the present invention.
- the supported catalyst component may be prepolymerized with olefin.
- a transition metal compound (AY) may be further supported on the catalyst component.
- the transition metal compound (AY) supported on the carrier (D) and the transition metal compound (AY) not supported on the carrier (D) may be the same as or different from each other. .
- the activation promoter component (B) not supported is added as necessary. They may be added to the polymerization tank in any order. In this case, the activation promoter component (B) supported on the support (D) and the activation promoter component (B) not supported on the support (D) are the same or different from each other. Also good.
- the transition metal compound (AY) is generally used in an amount of 10 ⁇ 12 to 10 ⁇ 2 mol, preferably 10 ⁇ 10 to 10 ⁇ 3 mol, per liter of reaction volume.
- the metal compound (B-1) When the organoaluminum oxy compound (B-1) is used as the activating co-catalyst component (B), the aluminum atom in the organoaluminum oxy compound (B-1) and the transition metal compound (AY)
- the molar ratio [Al / (AY)] is usually 10 to 500,000, preferably 20 to 100,000.
- the organoboron compound (B-2) When the organoboron compound (B-2) is used, the molar ratio [B / (AY)] between the boron atom in the organoboron compound (B-2) and the transition metal compound (AY) is The amount is usually 1 to 1,000, preferably 1 to 100.
- the method of (5), (6), (7), (8) in which each component is added to the polymerization tank in an arbitrary order is particularly preferable.
- the method (5) is more preferable.
- the above components constituting the polymerization catalyst (Y), transition metal compound (AY), activation promoter component (B), organometallic compound (C) and carrier A plurality of different polymerization catalysts (Y) formed such that at least one of (D) is different may be used.
- the co-catalyst for activation used to form both catalysts.
- Component (B), organometallic compound (C) used as an optional component, and carrier (D) used as an optional component may be the same or different in both catalysts.
- the activation co-catalyst component (B), the organometallic compound (C) and the transition metal compound (AX) previously contacted with each other.
- the carrier (D) may be used as a component for forming the polymerization catalyst (Y), and (D) on which the transition metal compound (AX) is previously supported is used as a component for forming the polymerization catalyst (Y). It may be used.
- the activation co-catalyst component (B), the organometallic compound (C) and the support (D), which have been contacted with the transition metal compound (AY) in advance, are used as components for forming the polymerization catalyst (X).
- (D) which previously supported the transition metal compound (AY) may be used as a component for forming the polymerization catalyst (X).
- Olefin used in the present invention is preferably an olefin having 2 to 20 carbon atoms, and examples thereof include ethylene, ⁇ -olefin, cyclic olefin, alkenyl alicyclic compound, and polar olefin.
- Examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene, 1-nonene, Examples include 1-decene.
- cyclic olefin examples include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 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 -Methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene
- alkenyl alicyclic compound examples include vinylcyclohexane.
- polar olefins examples include ⁇ , such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid.
- ⁇ -unsaturated carboxylic acid and its metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, acrylic ⁇ , ⁇ -unsaturated carboxylic acid esters such as 2-ethylhexyl acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; maleic acid, itaconic acid, etc.
- unsaturated dicarboxylic acids vinyl acetate, propi Vinyl esters such as vinyl acetate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate And so on.
- the olefin is preferably ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, a cyclic olefin having 3 to 20 carbon atoms, or an alkenyl alicyclic compound having 5 to 20 carbon atoms, and more preferably Ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, more preferably ethylene or an ⁇ -olefin having 3 to 10 carbon atoms, and most preferably ethylene or propylene.
- Olefins may be used alone or in combination of two or more.
- the addition method may be simultaneous or sequential, and the combination and use ratio of the olefins are not particularly limited.
- the olefin polymerization method may be either a liquid phase polymerization method such as a solvent polymerization method or a suspension polymerization method, or a gas phase polymerization method.
- the inert hydrocarbyl medium used in the liquid phase polymerization include aliphatic hydrocarbyl such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methyl.
- aliphatic hydrocarbyls such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene
- cyclopentane cyclohexane
- methyl examples include cycloaliphatic hydrocarbyls such as cyclopentane, aromatic hydrocarbyls such as benzene, toluene, and xylene, halohydrocarbyls such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof. Can also be
- the method for producing the olefin block polymer of the present invention is not limited as long as the olefin is polymerized using the polymerization catalyst (X), the polymerization catalyst (Y), and the organometallic compound (C), but the following polymerization method is used. Is mentioned.
- One method includes one or more polymerization catalysts (X), one or more polymerization catalysts (Y), one or more organometallic compounds (C), one or more olefins, and optionally an organic compound ( E) is a method for producing an olefin block polymer which performs single-stage polymerization consisting of a single polymerization step.
- the polymerization catalyst (X) and the polymerization catalyst (Y) are preferably formed almost simultaneously according to the method for forming the polymerization catalyst.
- the olefin is polymerized before the polymerization catalyst (X) or the polymerization catalyst (Y) is formed in the polymerization tank or outside the polymerization tank.
- the catalyst (Y) Before the catalyst (Y) is added to the polymerization tank, it is preferably added to the polymerization tank in advance.
- the concentration of olefin in the polymerization tank is kept constant during the polymerization so that the concentration and composition ratio of each olefin in the polymerization tank are kept constant during the polymerization. Olefin may be continuously added to the polymerization tank.
- Multistage polymerization method (2) Other methods include one or more polymerization catalysts (X), one or more polymerization catalysts (Y), one or more organic metal compounds (C), one or more olefins, and optionally an organic compound ( E), a method for producing an olefin block polymer that performs multi-stage polymerization comprising two or more polymerization steps, wherein each polymerization step has the same olefin composition and one adjacent two steps each.
- the multistage polymerization method (2) is an olefin having the same composition as that used in ⁇ Step 2X> in the presence of the polymerization catalyst (X) in the step ⁇ Step 2X> and in the presence of the polymerization catalyst (Y). At least a step of polymerizing ⁇ Step 2Y>.
- the polymerization catalyst (X) formed in ⁇ Step 2X> and the polymerization catalyst (Y) formed in ⁇ Step 2Y> in the multistage polymerization method (2) may be polymerized even if they are formed in a polymerization tank. A polymerization catalyst formed outside the tank may be added to the polymerization tank.
- the olefin used in ⁇ Step 2X> is the polymerization catalyst (X) formed before the polymerization catalyst (X) is formed in the polymerization tank or outside the polymerization tank.
- the olefin used in ⁇ Step 2Y> is preferably added in advance to the polymerization tank before being formed in the polymerization tank, or before the polymerization catalyst (Y) is formed in the polymerization tank. Before the formed polymerization catalyst (Y) is added to the polymerization tank, it is preferably added in advance to the polymerization tank.
- the concentration of olefin in the polymerization tank and the composition ratio are kept constant during the polymerization when the concentration of olefin in the polymerization tank is two or more olefins.
- olefin may be continuously added to the polymerization tank.
- the multistage polymerization method (2) is used in ⁇ Step 2X> and ⁇ Step 2Y> in the presence of a polymerization catalyst (X) or polymerization catalyst (Y) different from those used in ⁇ Step 2X> and ⁇ Step 2Y>. It may further include a step of polymerizing an olefin having the same composition as the former.
- the number of polymerization steps in the multistage polymerization method (2) is preferably 2 to 5 stages, more preferably 2 and 3 stages, and most preferably 2 stages.
- olefin polymerization is performed in the presence of the polymer obtained up to the previous polymerization step.
- the olefin is polymerized in the presence of the polymer produced in the previous polymerization step.
- Multistage polymerization method (3) Still other methods include one or more polymerization catalysts (X), one or more polymerization catalysts (Y), one or more organometallic compounds (C), one or more olefins, and optionally an organic compound.
- (E) is a method for producing an olefin block polymer that performs multi-stage polymerization comprising two or more polymerization steps, and each polymerization step is different in composition of olefins in two adjacent polymerization steps, and Two adjacent polymerization steps are a polymerization step using one or more types of polymerization catalysts (X) and a polymerization step using one or more types of polymerization catalysts (Y), which were obtained by the previous polymerization step.
- the multi-stage polymerization method (3) is used in the step ⁇ Step 3X> for polymerizing the olefin [X] in the presence of one or more kinds of polymerization catalysts (X) and in the ⁇ Step 3X> in the presence of the polymerization catalyst (Y). It includes at least a step ⁇ Step 3Y> of polymerizing olefin [Y] having a different composition from that of the conventional one.
- the polymerization catalyst (X) formed in ⁇ Step 3X> and the polymerization catalyst (Y) formed in ⁇ Step 3Y> in the multistage polymerization method (3) may be polymerized even if they are formed in a polymerization tank. A polymerization catalyst formed outside the tank may be added to the polymerization tank.
- the olefin [X] used in ⁇ Step 3X> is the polymerization catalyst (X) formed before the polymerization catalyst (X) is formed in the polymerization tank or outside the polymerization tank.
- the polymerization catalyst (Y) formed outside the polymerization tank is added to the polymerization tank, it is preferably added to the polymerization tank in advance.
- the olefin is one kind of olefin
- the concentration of olefin in the polymerization tank and the composition ratio are kept constant during the polymerization when the concentration of olefin in the polymerization tank is two or more olefins.
- olefin may be continuously added to the polymerization tank.
- the multistage polymerization method (3) is performed in ⁇ Step 3X> and ⁇ Step 3Y> in the presence of the same or different polymerization catalyst (X) or polymerization catalyst (Y) as used in ⁇ Step 3X> and ⁇ Step 3Y>.
- a step of polymerizing an olefin having a composition different from that used may be further included.
- the number of polymerization steps in the multistage polymerization method (3) is preferably 2 to 5 stages, more preferably 2 and 3 stages, and most preferably 2 stages.
- olefin polymerization is performed in the presence of the polymer obtained up to the previous polymerization step.
- the olefin is polymerized in the presence of the polymer produced in the previous polymerization step.
- the organometallic compound (C) can be added to the polymerization tank at any point in the reaction operation. It is preferably added to the polymerization tank before the start of polymerization, that is, before the polymerization catalyst (X) or the polymerization catalyst (Y) is formed.
- a method for adding the organometallic compound (C) for example, a method of adding the organometallic compound (C) to the polymerization tank by a specific method with stirring is preferable.
- the organometallic compound (C) may be added directly, or a solution dissolved in an organic solvent such as n-hexane may be added. Moreover, you may divide
- the organometallic compound (C) has a molar ratio [(C) / (A)] with the transition metal compound (A) of usually 1 to 100,000, preferably 10 to 10,000, more preferably 20 to 5,000. Used in quantity.
- the organic compound (E) When the organic compound (E) is used, it can be added to the polymerization tank either alone or as a contact mixture with the organometallic compound (C) at any point in the reaction operation.
- X) or the polymerization catalyst (Y) is preferably added to the polymerization tank before it is formed.
- a method for adding the organic compound (E) for example, a method of adding the organic compound (E) to the polymerization tank by a specific method with stirring is preferable.
- the organometallic compound (C) may be added directly, or a solution dissolved in an organic solvent such as n-hexane may be added. Moreover, you may divide
- the molar ratio [(E) / (C)] to the organometallic compound (C) is usually 0.001 to 10, preferably 0.005 to 2. Used in
- a polymerization catalyst (X) and a polymerization catalyst (Y) having different polymerization performance such as stereoregularity, introduction rate of branched structure, and copolymerization properties are selected. Furthermore, it is preferable to select the type and composition of the olefin so that two or more types of segments having different chemical or physical properties can be formed by the polymerization catalyst (X) and the polymerization catalyst (Y). Furthermore, in the multistage polymerization methods (2) and (3), the polymerization catalyst (X) and the polymerization catalyst used in each step so that the chemical or physical properties of the segments formed in the two adjacent polymerization steps are different from each other. It is preferable to select (Y).
- the polymerization catalyst (X) and the polymerization catalyst (Y) used in each step are different so that the chemical or physical properties of the segments formed in two adjacent polymerization steps are different from each other. It is preferred to select a combination of olefins.
- the single-stage polymerization method (1), multi-stage polymerization methods (2) and (3) may be continuous polymerization or batch polymerization, but are preferably batch polymerization. Furthermore, in the multistage polymerization methods (2) and (3), the subsequent polymerization step may be carried out in the same reaction vessel or reaction zone in the presence of the polymer produced up to the previous polymerization step. The polymer produced up to the previous polymerization step may be transferred to another reaction vessel or reaction zone, and the subsequent polymerization step may be carried out, but preferably the polymer produced up to the previous polymerization step In the same reaction vessel or reaction zone.
- Examples of the method for producing the olefin block polymer of the present invention include the single-stage polymerization method (1), the multi-stage polymerization method (2), and the multi-stage polymerization method (3), and preferably the single-stage polymerization method (1) and the multi-stage polymerization method. (3), more preferably the single-stage polymerization method (1).
- homopolymerization or copolymerization of one kind of olefin with the polymerization catalyst (X) and the polymerization catalyst (Y) having different stereoregularity or introduction rate of the branched structure are different from each other.
- the multi-stage polymerization method (3) is preferably a two-stage polymerization in which the olefin compositions are different from each other in the former stage and the latter stage, more preferably 2 consisting of copolymerization of two or more olefins and homopolymerization of one olefin.
- Stage polymerization previously stage and subsequent stage, regardless of the correspondence between copolymerization and homopolymerization
- two-stage polymerization consisting of ethylene / propylene copolymerization and propylene homopolymerization
- front stage and subsequent stage copolymerization and The correspondence of homopolymerization does not matter.
- an olefin is polymerized in the presence of a polymerization catalyst (X) and a polymerization catalyst (Y).
- the organometallic compound (C) has a molar ratio with the transition metal compound (AX) [(C) / (AX)] and a molar ratio with the transition metal compound (AY) [(C) / ( AY)] is usually used in an amount of 1 to 100,000, preferably 10 to 10,000, more preferably 20 to 5,000. Further, when the organic compound (E) is used, the molar ratio [(E) / (C)] to the organometallic compound (C) is usually 0.001 to 10, preferably 0.005 to 2. Used in quantity.
- the olefin to be polymerized by the single-stage polymerization method (1) is selected from one or more olefins having 2 to 20 carbon atoms. There is no restriction
- the olefin used is preferably one or more selected from ethylene, ⁇ -olefins having 3 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, or alkenyl alicyclic compounds having 5 to 20 carbon atoms.
- An olefin more preferably one or more olefins selected from ethylene or ⁇ -olefins having 3 to 20 carbon atoms, and more preferably selected from ethylene or ⁇ -olefins having 3 to 10 carbon atoms.
- the polymerization reaction temperature of the olefin in the single-stage polymerization method (1) is usually ⁇ 40 to 200 ° C., preferably 0 to 150 ° C., more preferably 40 to 130 ° C.
- the reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
- the reaction time is usually 5 minutes to 48 hours, preferably 5 minutes to 12 hours.
- ⁇ Step 2X> and ⁇ Step 2Y> may start from either of them.
- ⁇ Step 2X> front stage
- ⁇ Step 2Y> back stage
- the olefin is polymerized in the presence of the polymerization catalyst (X).
- the organometallic compound (C) has a molar ratio [(C) / (AX)] with the transition metal compound (AX).
- the amount is usually 1 to 100,000, preferably 10 to 10,000, more preferably 20 to 5,000.
- the organic compound (E) is used, the molar ratio [(E) / (C)] to the organometallic compound (C) is usually 0.001 to 10, preferably 0.005 to 2. Used in quantity.
- the olefin to be polymerized in ⁇ Step 2X> is selected from one or more olefins having 2 to 20 carbon atoms. There is no restriction
- the olefin used is preferably one or more selected from ethylene, ⁇ -olefins having 3 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, or alkenyl alicyclic compounds having 5 to 20 carbon atoms.
- An olefin more preferably one or more olefins selected from ethylene or ⁇ -olefins having 3 to 20 carbon atoms, and more preferably selected from ethylene or ⁇ -olefins having 3 to 10 carbon atoms.
- the polymerization reaction temperature of the olefin in ⁇ Step 2X> is usually ⁇ 40 to 200 ° C., preferably 0 to 150 ° C., more preferably 40 to 130 ° C.
- the reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
- the reaction time is usually 5 minutes to 48 hours, preferably 5 minutes to 12 hours.
- ⁇ Process 2Y> In ⁇ Step 2Y>, following ⁇ Step 2X>, an olefin having the same composition as that used in ⁇ Step 2X> is polymerized in the presence of the polymerization catalyst (Y).
- the organometallic compound (C) When the organometallic compound (C) is used in ⁇ Step 2Y>, the organometallic compound (C) has a molar ratio [(C) / (AY)] with the transition metal compound (AY).
- the amount is usually 1 to 100,000, preferably 10 to 10,000, more preferably 20 to 5,000.
- the organic compound (E) is used, the molar ratio [(E) / (C)] to the organometallic compound (C) is usually 0.001 to 10, preferably 0.005 to 2. Used in quantity.
- the olefin polymerized in ⁇ Step 2Y> is an olefin having the same composition as in ⁇ Step 2X>.
- the polymerization reaction temperature of the olefin in ⁇ Step 2Y> is usually ⁇ 40 to 200 ° C., preferably 0 to 150 ° C., more preferably 40 to 130 ° C.
- the reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
- the reaction time is usually 5 minutes to 48 hours, preferably 5 minutes to 12 hours.
- ⁇ Step 3X> and ⁇ Step 3Y> may start from either, but hereinafter, among the multi-stage polymerization method (3), ⁇ Step 3X> (front stage) and ⁇ Step 3Y> (back stage)
- ⁇ Step 3X> front stage
- ⁇ Step 3Y> back stage
- olefin [X] is polymerized in the presence of one or more polymerization catalysts (X).
- the organometallic compound (C) has a molar ratio [(C) / (AX)] with the transition metal compound (AX).
- the organic compound (E) is used, the molar ratio [(E) / (C)] to the organometallic compound (C) is usually 0.001 to 10, preferably 0.005 to 2. Used in quantity.
- the olefin to be polymerized in ⁇ Step 3X> is selected from one or more olefins having 2 to 20 carbon atoms. There is no restriction
- the olefin used is preferably one or more selected from ethylene, ⁇ -olefins having 3 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, or alkenyl alicyclic compounds having 5 to 20 carbon atoms.
- An olefin more preferably one or more olefins selected from ethylene or ⁇ -olefins having 3 to 20 carbon atoms, and more preferably selected from ethylene or ⁇ -olefins having 3 to 10 carbon atoms.
- the polymerization reaction temperature of the olefin in ⁇ Step 3X> is usually ⁇ 40 to 200 ° C., preferably 0 to 150 ° C., more preferably 40 to 130 ° C.
- the reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
- the reaction time is usually 5 minutes to 48 hours, preferably 5 minutes to 12 hours.
- ⁇ Process 3Y> In ⁇ Step 3Y>, following ⁇ Step 3X>, olefin [Y] having a composition different from that used in ⁇ Step 3X> is polymerized in the presence of the polymerization catalyst (Y).
- the organometallic compound (C) In the case where the organometallic compound (C) is used in ⁇ Step 3Y>, the organometallic compound (C) has a molar ratio [(C) / (AY)] with the transition metal compound (AY).
- the olefin to be polymerized in ⁇ Step 3Y> is selected from one or more olefins having 2 to 20 carbon atoms.
- the type of olefin to be used and the amount ratio in the case of using two or more types are not particularly limited as long as the composition differs from ⁇ Step 3X>.
- the olefin used is preferably one or more selected from ethylene, ⁇ -olefins having 3 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, or alkenyl alicyclic compounds having 5 to 20 carbon atoms.
- An olefin more preferably one or more olefins selected from ethylene or ⁇ -olefins having 3 to 20 carbon atoms, and more preferably selected from ethylene or ⁇ -olefins having 3 to 10 carbon atoms.
- the polymerization reaction temperature of the olefin in ⁇ Step 3Y> is usually ⁇ 40 to 200 ° C., preferably 0 to 150 ° C., more preferably 40 to 130 ° C.
- the reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
- the reaction time is usually 5 minutes to 48 hours, preferably 5 minutes to 12 hours.
- ⁇ Step 3X> and ⁇ Step 3Y> more preferably, at least one of ⁇ Step 3X> and ⁇ Step 3Y> is copolymerized with two or more types of olefins, and the other with one type of olefins. Is homopolymerized. More preferably, ethylene / propylene copolymerization is performed in one of ⁇ Step 3X> and ⁇ Step 3Y>, and propylene homopolymerization is performed in the other.
- the olefin block polymer is obtained by stopping the polymerization reaction after the entire polymerization process is completed.
- a method for stopping the polymerization reaction (1) a method of adding a specific substance that decreases the activity of the polymerization catalyst (X) and the polymerization catalyst (Y), or (2) heat treatment, or (3) removal of olefins.
- the method (1) is used.
- Examples of the substance that decreases the activity of the polymerization catalyst (X) and the polymerization catalyst (Y) include carbon monoxide, water, alcohol, and the like, preferably water and alcohol.
- the olefin block polymer produced by the method of the present invention comprises a polymer segment (X) formed by polymerizing one or more olefins selected from olefins having 2 to 20 carbon atoms with a polymerization catalyst (X).
- the olefin block polymer is a polymer segment having a different chemical or physical property from any of the polymer segment (X) and the polymer segment (Y).
- One or more (Z) may be included.
- the total number of polymer segments in the olefin block polymer is 2 or more.
- the average number of polymer segments in the olefin block polymer obtained by the single-stage polymerization method (1) is preferably 3 or more, more preferably 5 or more, still more preferably 7 or more, and most preferably 10 or more.
- the number of polymer segments in the olefin block polymer obtained by the multistage polymerization methods (2) and (3) is equal to or less than the number of polymerization steps included in the multistage polymerization to be carried out. 5, more preferably 2 to 4, still more preferably 2 and 3, and most preferably 2.
- Each polymer segment may be a homopolymer segment of one type of olefin selected from olefins having 2 to 20 carbon atoms, and a copolymer of two or more types of olefins selected from olefins having 2 to 20 carbon atoms. A combined segment may be used.
- the polymer segment is a copolymer segment obtained from two or more types of olefins
- the random copolymer segment in which the olefin composition is a constant ratio in the polymer segment the olefin composition changes continuously. It may be a tapered polymer segment or an alternating copolymer segment obtained by alternately polymerizing two kinds of olefins.
- Preferred homopolymer segments as the polymer segments (X), (Y) and (Z) are ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, a cyclic olefin having 3 to 20 carbon atoms, or 5 to 5 carbon atoms.
- a homopolymer segment of 20 alkenyl alicyclic compounds more preferably a homopolymer segment of ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, still more preferably ethylene or a carbon atom having 3 to 10 carbon atoms.
- An ⁇ -olefin homopolymer segment most preferably an ethylene or propylene homopolymer segment.
- the ethylene homopolymer segment may be a linear polyethylene segment, a short-chain branched polyethylene segment, a long-chain branched polyethylene segment, or a hyperbranched polyethylene segment, preferably a linear polyethylene segment and a hyperbranched polyethylene segment.
- the propylene homopolymer segment may be an isotactic polypropylene segment, an atactic polypropylene segment, or a syndiotactic polypropylene segment, but is preferably an isotactic polypropylene segment or an atactic polypropylene segment.
- Copolymer segment of ethylene and ⁇ -olefin having 3 to 20 carbon atoms specifically copolymer of ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.
- Polymer segments, Copolymer segment of propylene and ⁇ -olefin having 4 to 20 carbon atoms specifically, copolymer segment of propylene and 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.
- a copolymer segment of ethylene or propylene and a cyclic olefin having 5 to 20 carbon atoms specifically, a copolymer segment of tetracyclododecene, norbornene, methylnorbornene, etc.
- a copolymer segment of ethylene or propylene and an alkenyl alicyclic compound having 8 to 20 carbon atoms specifically, a copolymer segment of vinylcyclohexane, etc.
- a polymer segment, a propylene / butene copolymer segment, a propylene / hexene copolymer segment, and a propylene / octene copolymer segment are more preferable, and a polyethylene segment, a polypropylene segment, and an ethylene / propylene copolymer segment are more preferable.
- the olefin block polymer produced by the method of the present invention is preferably Block polymer having linear polyethylene segment and branched polyethylene segment, block polymer having polyethylene segment and polypropylene segment, block polymer having polyethylene segment and polybutene segment, block polymer having polyethylene segment and polyhexene segment, polyethylene segment And a block polymer having a polyoctene segment, Block polymer having isotactic polypropylene segment and syndiotactic polypropylene segment, block polymer having isotactic polypropylene segment and atactic polypropylene segment, block polymer having atactic polypropylene segment and syndiotactic polypropylene segment, polypropylene A block polymer having a segment and a polybutene segment, a block polymer having a polypropylene segment and a polyhexene segment, a block polymer having a polypropylene segment and a polyoctene segment, Block polymer having polyethylene segment and ethylene / prop
- Olefin block copolymer composition In addition to the olefin block polymer in which the polymer segment (X) and the polymer segment (Y) are chemically bonded, the olefin block copolymer composition obtained according to the production method of the present invention, It is composed of an unblocked polymer (X) having a structure equivalent to that of the polymer segment (X) and / or an unblocked polymer (Y) having a structure equivalent to that of the polymer segment (Y).
- the amount of the extracted component or the amount of the residual component at the time of solvent extraction is determined between the polymer (X) and the polymer (Y). Different from simple blend polymers. By utilizing this property, the production amount of the olefin block polymer in the olefin block copolymer composition can be evaluated.
- TREF fractionation was carried out for Sumitomo Nobren S131 (manufactured by Sumitomo Chemical Co., Ltd.) and Sumikasen-LFS150 (manufactured by Sumitomo Chemical Co., Ltd.) as two types of ethylene / ⁇ -olefin copolymers having a low ethylene content and a high ethylene content with a moderate composition distribution. The ethylene content of the components fractionated at each temperature is calculated.
- the range of the ethylene content of the ethylene / propylene copolymer as the soluble component and the range of the ethylene content of the ethylene / propylene copolymer as the insoluble component are as follows. Can be estimated (see also FIG. 1).
- ethylene / propylene copolymer when the ethylene / propylene copolymer was subjected to solvent fractionation by boiling hexane extraction with a solvent fractionation temperature of 68 ° C., ethylene / propylene having an ethylene composition of 9.3 mol% or less or 94.6 mol% or more.
- the copolymer remains in the boiling hexane insoluble (hereinafter BHIS) component, and the ethylene / propylene copolymer having an ethylene composition greater than 9.3 mol% and less than 94.6 mol% is soluble in boiling hexane (hereinafter, BHS) component.
- BHIS boiling hexane insoluble
- BHS boiling hexane
- ethylene / propylene copolymer having a low ethylene content ethylene content is less than 0.1 mol% or more 9.0 mol% (hereinafter, L EP) to segment BHIS component, an ethylene content of 80.
- L EP 9.0 mol%
- H EP ethylene / propylene copolymer having a high ethylene content which is at least 0 mol% 94.5 mol% or less
- L EP-b- H EP ethylene / propylene block copolymer composition composed of L EP, H EP, and a block polymer in which L EP and H EP are chemically bonded
- H EP content in BHIS component (hereafter, H EP BHIS), ethylene content of H EP component in BHIS component (H C 2 'BHIS), L EP content in BHIS component (below, L EP BHIS), BHIS It described below calculation method of the ethylene content in L EP component in the component (L C 2 'BHIS).
- the ratios PPP, PPE, PEP, EPE, EEP, and EEE of all triplets obtained by 13 CNMR with respect to all triplets are calculated.
- H EP BHIS, H C 2 'BHIS, L EP BHIS, L C 2' BHIS can be calculated by the following equation.
- H EP content in BHS component (hereinafter, H EP BHS), ethylene content of H EP component in BHS component (H C 2 'BHS), L EP content in BHS component (hereinafter, L EP BHS), BHS It can be calculated similarly for the calculation method of the ethylene content of L EP component in the component (L C 2 'BHS).
- Polypropylene having high stereoregularity has a higher melting point than polyethylene and is excellent in heat resistance, but the melting point decreases as the comonomer composition increases and as the stereoregularity decreases. .
- the melting point of L EP segment of ethylene / propylene block copolymer composition of the present invention relies on the stereoregularity of the propylene chain of L C 2 'and in the L EP segment, of which the catalyst used Depends on the reactivity ratio of ethylene and propylene and the stereoregularity in propylene polymerization.
- the ethylene / propylene block copolymer composition of the present invention preferably has a high melting point in terms of heat resistance and mechanical properties, and preferably has a melting point of 130 ° C. or higher in order to exhibit higher heat resistance than polyethylene. More preferably, it has one or more melting points of 135 ° C. or more, more preferably one or more melting points of 140 ° C. or more, and particularly preferably one or more melting points of 145 ° C. or more.
- H EP BHIS ethylene / propylene block copolymer composition of the present invention is at least 2.0 wt%, more preferably 3.0 wt% or more, more preferably 4.0 wt% or more, particularly preferably It is 5.0 wt% or more, most preferably 6.0 wt% or more.
- the value of the H C 2 'BHIS ethylene / propylene block copolymer composition of the present invention is less than 80.0mol% 94.5mol%, more preferably at least 80.0mol% 94.0mol% or less, More preferably, it is 80.0 mol% or more and 93.5 mol% or less, Most preferably, it is 80.0 mol% or more and 93.0 mol% or less, Most preferably, it is 80.0 mol% or more and 92.8 mol% or less.
- the L C 2 ′ BHIS value of the ethylene / propylene block copolymer composition of the present invention is preferably 0.1 mol% or more and 9.0 mol% or less, more preferably 0.1 mol% or more and 6.0 mol% or less, More preferably, they are 0.1 mol% or more and 4.0 mol% or less, Especially preferably, they are 0.1 mol% or more and 3.0 mol% or less, Most preferably, they are 0.1 mol% or more and 2.0 mol% or less.
- the absolute value of the H C 2 'BHIS and H C 2' difference BHS ethylene / propylene block copolymer composition of the present invention is preferably 5.0mol % Or less, more preferably 4.0 mol% or less, further preferably 3.0 mol% or less, particularly preferably 2.5 mol% or less, and most preferably 2.3 mol% or less.
- the value of the weight ratio of the BHIS component of the ethylene / propylene block copolymer composition of the present invention to the entire composition is preferably 10.0 wt% or more, more preferably 20.0 wt% or more, and even more preferably 30. It is 0 wt% or more, particularly preferably 40.0 wt% or more, and most preferably 50.0 wt% or more.
- the BHS component of the composition has one or more melting points of 5.0 ° C. or more and 150.0 ° C. or less, more preferably those melting points are The heat of fusion of 5.0 J / g or more and 200.0 J / g or less is shown.
- the value of the weight-average molecular weight A w of ethylene / propylene block copolymer composition of the present invention is 100 to 50,000, more preferably 500 or more to 25,000 or less, more preferably 2,500 or more 25 5,000 or less, particularly preferably 2,500 or more and 10,000 or less, and most preferably 5,000 or more and 10,000 or less.
- the value of the molecular weight distribution A w / A n of the ethylene / propylene block copolymer composition of the present invention is 1.7 to 15.0 or less, more preferably 1.7 to 10.0, more preferably Is 1.8 or more and 5.0 or less, particularly preferably 1.8 or more and 4.0 or less, and most preferably 1.9 or more and 3.0 or less.
- a n represents an ethylene / propylene block copolymer composition has a number average molecular weight of the present invention.
- the ethylene / propylene block copolymer composition of the present invention preferably has a PPP chain in the BHIS component of the composition of 29% or more and an EEE chain of 1.5% or more, more preferably 50% of the PPP chain.
- EEE chain is 2.5% or more, more preferably PPP chain is 60% or more and EEE chain is 3.5% or more, particularly preferably PPP chain is 65% or more and EEE chain is 4.5% or more. It is.
- the ethylene / propylene block copolymer composition of the present invention preferably satisfies the following formula (M-1) from the viewpoint of the balance between rigidity and impact resistance, more preferably satisfies the formula (M-2), and more preferably Satisfies the formula (M-3), particularly preferably (M-4), most preferably the formula (M-5).
- M-1 Young's modulus
- M-2 Tensile impact
- M-3 particularly preferably (M-4)
- M-5 most preferably the formula (M-5).
- (M-2) 25000 ⁇ Young's modulus (MPa) ⁇ Tensile impact (kJ / m 2 ) .. (M-3) 33000 ⁇ Young's modulus (MPa) ⁇ Tensile impact (kJ / m 2 ) .. (M-4) 42000 ⁇ Young's modulus (MPa) ⁇ Tensile impact (kJ / m 2 ) .. (M-5)
- the ethylene / propylene block copolymer composition of the present invention has a haze value of preferably 18% or less, more preferably 15% or less, and even more preferably 13% or less from the viewpoint of transparency.
- a preferred embodiment of the ethylene / propylene block copolymer composition of the present invention satisfies all of the following requirements (1) to (5).
- (1) having at least one melting point of 130 ° C. or higher (2) content of H EP BHIS is 2.0 wt% or higher (3) H C 2 ′ BHIS is 80.0 mol% or higher and 94.5 mol% or lower (4) L C 2 ′ BHIS is 0.1 mol% or more and 9.0 mol% or less (5)
- the absolute value of the difference between H C 2 ′ BHIS and H C 2 ′ BHS is 5.0 mol% or less.
- a more preferable embodiment of the ethylene / propylene block copolymer composition of the present invention satisfies all of the above requirements (1) to (5) and satisfies the following requirement (6).
- a further preferred embodiment of the ethylene / propylene block copolymer composition of the present invention satisfies all of the above requirements (1) to (6) and satisfies the following requirement (7).
- Haze value is 18% or less
- the ethylene / propylene block copolymer composition of the present invention has high heat resistance, and is excellent in the balance between rigidity and impact resistance and transparency.
- 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 evaporating 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 evaporated under reduced pressure to obtain 19.2 g of a mixture containing 2- (1-adamantyl) -5-methylsalicylaldehyde.
- reaction solution was filtered, and volatile components were removed 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 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 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 4.2 g of a mixture containing 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) salicylaldehyde (yield 96%).
- TREF fractionation of the ethylene / propylene block copolymer composition was carried out as follows. Apparatus PREPmc2 Solvent manufactured by PolymerChar, 1,2-dichlorobenzene solvent amount Each fraction was dissolved in 100 ml. Polymer amount 500mg TREF sorting conditions (1) Dissolution step 130 ° C., 90 minutes Stabilization temperature 120 ° C., 45 minutes Crystallization temperature 0.2 ° C./min. Eight fractions of C, 110 C, and 130 C were used.
- TREF sorting conditions (2) Melting step 130 ° C., 90 minutes Stabilization temperature 120 ° C., 45 minutes Crystallization temperature Cooling fractionation temperature 30 ° C., 40 ° C., 50 ° C., 60 ° C., 70 ° C. Eleven fractions of C, 90 C, 100 C, 110 C, 120 C, and 130 C were used.
- 1 liter of acetone was added to precipitate the polymer, and then the polymer was recovered by vacuum filtration. The collected polymer was vacuum-dried at 70 ° C. for 12 hours or more to obtain a sample for analysis.
- Young's modulus (rigidity) JIS K6251-7 test piece was prepared from the above 0.3 mmt press sheet, and a tensile test was performed at a speed of 5.0 mm / min using a tensile testing machine (STA-1225 manufactured by Orientec). The initial elastic modulus was obtained from the slope of the tangent at the zero point of the tensile-stress curve. Yield strength, tensile strength and elongation were measured by a method based on JIS K6251. A JIS K6251-7 test piece was prepared from the 0.3 mmt press sheet and measured at a tensile speed of 50 mm / min using a tensile tester (STA-1225 manufactured by Orientec Corp.).
- Example 1 (1) Single-stage polymerization of ethylene / propylene copolymer After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 40 mL of toluene and 80 g of propylene were added, the temperature was raised to 50 ° C., and ethylene was reduced to 0 at a partial pressure. .05 MPa was added. Next, a mixed solution of 0.50 mmol of triisobutylaluminum (organometallic compound (C)) and 0.05 mmol of diethyl zinc (organometallic compound (C)) and a toluene solution of the transition metal compound (A-X2) were introduced from the pressure feeder.
- the toluene solution of the co-catalyzing component (B)) was added to the autoclave in the order of 1.25 mL (4.0 mM, 5.0 ⁇ mol), and polymerization was carried out at 50 ° C. for 30 minutes.
- Example 2 (1) Single-stage polymerization of ethylene / propylene copolymer After sufficiently drying an autoclave with a stirrer with an internal volume of 1 liter, 100 ml of toluene and 200 g of propylene are added and the temperature is raised to 50 ° C. Added. Next, a mixed solution of 0.50 mmol of triisobutylaluminum (organometallic compound (C)) and 0.05 mmol of diethyl zinc (organometallic compound (C)) and a toluene solution of the transition metal compound (A-X2) were introduced from the pressure feeder.
- Toluene solution 2.50 mL (4.0 mM, 10.0 ⁇ mol) of the co-catalyzing component (B)) was added to the autoclave in this order, and polymerization was carried out at 50 ° C. for 30 minutes.
- Example 2 Solvent fractionation of single-stage polymerization polymer Except for using the two-stage polymerization polymer synthesized in Example 2 (1), the process was carried out according to the method described in Example 1 (2), and 1.13 g of BHIS component was obtained. 0.87 g of BHS component was obtained.
- Example 3 (1) Single-stage polymerization of ethylene / propylene copolymer 2.00 mL (2.0 mM, 4.0 ⁇ mol) of a toluene solution of a transition metal compound (AX2) and 2.00 mL of a toluene solution of a transition metal compound (AY1) (1.0 mM, 2.0 ⁇ mol) mixed solution of transition metal compound (AX2) in toluene solution 1.00 mL (2.0 mM, 2.0 ⁇ mol) and transition metal compound (AY1) in toluene solution 2 Except that the mixed solution was 0.000 mL (2.0 mM, 4.0 ⁇ mol), it was carried out according to the method described in Example 2 (1) to obtain 22.1 g of a single-stage polymer.
- AX2 transition metal compound
- AY1 transition metal compound
- Example 4 (1) Single-stage polymerization of ethylene / propylene copolymer 2.00 mL (2.0 mM, 4.0 ⁇ mol) of a toluene solution of a transition metal compound (AX2) and 2.00 mL of a toluene solution of a transition metal compound (AY1) A mixed solution of (1.0 mM, 2.0 ⁇ mol) was added to a toluene solution 3 of a transition metal compound (A-X2) in toluene (3.00 mL (1.0 mM, 3.0 ⁇ mol) and a transition metal compound (AY1)).
- Example 5 Single-stage polymerization of ethylene / propylene copolymer 2.00 mL (2.0 mM, 4.0 ⁇ mol) of a toluene solution of a transition metal compound (AX2) and 2.00 mL of a toluene solution of a transition metal compound (AY1) (1.0 mM, 2.0 ⁇ mol) mixed solution of transition metal compound (AX2) in toluene solution 1.00 mL (5.0 mM, 5.0 ⁇ mol) and transition metal compound (AY1) in toluene solution 1
- Example 6 Single-stage polymerization of ethylene / propylene copolymer 0.05 mmol of diethyl zinc (organometallic compound (C)) was changed to 0.10 mmol, and 2.00 mL of toluene solution of transition metal compound (A-X2) (2.
- a mixed solution of 2.00 mL (1.0 mM, 2.0 ⁇ mol) of a toluene solution of 0 mM, 4.0 ⁇ mol) and a transition metal compound (AY1) was added to 3.00 mL of a toluene solution of a transition metal compound (A-X2) ( A mixed solution of a toluene solution of 1.0 mM, 3.0 ⁇ mol) and a transition metal compound (AY1) 3.00 mL (1.0 mM, 3.0 ⁇ mol), trityltetrakis (pentafluorophenyl) borate (activated
- the addition amount of 2.50 mL (4.0 mM, 10.0 ⁇ mol) of the toluene solution of the co-catalyst component (B) for use was 3.75 mL (4.0 mM, 1 Except that the .0Myumol) is performed according to the method described in Example 2 (1), a single-stage polymerization polymer was obtained 29.2
- Example 7 Single-stage polymerization of ethylene / propylene copolymerization
- the polymerization temperature was changed to 40 ° C., and 2.00 mL (2.0 mM, 4.0 ⁇ mol) of a transition metal compound (AX2) in toluene and a transition metal compound (A -Y1) toluene solution 2.00 mL (1.0 mM, 2.0 ⁇ mol), transition metal compound (AX2) toluene solution 3.00 mL (1.0 mM, 3.0 ⁇ mol) and transition metal compound (AY1) toluene solution 3.00 mL (1.0 mM, 3.0 ⁇ mol) mixed solution, trityltetrakis (pentafluorophenyl) borate (activation promoter component (B)) in toluene solution 2
- the method described in Example 2 (1) except that the addition amount of .50 mL (4.0 mM, 10.0 ⁇ mol) was changed to 3.75 mL (4.0 m
- Example 8 Single-stage polymerization of ethylene / propylene copolymer 0.50 mmol of triisobutylaluminum (organometallic compound (C)) was changed to 0.25 mmol, and 2.00 mL (2.0 mM) of a toluene solution of a transition metal compound (AX2).
- a transition solution of a transition metal compound (AY1) in toluene (2.00 mL (1.0 mM, 2.0 ⁇ mol)) was added to a transition metal compound (A-X2) in toluene solution (3.00 mL (1 0.03 mM, 3.0 ⁇ mol) and 3.00 mL (1.0 mM, 3.0 ⁇ mol) of a toluene solution of transition metal compound (AY1), and trityltetrakis (pentafluorophenyl) borate (for activation)
- the addition amount of 2.50 mL (4.0 mM, 10.0 ⁇ mol) of a toluene solution of the promoter component (B)) was 3.75 mL (4.0 M, except that the 15.0Myumol) performed according to the method described in Example 2 (1), a single-stage polymerization polymer was obtained 41.0 g.
- Example 9 (1) Single-stage polymerization of ethylene / propylene copolymer After sufficiently drying an autoclave with a stirrer with an internal volume of 0.4 liter, 40 mL of toluene and 80 g of propylene were added, the temperature was raised to 40 ° C., and ethylene was reduced to 0 at a partial pressure. .05 MPa was added. Next, a mixed solution of 2.0 mmol of MMAO-3A (organometallic compound (C)) and 0.05 mmol of diethylzinc (organometallic compound (C)) and a toluene solution of transition metal compound (AX2) were introduced from the pressure feeder.
- MMAO-3A organometallic compound (C)
- diethylzinc organometallic compound (C)
- AX2 transition metal compound
- a mixed solution of 0.40 mL (1.0 mM, 0.40 ⁇ mol) and a transition metal compound (AY1) in toluene solution 0.20 mL (0.50 mM, 0.10 ⁇ mol) was added to the autoclave in this order, and the mixture was added at 40 ° C. for 30 minutes. Polymerization was performed. A small amount of ethanol was added to stop the reaction, the unreacted monomer was purged, the autoclave was opened, 500 mL of ethanol and 5 mL of 1N aqueous hydrochloric acid were added, and the mixture was stirred at room temperature for 30 minutes. The precipitated polymer was subjected to suction filtration, and then sufficiently dried under reduced pressure in a vacuum dryer to obtain 9.4 g of a single-stage polymer.
- AY1 transition metal compound
- Example 10 (1) Single-stage polymerization of ethylene / propylene copolymer After sufficiently drying an autoclave with a stirrer with an internal volume of 1 liter, 100 mL of toluene and 200 g of propylene were added, the temperature was raised to 40 ° C., and ethylene was further added to a partial pressure of 0.05 MPa. Added. Next, MMAO-3A (organometallic compound (C)) 2.0 mmol, diethylzinc (organometallic compound (C)) 0.05 mmol, transition metal compound (A-X2) in toluene solution 2.00 mL from the pressure feeder.
- transition metal compound (AY1) in toluene solution 0.20 mL (1.0 mM, 0.20 ⁇ mol) in this order in a mixed solution in an autoclave and polymerized at 40 ° C. for 30 minutes. It was. A small amount of ethanol was added to stop the reaction, the unreacted monomer was purged, the autoclave was opened, 500 mL of ethanol and 5 mL of 1N aqueous hydrochloric acid were added, and the mixture was stirred at room temperature for 30 minutes. The precipitated polymer was subjected to suction filtration and then sufficiently dried under reduced pressure in a vacuum dryer to obtain 14.0 g of a single-stage polymer.
- Example 11 (1) Single-stage polymerization of ethylene / propylene copolymer 2.00 mL (1.0 mM, 2.0 ⁇ mol) of toluene solution of transition metal compound (A-X2) and 0.20 mL of toluene solution of transition metal compound (AY1) (1.0 mM, 0.2 ⁇ mol) of a mixed solution of transition metal compound (A-X2) in toluene solution 1.00 mL (1.0 mM, 1.0 ⁇ mol) and transition metal compound (AY1) in toluene solution Except that the mixed solution was 20 mL (1.0 mM, 0.20 ⁇ mol), the reaction was performed according to the method described in Example 10 (1) to obtain 8.2 g of a single-stage polymer.
- Example 12 Single-stage polymerization of ethylene / propylene copolymer: 100 mL of toluene is 300 mL, 200 g of propylene is 100 g, 2.00 mL (1.0 mM, 2.0 ⁇ mol) of transition metal compound (AX2) in toluene and transition metal Transition of a mixed solution of 0.20 mL (1.0 mM, 0.2 ⁇ mol) of a toluene solution of the compound (AY1) and 1.00 mL (1.0 mM, 1.0 ⁇ mol) of a toluene solution of the transition metal compound (A-X2)
- a single-stage polymer was obtained according to the method described in Example 10 (1) except that a mixed solution of 0.20 mL (1.0 mM, 0.20 ⁇ mol) of a toluene solution of the metal compound (AY1) was used. 8 g was obtained.
- Example 13 (1) Single-stage polymerization of ethylene / propylene copolymer 0.05 mmol of diethyl zinc (organometallic compound (C)) was changed to 0.10 mmol, and 2.00 mL (1.0 mM, 2.0 ⁇ mol) and a toluene solution of transition metal compound (AY1) 0.20 mL (1.0 mM, 0.2 ⁇ mol) were mixed with a transition metal compound (A-X2) toluene solution 1.00 mL (1.0 mM).
- Example 14 Single-stage polymerization of ethylene / propylene copolymer 0.05 mmol of diethyl zinc (organometallic compound (C)) is 0.30 mmol, and 2.00 mL (1.0 mM, 1.0 mM, toluene solution of transition metal compound (AX2) 2.0 ⁇ mol) and a toluene solution of transition metal compound (AY1) 0.20 mL (1.0 mM, 0.2 ⁇ mol) were mixed with a transition metal compound (A-X2) toluene solution 1.00 mL (1.0 mM).
- Example 15 Single-stage polymerization of ethylene / propylene copolymer The single-stage polymerization was performed according to the method described in Example 10 (1) except that 0.05 mmol of diethylzinc (organometallic compound (C)) was changed to 0.02 mmol. 16.5 g of polymer was obtained.
- Example 16 Single-stage polymerization of ethylene / propylene copolymer The single-stage polymerization was carried out according to the method described in Example 10 (1) except that 0.05 mmol of diethyl zinc (organometallic compound (C)) was changed to 0.01 mmol. 14.7 g of polymer were obtained.
- Table 1 summarizes the BHIS ratio, Tm1, Tm2, ⁇ H, Aw, and Aw / An for the single-stage polymer (Whole) obtained from Examples 1 to 16 and Comparative Examples 1 to 4 (1). It was.
- BHS BHS component
- BHIS a single-stage polymerization polymer
- Examples 1 to 16 in which ethylene / propylene copolymerization was carried out using polymerization catalysts (X) and (Y) according to the single-stage polymerization method (1) should all be present in the BHS component. H EP of the composition are present. Therefore, it has shown that the olefin block polymer is producing
- Example 4 in which ethylene / propylene copolymerization was performed using polymerization catalysts (X) and (Y) according to the single-stage polymerization method (1), and ethylene using only the polymerization catalyst (Y) under the same polymerization conditions /
- the results of NMR analysis of TREF fractionation and the fractionated component are shown below (see also Table 3, Table 4 and FIG. 2).
- Polymerization is a catalyst (Y) only the ethylene / propylene block copolymer compositions using Reference Example 11 are all H EP component, it is understood that eluted at 50 ° C. or less by TREF fractionation.
- the polymerization catalyst (X) and (Y) Example 4 is an ethylene / propylene block copolymer compositions using are contained H EP component and L EP component, eluting with 50 ° C. or less components
- components eluting at 90 to 110 ° C. were confirmed. From the components NMR analysis of eluting with 90 ⁇ 110 °C, H EP component was confirmed from 9.7 to 23.0%.
- H EP component has a substantially equal composition as in Reference Example 11, even though a component to be eluted at 50 ° C. or less, is present in components eluted at 90 ⁇ 110 ° C.. That is, this alone H EP component to be eluted at 50 ° C. or less is, by the nature of L EP component chemically linked to H EP component, represents that eluted at 90 ⁇ 110 ° C., carried out This result strongly suggests that the olefin block polymer is present in the ethylene / propylene block copolymer composition obtained in Example 4.
- Example 17 (1) Single-stage polymerization of ethylene / propylene copolymer After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 100 mL of toluene and 50 g of propylene were added, the temperature was raised to 70 ° C., and ethylene was reduced to 0 at a partial pressure. .6 MPa was added. Next, 0.50 mmol of triisobutylaluminum (organometallic compound (C)), 0.05 mmol of diethyl zinc (organometallic compound (C)), and 1.00 mL of a toluene solution of a transition metal compound (A-X1) from a pressure feeder.
- organometallic compound (C) triisobutylaluminum
- organic compound (C) 0.05 mmol of diethyl zinc
- A-X1 transition metal compound
- a toluene solution of catalyst component (B)) was added to an autoclave in the order of 1.00 mL (4.0 mM, 4.0 ⁇ mol), and polymerization was performed at 70 ° C. for 30 minutes.
- Example 18 (1) Instead of a single-stage polymerization transition metal compound (A-X1) of ethylene / propylene copolymer, 1.00 mL (1.0 mM, 1.0 ⁇ mol) of a toluene solution of a transition metal compound (A-X2) is added to perform polymerization. The procedure was as described in Example 17 (1) except that the time was 15 minutes, to obtain 7.8 g of a single-stage polymer.
- Example 18 (1) Solvent fractionation of single-stage polymerized polymer The same procedure as in Example 17 (2) was conducted except that the single-stage polymerized polymer obtained in Example 18 (1) was used, and the CXIS component was 1.55 g, CXS. 0.45g of component was obtained.
- Example 19 (1) Single-stage polymerization of ethylene / propylene copolymer Instead of transition metal compound (A-X1), 1.00 mL (1.0 mM, 1.0 ⁇ mol) of a toluene solution of transition metal compound (A-X2) was added, and trityl was added. The method described in Example 17 (1), except that 31.0 mg of d-MAO (activation co-catalyst component (B)) was added in place of tetrakis (pentafluorophenyl) borate, and triisobutylaluminum was not added. To obtain 15.1 g of a single-stage polymer.
- d-MAO activation co-catalyst component (B)
- Example 17 (2) Solvent fractionation of single-stage polymerized polymer The same procedure as in Example 17 (2) was conducted except that the single-stage polymerized polymer obtained in Example 19 (1) was used, and the CXIS component was 0.87 g and CXS. 1.13 g of component was obtained.
- Example 20 Single-stage polymerization of ethylene / propylene copolymer 0.50 mL (1.0 mM, 0.5 ⁇ mol) of a toluene solution of transition metal compound (AY2) was added instead of transition metal compound (AY1). Except for the above, it was carried out according to the method described in Example 17 (1) to obtain 8.9 g of a single-stage polymer.
- Example 20 (1) Solvent fractionation of single-stage polymerization polymer Except that the single-stage polymerization polymer obtained in Example 20 (1) was used, the same procedure as in Example 17 (2) was carried out, and the CXIS component was 0.47 g, CXS. 1.53 g of component was obtained.
- Example 21 (1) Single-stage polymerization of ethylene / propylene copolymer Instead of the transition metal compound (A-X1), 1.00 mL (1.0 mM, 1.0 ⁇ mol) of a toluene solution of the transition metal compound (A-X2) is added to perform polymerization. The procedure was as described in Example 20 (1) except that the time was 15 minutes, and 4.5 g of a single-stage polymer was obtained.
- Example 21 (2) Solvent fractionation of single-stage polymerized polymer The same procedure as in Example 17 (2) was conducted except that the single-stage polymerized polymer obtained in Example 21 (1) was used, and 1.19 g of CXIS component, CXS. 0.81 g of component was obtained.
- Table 7 shows the intrinsic viscosity [ ⁇ ], An, Aw, Aw / An, Tm, Tc, Tg, ⁇ H, and ethylene content.
- amorphous ethylene / propylene copolymer segment (X) derived from the polymerization catalyst (X) is present in the CXIS component.
- the segment (X) usually has a composition that is all fractionated into CXS components based on the Tg value. Therefore, this means that the crystalline ethylene / propylene copolymer segment (X), which is to be separated by itself as a CXS component, is chemically linked to the segment (X).
- the properties of the polymer segment (Y) indicate that it is present in the CXIS component as an insoluble component, and in the single-stage polymer obtained in Examples 17 to 21, an olefin block polymer is formed. It is suggested.
- Example 22 (1) Single-stage polymerization of ethylene After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 200 mL of toluene was added, the temperature was raised to 40 ° C., and ethylene was further added at a partial pressure of 0.6 MPa.
- Table 8 shows the intrinsic viscosity [ ⁇ ], An, Aw, Aw / An, Tm, Tc, Tg, and ⁇ H for the single-stage polymer (Whole) obtained from Example 22 and Comparative Example 8 (1). Summarized.
- Example 23 Two-stage polymerization of ethylene / propylene copolymerization (first stage) and propylene homopolymerization (second stage) First stage: After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 160 mL of toluene and 20 g of propylene were added, and the temperature was 50 ° C. Then, ethylene was further added at a partial pressure of 0.4 MPa.
- Example 24 Two-stage polymerization of ethylene / propylene copolymerization (first stage) and propylene homopolymerization (second stage) First stage: After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 160 mL of toluene and 20 g of propylene were added, and the temperature was 50 ° C. Then, ethylene was further added at a partial pressure of 0.2 MPa. Next, 0.50 mmol of triisobutylaluminum (organometallic compound (C)), 0.05 mmol of diethyl zinc (organometallic compound (C)), 0.20 mL of a toluene solution of transition metal compound (AY4) from the pressure feeder.
- first stage After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 160 mL of toluene and 20 g of propylene were added, and the temperature was 50 ° C. Then, ethylene was further added at
- Example 25 Two-stage polymerization of ethylene / propylene copolymerization (first stage) and propylene homopolymerization (second stage) First stage: After sufficiently drying an autoclave with a stirrer having an internal volume of 0.4 liter, 160 mL of toluene and 20 g of propylene were added, and the temperature was 50 ° C. Then, ethylene was further added at a partial pressure of 0.2 MPa.
- Toluene solution 1.00 mL (4.0 mM, 4.0 ⁇ mol) was added to the autoclave in this order, and polymerization was carried out at 50 ° C. for 60 minutes.
- a small amount of ethanol was added to stop the reaction, the unreacted monomer was purged, the autoclave was opened, 500 mL of ethanol and 5 mL of 1N aqueous hydrochloric acid were added, and the mixture was stirred at room temperature for 30 minutes.
- the precipitated polymer was filtered with suction and then sufficiently dried under reduced pressure in a vacuum dryer to obtain 15.3 g of a two-stage polymer.
- Example 2 in which ethylene / propylene copolymerization was carried out using a polymerization catalyst (Y) in the former stage and propylene homopolymerization was carried out using the polymerization catalyst (X) in the latter stage.
- a polymerization catalyst (Y) for each of ⁇ 25, NMR and DSC measurements were performed on the Whole, CXIS, and CXS components.
- an NMR sequence derived from Tg and an ethylene / propylene copolymer was observed in the CXIS component. This indicates that an ethylene / propylene copolymer segment (Y) derived from the polymerization catalyst (Y) is present in the CXIS component.
- the segment (Y) usually has a composition that is all fractionated into CXS components based on the Tg value. Therefore, this means that a crystalline propylene homopolymer in which an amorphous ethylene / propylene copolymer segment (Y) to be separated as a CXS component alone is chemically linked to the segment (Y).
- the properties of the segment (X) indicate that it exists in the CXIS component as an insoluble component, and in the two-stage polymer obtained in Examples 23 to 25, an olefin block polymer is generated. It is suggested. Furthermore, in Examples 23 to 25 described above, the value of the EP content in the CXIS component is large and the production efficiency of the olefin block polymer is high as compared with Comparative Example 9 using only the polymerization catalyst (Y).
- an olefin block polymer can be produced with high productivity, which is extremely valuable industrially.
Abstract
Description
そこで、本発明が解決しようとする課題は、可逆的連鎖移動重合によるオレフィンブロックポリマーの合成において、副生成物がより少なくオレフィンブロックポリマーの生成効率が高いオレフィンブロックポリマーの製造方法を提供することにある。
元素周期律表第2族、12族および13族から選ばれる原子を含む有機金属化合物(C)(活性化用助触媒成分(B)を除く)とを用いて、オレフィンを重合するオレフィンブロックポリマーの製造方法であって、
重合触媒(X)は、下記一般式(1-X)で表される遷移金属化合物(A-X)と、有機アルミニウムオキシ化合物(B-1)、有機ホウ素化合物(B-2)、亜鉛助触媒成分(B-3)およびイオン交換性層状珪酸塩(B-4)から選ばれる活性化用助触媒成分(B)とを接触させて形成され、
重合触媒(Y)は、下記一般式(1-Y)(但し、下記一般式(1-X)で表される遷移金属化合物を除く)から選ばれる遷移金属化合物(A-Y)と、有機アルミニウムオキシ化合物(B-1)、有機ホウ素化合物(B-2)、亜鉛助触媒成分(B-3)およびイオン交換性層状珪酸塩(B-4)から選ばれる活性化用助触媒成分(B)とを接触させて形成される、製造方法である。
MXは、チタニウム原子、ジルコニウム原子またはハフニウム原子を表す。
RX1~RX8は、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数2~20のアルケニル基、
炭素原子数2~20のアルキニル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基を表す。
RX1~RX8における上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アルキニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記へテロ環式化合物残基はそれぞれ置換基を有していてもよい。
上記RX1~RX8の定義に関わらず、RX1とRX2、RX2とRX3、RX3とRX4、RX5とRX6、RX6とRX7、RX7とRX8はそれぞれ相互に連結して環を形成してもよく、これらの環は置換基を有していてもよい。
XXは、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数2~20のアルケニル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
炭素原子数1~20の置換シリル基、
炭素原子数1~20の置換アミノ基、
炭素原子数1~20の置換チオラート基、または
炭素原子数1~20のカルボキシラート基を表す。
XXにおける上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記カルボキシラート基はそれぞれ置換基を有していてもよい。
XX同士は、相互に連結して環を形成してもよい。
EXは中性のルイス塩基を表す。EXが複数ある場合は、複数のEXは同一でも異なっていてもよい。EXの個数を示す下付のxは、0、1、または2である。)
Lは、水素原子を除いて70個までの原子を含有し、共役系π電子を介してMに結合するπ電子共役系アニオン性基であり、aが2以上の場合、Lは互いに同一でも異なっていてもよい。
Xは、水素原子を除いて70個までの原子を含有する非共役系アニオン性基であり、bが2以上の場合、Xは互いに同一でも異なっていてもよい。
Eは、水素原子を除いて70個までの原子を含有し、1つ以上の非共有電子対を介してMに結合する中性ルイス塩基性配位子であり、cが2以上の場合、Eは互いに同一でも異なっていてもよい。
aは0~6の整数であり、bは0~8の整数であり、cは0~9の整数であり、nは1~4の整数である。また、M、L、Xの価数がそれぞれme、le、xeのとき、me=le×a+xe×bの関係を満たす。また、L、X、Eは、これらのうち2個以上が互いに連結して環を形成していてもよく、さらにaが2以上の場合、L同士が、bが2以上の場合、X同士が、cが2以上の場合、E同士が、nが2以上の場合、L同士、X同士、E同士が互いに連結して環を形成していてもよい。)
さらに、そのようなオレフィンブロックポリマーの生成効率の高いオレフィンブロックポリマーは、例えば、ポリプロピレン系樹脂組成物と混合した際に、剛性および耐衝撃性を向上させることができる。
本発明において用いられる遷移金属化合物(A-X)は、下記一般式(1-X)で表される。以下、式(1-X)で表される遷移金属化合物(A-X)について説明する。
MXは、チタニウム原子、ジルコニウム原子またはハフニウム原子を表す。
RX1~RX8は、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数2~20のアルケニル基、
炭素原子数2~20のアルキニル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基を表す。
RX1~RX8における上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アルキニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記へテロ環式化合物残基はそれぞれ置換基を有していてもよい。
上記RX1~RX8の定義に関わらず、RX1とRX2、RX2とRX3、RX3とRX4、RX5とRX6、RX6とRX7、RX7とRX8はそれぞれ相互に連結して環を形成してもよく、これらの環は置換基を有していてもよい。
XXは、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数2~20のアルケニル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
炭素原子数1~20の置換シリル基、
炭素原子数1~20の置換アミノ基、
炭素原子数1~20の置換チオラート基、または
炭素原子数1~20のカルボキシラート基を表す。
XXにおける上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記カルボキシラート基はそれぞれ置換基を有していてもよい。
XX同士は、相互に連結して環を形成してもよい。
EXは中性のルイス塩基を表す。EXが複数ある場合は、複数のEXは同一でも異なっていてもよい。EXの個数を示す下付のxは、0、1、または2である。)
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基であり、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、または
炭素原子数6~30のアリール基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基であり、
RX1とRX5は、特に好ましくは、RX1とRX5とが同一であって、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、または
置換シリル基である。
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基であり、
より好ましくは、それぞれ独立して、
水素原子、
ハロゲン原子
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、または
置換シリル基である。
RX2、RX4、RX6およびRX8は、さらに好ましくは、水素原子である。
RX3およびRX7はさらに好ましくは、それぞれ独立して、
ハロゲン原子、
炭素原子数1~20のアルキル基
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、または
置換シリル基である。
RX3およびRX7は、特に好ましくは、RX3とRX7とが同一であって、
炭素原子数1~20のアルキル基
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、または
置換シリル基であり、
最も好ましくは、
RX3とRX7とが同一であって、炭素原子数1~20のアルキル基である。
より好ましくは、tert-ブチル基、tert-ペンチル基、テキシル基などの炭素原子数4~6の第3級アルキル基である。
より好ましくは、パーフルオロメチル基、メチル基、イソプロピル基、イソブチル基、tert-ブチル基、イソペンチル基、tert-ペンチル基、ネオペンチル基、テキシル基などの炭素原子数1~6のアルキル基であり、
さらに好ましくは、パーフルオロメチル基、メチル基、イソプロピル基、イソブチル基、tert-ブチル基などの炭素原子数1~4のアルキル基である。
好ましくは、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、1-メチルシクロペンチル基、1-メチルシクロヘキシル基、1-インダニル基、2-インダニル基、ノルボルニル基、ボルニル基、メンチル基、1-アダマンチル基、2-アダマンチル基などの環を構成する炭素原子数が5~10のシクロアルキル基であり、
より好ましくは、シクロヘキシル基、1-メチルシクロヘキシル基、ノルボルニル基、ボルニル基、1-アダマンチル基、2-アダマンチル基などの、環を構成する炭素原子数が6~10のシクロアルキル基である。
さらにこれらのシクロアルキル基は、炭素原子数1~10のハイドロカルビル基を置換基として有していてもよい。例えば、環を構成する基が1-アダマンチル基であれば、3,5-ジメチルアダマンチル基、3,5,7-トリメチルアダマンチル基、3,5-ジエチルアダマンチル基、3,5,7-トリエチルアダマンチル基、3,5-ジイソプロピルアダマンチル基、3,5,7-トリイソプロピルアダマンチル基、3,5-ジイソブチルアダマンチル基、3,5,7-トリイソブチルアダマンチル基、3,5-ジフェニルアダマンチル基、3,5,7-トリフェニルアダマンチル基、3,5-ジ(p-トルイル)アダマンチル基、3,5,7-トリ(p-トルイル)アダマンチル基、3,5-ジ(3,5-キシリル)アダマンチル基、および3,5,7-トリ(3,5-キシリル)アダマンチル基などが挙げられ、より好ましくは3,5-ジメチルアダマンチル基、3,5-ジエチルアダマンチル基、3,5-ジイソプロピルアダマンチル基、3,5-ジイソブチルアダマンチル基、3,5-ジフェニルアダマンチル基、3,5-ジ(p-トルイル)アダマンチル基、および3,5-ジ(3,5-キシリル)アダマンチル基である。
好ましくは、ジメチル(フェニル)メチル基、ジメチル(4-メチルフェニル)メチル基、ジメチル(1-ナフチル)メチル基、ジメチル(2-ナフチル)メチル基、メチル(ジフェニル)メチル基、メチルビス(4-メチルフェニル)メチル基、トリフェニルメチル基などの炭素原子数9~20の第3級アラルキル基である。
好ましくは、フェニル基、2-トリル基、3-トリル基、4-トリル基、2,3-キシリル基、2,4-キシリル基、2,5-キシリル基、2,6-キシリル基、3,4-キシリル基、3,5-キシリル基、2,3,4-トリメチルフェニル基、2,3,5-トリメチルフェニル基、2,3,6-トリメチルフェニル基、2,4,6-トリメチルフェニル基、3,4,5-トリメチルフェニル基、エチルフェニル基、n-プロピルフェニル基、イソプロピルフェニル基、3,5-ジイソプロピルフェニル基、2,6-ジイソプロピルフェニル基、3,5-ジtert-ブチルフェニル基などの炭素原子数6~20のフェニル基;2-フルオロフェニル基、3-フルオロフェニル基、4-フルオロフェニル基、ペンタフルオロフェニル基、2,3-ジフルオロフェニル基、2,4-ジフルオロフェニル基、2,5-ジフルオロフェニル基、2,6-ジフルオロフェニル基などのフッ素化フェニル基;2-トリフルオロメチルフェニル基、3-トリフルオロメチルフェニル基、4-トリフルオロメチルフェニル基などのフッ素化アルキルフェニル基である。
好ましくはトリメチルシリル基、トリエチルシリル基、トリ-n-プロピルシリル基、トリイソプロピルシリル基、tert-ブチルジメチルシリル基などの炭素原子数3~20のトリアルキルシリル基;メチルビス(トリメチルシリル)シリル基、ジメチル(トリメチルシリル)シリル基、トリス(トリメチルシリル)シリル基などの炭素原子数3~20のハイドロカルビルシリル基を置換基として有するシリル基である。
好ましくは炭素原子数1~4のアルコキシ基であり、より好ましくはメトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、またはn-ブトキシ基である。
好ましくは炭素原子数6~14のアリールオキシ基であり、より好ましくは2,4,6-トリメチルフェノキシ基、3,4,5-トリメチルフェノキシ基、2,6-ジイソプロピルフェノキシ基、またはペンタフルオロフェノキシ基である。
好ましくは炭素原子数7~12のアラルキルオキシ基であり、より好ましくはベンジルオキシ基である。
好ましくはチエニル基、フリル基、1-ピロリル基、ピリジル基、ピリミジニル基、2-イソインドリル基、1-インドリル基、キノリル基、ジベンゾ-1H-ピロール-1-イル基、またはN-カルバゾリル基である。
好ましくは、ジメチルアミノ基、ジエチルアミノ基、ジn-プロピルアミノ基、ジイソプロピルアミノ基またはジベンジルアミノ基である。
好ましくはチオフェノキシ基、2,4,6-トリメチルチオフェノキシ基、3,4,5-トリメチルチオフェノキシ基、2,3,4,5-テトラメチルチオフェノキシ基、2,3,4,6-テトラメチルチオフェノキシ基、2,3,5,6-テトラメチルチオフェノキシ基、ペンタメチルチオフェノキシ基またはペンタフルオロチオフェノキシ基である。
好ましくは炭素原子数2~10のハイドロカルビルカルボキシラート基であり、より好ましくは、アセテート基、プロピオネート基、2-エチルヘキサノエート基またはトリフルオロアセテート基である。
下付のxは、EXの個数を表し、0、1、または2であり、好ましくは0または1であり、さらに好ましくは0である。EXが複数ある場合は、複数のEXは同一でも異なっていてもよい。
化合物(4)に1.0~4.0当量、好ましくは1.0~1.5当量の化合物(5)を塩基存在下で反応させ、化合物(6)を合成することができる。
化合物(6)に1.0~4.0当量、好ましくは1.0~1.5当量の化合物(7)を塩基存在下で反応させ、化合物(2)を合成することができる。
本発明において用いられる遷移金属化合物(A-Y)は、1つまたは複数の遷移金属原子、およびπ電子共役系アニオン性基、非共役系アニオン性基、中性ルイス塩基性配位子から選ばれる1つまたは複数の基・配位子を含有する下記一般式(1-Y)で表される遷移金属化合物のうち、前記一般式(1-X)で表される遷移金属化合物を除いた遷移金属化合物の群から選ばれる。
例として、メタロセン、ハーフメタロセン、もしくはヘテロ原子を配位元素とする多座キレート型基を有する遷移金属化合物などが含まれる。以下、式(1-Y)で表される遷移金属化合物について説明する。
Lは、水素原子を除いて70個までの原子を含有し、共役系π電子を介してMに結合するπ電子共役系アニオン性基であり、aが2以上の場合、Lは互いに同一でも異なっていてもよい。
Xは、水素原子を除いて70個までの原子を含有する非共役系アニオン性基であり、bが2以上の場合、Xは互いに同一でも異なっていてもよい。
Eは、水素原子を除いて70個までの原子を含有し、1つ以上の非共有電子対を介してMに結合する中性ルイス塩基性配位子であり、cが2以上の場合、Eは互いに同一でも異なっていてもよい。
aは0~6の整数であり、bは0~8の整数であり、cは0~9の整数であり、nは1~4の整数である。また、M、L、Xの価数がそれぞれme、le、xeのとき、me=le×a+xe×bの関係を満たす。また、L、X、Eは、これらのうち2個以上が互いに連結して環を形成していてもよく、さらにaが2以上の場合、L同士が、bが2以上の場合、X同士が、cが2以上の場合、E同士が、nが2以上の場合、L同士、X同士、E同士が互いに連結して環を形成していてもよい。
ハイドロカルビル基として具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基などの炭素原子数が1~30、好ましくは1~20の直鎖状または分岐状のアルキル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基などの炭素原子数3~30、好ましくは3~20の環状アルキル基、フェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基、ターフェニル基などの炭素原子数6~30、好ましくは6~20のアリール(aryl)基、ビニル基、アリル(allyl)基、イソプロペニル基などの炭素原子数2~30、好ましくは2~20の直鎖状または分岐状のアルケニル基、エチニル基、プロパルギル基など炭素原子数2~30、好ましくは2~20の直鎖状または分岐状のアルキニル基、また、上記ハイドロカルビル基は、水素原子の一部もしくは全てが他のハイドロカルビル基で置換されていてもよく、例えば、ベンジル、クミルなどのアラルキル基、トリル基、イソプロピルフェニル基、tert-ブチルフェニル基、ジメチルフェニル基、ジ-tert-ブチルフェニル基などのアルキル置換アリール基などが挙げられる。
Rcによって置換されたフェニル基として好ましくは、2,4,6-トリメチルフェニル基、2,4,6-トリエチルフェニル基、2,4,6-トリイソプロピルフェニル基、2,4,6-トリシクロヘキシルフェニル基、2,6-ジメチルフェニル基、2,6-ジエチルフェニル基、2,6-ジイソプロピルフェニル基、2,6-ジシクロヘキシルフェニル基、2-メチルフェニル基、2-エチルフェニル基、2-イソプロピルフェニル基、2-シクロヘキシルフェニル基であり、またRc同士の結合によって形成された縮合環誘導体として好ましくは、ナフタレニル基、アントリル基、フェナントリル基である。
bは1~4の整数である。またbが2以上の場合、X同士は互いに同一でも異なっていてもよく、2つ以上のX同士が互いに連結して環を形成していてもよい。
bは1~3の整数である。またbが2以上の場合、X同士は互いに同一でも異なっていてもよく、2つ以上のX同士が互いに連結して環を形成していてもよい。
ビス(シクロペンタジエニル)ジルコニウムジクロライド、ビス(メチルシクロペンタジエニル)ジルコニウムジクロライド、ビス(n-ブチルシクロペンタジエニル)ジルコニウムジクロライド、ビス(t-ブチルシクロペンタジエニル)ジルコニウムジクロライド、ビス(ペンタメチルシクロペンタジエニル)ジルコニウムジクロライド、ビス(インデニル)ジルコニウムジクロライド、ビス(フルオレニル)ジルコニウムジクロライド、
本発明において用いられる活性用助触媒成分(B)としては、以下に挙げる有機アルミニウムオキシ化合物(B-1)、有機ホウ素化合物(B-2)、亜鉛助触媒成分(B-3)およびイオン交換性層状珪酸塩(B-4)から選ばれる1種類以上の化合物が挙げられる。
有機アルミニウムオキシ化合物(B-1)としては、下記の化合物(B-1-1)および(B-1-2)から選ばれる1種類以上の化合物が挙げられる。
(B-1-1):一般式 RB1{-Al(RB1)-O-}B1AlRB1 2 で表される鎖状アルミノキサン
(B-1-2):一般式 {-Al(RB2)-O-}B2 で表される環状アルミノキサン
RB1およびRB2は炭素原子数1~20のハイドロカルビル基を表し、RB1同士およびRB2同士は同一でも異なっていてもよい。下付のB1およびB2は2以上の整数を表す。
(1)吸着水を含有する化合物または結晶水を含有する塩類、例えば塩化マグネシウム水和物、硫酸銅水和物、硫酸アルミニウム水和物、硫酸ニッケル水和物、塩化第1セリウム水和物などのハイドロカルビル懸濁液に、トリアルキルアルミニウムなどの有機アルミニウム化合物を添加して、吸着水または結晶水と有機アルミニウム化合物とを反応させる方法。
(2)ベンゼン、トルエン、エチルエーテル、テトラハイドロフランなどの溶媒中で、トリアルキルアルミニウムなどの有機アルミニウム化合物に、水、氷または水蒸気を反応させる方法。
(3)デカン、ベンゼン、トルエンなどの溶媒中で、トリアルキルアルミニウムなどの有機アルミニウム化合物に、ジメチルスズオキシド、ジブチルスズオキシドなどの有機スズ酸化物を反応させる方法。
有機ホウ素化合物(B-2)としては、下記の化合物(B-2-1)、(B-2-2)、および(B-2-3)から選ばれる1種類以上の化合物が挙げられる。
(B-2-1):一般式 BRB3 3 で表されるボラン化合物
(B-2-2):一般式 QB+BRB4 4 - で表されるボレート化合物
(B-2-3):一般式 EBH+BRB5 4 - で表されるボレート化合物
亜鉛助触媒成分(B-3)としては、下記の化合物(B-3a)および化合物(B-3b)を接触させて得られる亜鉛助触媒成分(B-3-1)または下記の化合物(B-3a)~(B-3c)を接触させて得られる亜鉛助触媒成分(B-3-2)が挙げられる。
(B-3a):一般式 ZnRB6 2 で表される化合物
(B-3b):一般式 RB7 B3-1TB1H で表される化合物
(B-3c):一般式 RB8 B4-1TB2H2 で表される化合物
RB6は水素原子、ハロゲン原子、ヒドロカルビル基またはハロゲン化ヒドロカルビル基を表し、RB6同士は同一でも異なっていてもよい。RB7およびRB8はそれぞれ独立にヒドロカルビル基、ハロゲン化ヒドロカルビル基、電子求引性基または電子求引性基を含有する基を表し、RB7同士およびRB8同士は同一でも異なっていてもよい。TB1およびTB2はそれぞれ独立に周期律表第15族または第16族の原子を表す。B3はTB1の原子価を表し、B4はTB2の原子価を表す。
トルエン溶媒に、ジエチル亜鉛のヘキサン溶液を加え、0℃に冷却し、そこへジエチル亜鉛に対して2モル~4モル量のハロゲン化アルコールを滴下した後に、90℃~120℃で10分間~24時間攪拌する。減圧下、揮発性物質を留去した後に、残渣を室温で減圧下1~20時間乾燥する。これによって成分(B-3-1)を製造できる。
(1)(B-3a)と(B-3b)とを接触させた後に(B-3c)を接触させる方法。
(2)(B-3a)と(B-3c)とを接触させた後に(B-3b)を接触させる方法。
(3)(B-3b)と(B-3c)とを接触させた後に(B-3a)を接触させる方法。
接触順序として好ましくは(1)または(2)であり、より好ましくは(1)である。すなわち、成分(B-3-2)として好ましくは、(B-3a)と(B-3b)とを接触させて得られた接触物と(B-3c)とを接触させて得られる成分、または(B-3a)と(B-3c)とを接触させて得られた接触物と(B-3b)とを接触させて得られる成分であり、より好ましくは(B-3a)と(B-3b)とを接触させて得られた接触物と(B-3c)とを接触させて得られる成分である。
|2-y-2z|≦1 [B1]
0<y<2 [B2]
0<z [B3]
上記式[B1]および[B2]におけるyとしてより好ましくは0.20~1.80の数であり、特に好ましくは0.25~1.50の数であり、最も好ましくは0.50~1.00の数である。
本発明において用いるイオン交換性層状珪酸塩(以下、単に「珪酸塩」と略記する)は、イオン結合などによって構成される面が互いに結合力で平行に積み重なった結晶構造を有し、かつ、含有されるイオンが交換可能である珪酸塩化合物をいう。大部分の珪酸塩は、天然には主に粘土鉱物の主成分として産出されるため、イオン交換性層状珪酸塩以外の夾雑物(石英、クリストバライト等)が含まれることが多いが、それらを含んでもよい。珪酸塩の具体例としては、例えば、参考文献:白水春雄著「粘土鉱物学」朝倉書店(1995年)に記載されている以下の層状珪酸塩が挙げられる。
化学処理を施すことが好ましい。化学処理は、表面に付着している不純物を除去する表面処理および粘土の構造に影響を与える処理のいずれをも用いることができる。本発明における化学処理としては、具体的には、以下の(1)酸処理、(2)塩類処理、(3)アルカリ処理、および(4)有機物処理、などが挙げられる。
酸処理は珪酸塩の表面の不純物を取り除くほか、結晶構造のAl、Fe、Mgなどの陽イオンの一部または全部を溶出させることができる。
酸処理で用いられる酸として好ましくは、塩酸、硫酸、硝酸、リン酸、酢酸またはシュウ酸である。処理に用いる酸は、2種以上であってもよい。酸により珪酸塩を処理する条件は、通常、酸濃度は0.1~50重量%、処理温度は室温~沸点、処理時間は5分~24時間である。酸は一般的には水溶液で用いられる。
本発明においては、塩類で処理される前の、珪酸塩の含有する交換可能な1族金属の陽イオンの40%以上、好ましくは60%以上を、下記に示す塩類から解離した陽イオンと、イオン交換することが好ましい。
アルカリ処理で用いられる処理剤としては、例えば、LiOH、NaOH、KOH、Mg(OH)2、Ca(OH)2、Sr(OH)2、Ba(OH)2が挙げられる。
有機物処理に用いられる有機物としては、例えば、トリメチルアンモニウム、トリエチルアンモニウム、N,N-ジメチルアニリニウム、トリフェニルホスホニウムなどが挙げられる。
有機物処理剤を構成する陰イオンとしては、例えば、塩類処理剤を構成する陰イオンとして例示した陰イオン、ヘキサフルオロフォスフェート、テトラフルオロボレート、テトラフェニルボレートなどが挙げられる。
珪酸塩の吸着水および層間水は、珪酸塩を加熱して除去できるが、層間水が残存しないように、また構造破壊を生じないよう加熱条件を選ぶことが必要である。加熱時間は0.5時間以上、好ましくは1時間以上である。温度200℃、圧力1mmHgの条件下で2時間珪酸塩を脱水して得られた珪酸塩の水分含有率を0重量%とした時、珪酸塩の水分含有率が3重量%以下、好ましくは1重量%以下、となるように、珪酸塩を加熱することが好ましい。
珪酸塩は、触媒の原料または触媒として使用する前に、後述する有機金属化合物(C)で処理を行うことが好ましい。珪酸塩1gに対する有機金属化合物(C)の使用量は、通常20mmol以下、好ましくは0.5mmol以上、10mmol以下である。処理温度は、通常0℃以上70℃以下であり、処理時間は10分以上3時間以下である。処理後に珪酸塩を洗浄することが好ましい。洗浄に用いる溶媒は後述する予備重合またはスラリー重合で使用する溶媒と同様の炭化水素溶媒を使用する。
造粒法としては、例えば攪拌造粒法、噴霧造粒法が挙げられる。
造粒の際に有機物、無機溶媒、無機塩、各種バインダ-を用いてもよい。
上記のようにして得られた球状粒子は、重合工程での破砕または微粉の生成を抑制する観点からは0.2MPa以上、特に好ましくは0.5MPa以上の圧縮破壊強度を有することが望ましい。このような強度の粒子を用いると、特に予備重合を行う場合に、ポリマー粒子性状改良効果が有効に発揮される。
本発明に用いる有機金属化合物(C)は、元素周期律表第2、12および13族から選ばれる元素を含む化合物(活性化用助触媒成分(B)を除く)であれば特に制限はないが、下式で表される化合物の群から選ばれる1種類以上の化合物が用いられる。
MCRC p(NRC 2)q(ORC)rXC s
アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、およびn-オクチル基などの直鎖状アルキル基、イソプロピル基、イソブチル基、tert-ブチル基、イソペンチル基、ネオペンチル基、イソアミル基、および2-エチルヘキシル基などの分岐状アルキル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基、およびシクロオクチル基などの環状アルキル基などが挙げられ、好ましくは炭素原子数1~20の直鎖状または分岐状アルキル基である。
アラルキル基としては、例えば、ベンジル基およびフェネチル基などが挙げられ、好ましくは炭素原子数7~20のアラルキル基である。
アリール基としては、例えば、フェニル基、ナフチル基およびトリル基などが挙げられ、好ましくは炭素原子数6~20のアリール基である。
アルケニル基としては、例えば、ビニル基、アリル基、3-ブテニル基、および5-ヘキセニル基などの直鎖状アルケニル基、イソブテニル基、および4-メチル-3-ペンテニル基などの分岐状アルケニル基、2-シクロヘキセニル基、および3-シクロヘキセニル基などの環状アルケニル基などが挙げられ、好ましくは炭素原子数2~20の直鎖状または分岐状アルケニル基である。
トリイソプロピルアルミニウム、トリイソブチルアルミニウム、トリsec-ブチルアルミニウム、トリtert-ブチルアルミニウム、トリ2-メチルブチルアルミニウム、トリ3-メチルブチルアルミニウム、トリ2-メチルペンチルアルミニウム、トリ3-メチルペンチルアルミニウム、トリ4-メチルペンチルアルミニウム、トリ2-メチルヘキシルアルミニウム、トリ3-メチルヘキシルアルミニウム、トリ2-エチルヘキシルアルミニウムなどのトリ分岐鎖アルキルアルミニウム;
トリシクロヘキシルアルミニウム、トリシクロオクチルアルミニウムなどのトリシクロアルキルアルミニウム;
トリフェニルアルミニウムなどのトリアリールアルミニウム、
ジエチルアルミニウムブロマイド、ジn-プロピルアルミニウムブロマイド、ジn-ブチルアルミニウムブロマイド、ジn-ペンチルアルミニウムブロマイド、ジn-ヘキシルアルミニウムブロマイド、ジエチルアルミニウムクロライド、ジn-プロピルアルミニウムクロライド、ジn-ブチルアルミニウムクロライド、ジn-ペンチルアルミニウムクロライド、ジn-ヘキシルアルミニウムクロライドなどのジn-アルキルアルミニウムハライド;
ジイソプロピルアルミニウムブロマイド、ジイソブチルアルミニウムブロマイド、ジsec-ブチルアルミニウムブロマイド、ジtert-ブチルアルミニウムブロマイド、ジ2-メチルブチルアルミニウムブロマイド、ジ3-メチルブチルアルミニウムブロマイド、ジ2-メチルペンチルアルミニウムブロマイド、ジ3-メチルペンチルアルミニウムブロマイド、ジ4-メチルペンチルアルミニウムブロマイド、ジ2-メチルヘキシルアルミニウムブロマイド、ジ3-メチルヘキシルアルミニウムブロマイド、ジ2-エチルヘキシルアルミニウムブロマイド、ジイソプロピルアルミニウムクロライド、ジイソブチルアルミニウムクロライド、ジsec-ブチルアルミニウムクロライド、ジtert-ブチルアルミニウムクロライド、ジ2-メチルブチルアルミニウムクロライド、ジ3-メチルブチルアルミニウムクロライド、ジ2-メチルペンチルアルミニウムクロライド、ジ3-メチルペンチルアルミニウムクロライド、ジ4-メチルペンチルアルミニウムクロライド、ジ2-メチルヘキシルアルミニウムクロライド、ジ3-メチルヘキシルアルミニウムクロライド、ジ2-エチルヘキシルアルミニウムクロライドなどのジ分岐鎖アルキルアルミニウムハライド;
ジフェニルアルミニウムブロマイド、ジメチルフェニルアルミニウムブロマイド、ジエチルフェニルアルミニウムブロマイド、ジブロモフェニルアルミニウムブロマイド、ジクロロフェニルアルミニウムブロマイド、ジフルオロフェニルアルミニウムブロマイド、ジシアノフェニルアルミニウムブロマイド、ジフェニルアルミニウムクロライド、ジメチルフェニルアルミニウムクロライド、ジエチルフェニルアルミニウムクロライド、ジブロモフェニルアルミニウムクロライド、ジクロロフェニルアルミニウムクロライド、ジフルオロフェニルアルミニウムクロライド、ジシアノフェニルアルミニウムクロライドなどのジアリール(aryl)アルミニウムハライド;などが挙げられ、
好ましくは、炭素原子数3~24の有機アルミニウム化合物であり、より好ましくは、炭素原子数3~24のトリn-アルキルアルミニウム、トリ分岐鎖アルキルアルミニウム、またはトリアリールアルミニウムであり、さらに好ましくは、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、またはトリn-オクチルアルミニウムである。
ジイソプロピル亜鉛、ジイソブチル亜鉛、ジsec-ブチル亜鉛、ジtert-ブチル亜鉛、ジ2-メチルブチル亜鉛、ジ3-メチルブチル亜鉛、ジ2-メチルペンチル亜鉛、ジ3-メチルペンチル亜鉛、ジ4-メチルペンチル亜鉛、ジ2-メチルヘキシル亜鉛、ジ3-メチルヘキシル亜鉛、ジ2-エチルヘキシル亜鉛などのジ分岐鎖アルキル亜鉛、
ジシクロヘキシル亜鉛、ジシクロオクチル亜鉛などのジシクロアルキル亜鉛、
ジフェニル亜鉛などのジアリール亜鉛;
エチル亜鉛ブロマイド、n-プロピル亜鉛ブロマイド、n-ブチル亜鉛ブロマイド、n-ペンチル亜鉛ブロマイド、n-ヘキシル亜鉛ブロマイド、エチル亜鉛クロライド、n-プロピル亜鉛クロライド、n-ブチル亜鉛クロライド、n-ペンチル亜鉛クロライド、n-ヘキシル亜鉛クロライドなどのn-アルキル亜鉛ハライド;
イソプロピル亜鉛ブロマイド、イソブチル亜鉛ブロマイド、sec-ブチル亜鉛ブロマイド、tert-ブチル亜鉛ブロマイド、2-メチルブチル亜鉛ブロマイド、3-メチルブチル亜鉛ブロマイド、2-メチルペンチル亜鉛ブロマイド、3-メチルペンチル亜鉛ブロマイド、4-メチルペンチル亜鉛ブロマイド、2-メチルヘキシル亜鉛ブロマイド、3-メチルヘキシル亜鉛ブロマイド、2-エチルヘキシル亜鉛ブロマイド、イソプロピル亜鉛クロライド、イソブチル亜鉛クロライド、sec-ブチル亜鉛クロライド、tert-ブチル亜鉛クロライド、2-メチルブチル亜鉛クロライド、3-メチルブチル亜鉛クロライド、2-メチルペンチル亜鉛クロライド、3-メチルペンチル亜鉛クロライド、4-メチルペンチル亜鉛クロライド、2-メチルヘキシル亜鉛クロライド、3-メチルヘキシル亜鉛クロライド、2-エチルヘキシル亜鉛クロライドなどの分岐鎖アルキル亜鉛ハライド、
フェニル亜鉛ブロマイド、メチルフェニル亜鉛ブロマイド、エチルフェニル亜鉛ブロマイド、ブロモフェニル亜鉛ブロマイド、クロロフェニル亜鉛ブロマイド、フルオロフェニル亜鉛ブロマイド、シアノフェニル亜鉛ブロマイド、フェニル亜鉛クロライド、メチルフェニル亜鉛クロライド、エチルフェニル亜鉛クロライド、ブロモフェニル亜鉛クロライド、クロロフェニル亜鉛クロライド、フルオロフェニル亜鉛クロライド、シアノフェニル亜鉛クロライドなどのアリール(aryl)亜鉛ハライド;などが挙げられ、
好ましくは、炭素原子数2~16の有機亜鉛化合物であり、より好ましくは、炭素原子数2~16のジn-アルキル亜鉛、ジ分岐鎖アルキル亜鉛、またはジアリール亜鉛であり、さらに好ましくは、ジメチル亜鉛、ジエチル亜鉛、ジイソブチル亜鉛、またはジn-オクチル亜鉛である。
本発明において、担体(D)は遷移金属化合物(A-X)および/または遷移金属化合物(A-Y)および/または活性化用助触媒成分(B)を担持する目的で必要に応じて使用される。
本発明において、有機化合物(E)は重合性能および生成ポリマーの物性を向上させる目的で必要に応じて使用される。有機化合物(E)としては、例えばアルコール類、フェノール類、カルボン酸類、アミン類、リン化合物、ならびにスルホン酸およびその塩が挙げられる。
RE5およびRE6は炭素原子数1~20のハイドロカルビル基または炭素原子数1~20のハロハイドロカルビル基である。
tおよびuは、1~4のいずれかの整数であり、MEの原子価をvとするとき、t=u×vを満たす。
重合触媒(X)を形成する方法としては、特に限定されるものではないが、遷移金属化合物(A-X)、活性化用助触媒成分(B)、任意成分として有機金属化合物(C)、および任意成分として担体(D)を接触させる方法が挙げられる。接触は溶媒の存在下または非存在下で行われ、これらの接触混合物を重合槽に添加してもよいし、これらを別々に任意の順序で重合槽に添加して重合槽中で接触させてもよいし、任意の二成分の接触混合物と残りの成分とを別々に重合槽に添加してもよい。
(1)遷移金属化合物(A-X)および活性化用助触媒成分(B)の接触混合物を重合槽に添加する方法。
(2)遷移金属化合物(A-X)、活性化用助触媒成分(B)および担体(D)の接触混合物を重合槽に添加する方法。
(3)遷移金属化合物(A-X)を担体(D)に担持した触媒成分と、活性化用助触媒成分(B)との接触混合物を重合槽に添加する方法。
(4)活性化用助触媒成分(B)を担体(D)に担持した触媒成分と、遷移金属化合物(A-X)との接触混合物を重合槽に添加する方法。
(5)遷移金属化合物(A-X)および活性化用助触媒成分(B)を任意の順序で重合槽に添加する方法。
(6)遷移金属化合物(A-X)、活性化用助触媒成分(B)および担体(D)を任意の順序で重合槽に添加する方法。
(7)遷移金属化合物(A-X)を担体(D)に担持した触媒成分と、活性化用助触媒成分(B)とを任意の順序で重合槽に添加する方法。
(8)活性化用助触媒成分(B)を担体(D)に担持した触媒成分と、遷移金属化合物(A-X)とを任意の順序で重合槽に添加する方法。
(9)遷移金属化合物(A-X)および活性化用助触媒成分(B)を担体(D)に担持した触媒成分を重合槽に添加する方法。
重合触媒(Y)を形成する方法としては、特に限定されるものではないが、遷移金属化合物(A-Y)、活性化用助触媒成分(B)、任意成分として有機金属化合物(C)、および任意成分として担体(D)を接触させる方法が挙げられる。接触は溶媒の存在下または非存在下で行われ、これらの接触混合物を重合槽に添加してもよいし、これらを別々に任意の順序で重合槽に添加して重合槽中で接触させてもよいし、任意の二成分の接触混合物と残りの成分とを別々に重合槽に添加してもよい。
(1)遷移金属化合物(A-Y)および活性化用助触媒成分(B)の接触混合物を重合槽に添加する方法。
(2)遷移金属化合物(A-Y)、活性化用助触媒成分(B)および担体(D)の接触混合物を重合槽に添加する方法。
(3)遷移金属化合物(A-Y)を担体(D)に担持した触媒成分と、活性化用助触媒成分(B)との接触混合物を重合槽に添加する方法。
(4)活性化用助触媒成分(B)を担体(D)に担持した触媒成分と、遷移金属化合物(A-Y)との接触混合物を重合槽に添加する方法。
(5)遷移金属化合物(A-Y)および活性化用助触媒成分(B)を任意の順序で重合槽に添加する方法。
(6)遷移金属化合物(A-Y)、活性化用助触媒成分(B)および担体(D)を任意の順序で重合槽に添加する方法。
(7)遷移金属化合物(A-Y)を担体(D)に担持した触媒成分と、活性化用助触媒成分(B)とを任意の順序で重合槽に添加する方法。
(8)活性化用助触媒成分(B)を担体(D)に担持した触媒成分と、遷移金属化合物(A-Y)とを任意の順序で重合槽に添加する方法。
(9)遷移金属化合物(A-Y)および活性化用助触媒成分(B)を担体(D)に担持した触媒成分を重合槽に添加する方法。
本発明で用いるオレフィンとしては、炭素原子数2~20のオレフィンが好ましく、例えば、エチレン、α-オレフィン、環状オレフィン、アルケニル脂環式化合物、極性オレフィンが挙げられる。
α-オレフィンとしては、例えば、プロピレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、5-メチル-1-ヘキセン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセンなどが挙げられる。
環状オレフィンとしては、例えば、シクロブテン、シクロペンテン、シクロヘキセン、シクロヘプテン、シクロオクテン、シクロノネン、シクロデセン、ノルボルネン、5-メチルノルボルネン、5-エチルノルボルネン、5-ブチルノルボルネン、5-フェニルノルボルネン、5-ベンジルノルボルネン、テトラシクロドデセン、トリシクロデセン、トリシクロウンデセン、ペンタシクロペンタデセン、ペンタシクロヘキサデセン、8-メチルテトラシクロドデセン、8-エチルテトラシクロドデセン、5-アセチルノルボルネン、5-アセチルオキシノルボルネン、5-メトキシカルボニルノルボルネン、5-エトキシカルボニルノルボルネン、5-メチル-5-メトキシカルボニルノルボルネン、5-シアノノルボルネン、8-メトキシカルボニルテトラシクロドデセン、8-メチル-8-テトラシクロドデセン、8-シアノテトラシクロドデセンなどが挙げられる。
アルケニル脂環式化合物としては、例えば、ビニルシクロヘキサンなどが挙げられる。
極性オレフィンとしては、例えば、アクリル酸、メタクリル酸、フマル酸、無水マレイン酸、イタコン酸、無水イタコン酸、ビシクロ(2,2,1)-5-ヘプテン-2,3-ジカルボン酸などのα,β-不飽和カルボン酸、およびそのナトリウム、カリウム、リチウム、亜鉛、マグネシウム、カルシウムなどの金属塩;アクリル酸メチル、アクリル酸エチル、アクリル酸n-プロピル、アクリル酸イソプロピル、アクリル酸t-ブチル、アクリル酸2-エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-プロピル、メタクリル酸イソプロピル、メタクリル酸n-ブチル、メタクリル酸イソブチルなどのα,β-不飽和カルボン酸エステル;マレイン酸、イタコン酸などの不飽和ジカルボン酸;酢酸ビニル、プロピオン酸ビニル、カプロン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、トリフルオロ酢酸ビニルなどのビニルエステル;アクリル酸グリシジル、メタクリル酸グリシジル、イタコン酸モノグリシジルエステルなどの不飽和カルボン酸グリシジルエステル;などが挙げられる。
上記のオレフィンとして好ましくは、エチレン、炭素原子数3~20のα-オレフィン、炭素原子数3~20の環状オレフィン、または炭素原子数5~20のアルケニル脂環式化合物であり、より好ましくは、エチレンまたは炭素原子数3~20のα-オレフィンであり、さらに好ましくは、エチレンまたは炭素原子数3~10のα-オレフィンであり、最も好ましくは、エチレンまたはプロピレンである。
本発明では、オレフィンの重合法は溶媒重合法、懸濁重合法などの液相重合法または気相重合法のいずれでもよい。
1つの方法は、1種類以上の重合触媒(X)、1種類以上の重合触媒(Y)、1種類以上の有機金属化合物(C)、1種類以上のオレフィン、さらに必要に応じて有機化合物(E)を用いて、単一の重合工程からなる単段重合を行うオレフィンブロックポリマーの製造方法である。
該単段重合法(1)において、重合触媒(X)および重合触媒(Y)の形成は、それぞれ、前記重合触媒の形成方法に従い、ほぼ同時に行われることが好ましい。
該単段重合法(1)において、オレフィンは、重合触媒(X)または重合触媒(Y)が重合槽内で形成される前に、もしくは重合槽外で形成された重合触媒(X)または重合触媒(Y)が重合槽内に添加される前に、あらかじめ重合槽内に添加されることが好ましい。また1種類のオレフィンを用いる場合には重合槽内のオレフィン濃度が、2種以上のオレフィンを用いる場合には重合槽内の各オレフィン濃度および組成比が、重合中一定に保たれるように、オレフィンを重合槽に連続的に添加してもよい。
他の方法は、1種類以上の重合触媒(X)、1種類以上の重合触媒(Y)、1種類以上の有機金属化合物(C)、1種類以上のオレフィン、さらに必要に応じて有機化合物(E)を用いて、2つ以上の重合工程からなる多段重合を行うオレフィンブロックポリマーの製造方法であって、各重合工程は、オレフィンの組成が等しく、かつ、隣り合う2つの工程がそれぞれ1種類以上の重合触媒(X)を用いる重合工程と、1種類以上の重合触媒(Y)を用いる重合工程であり、1つ前の重合工程までに得られた重合体の存在下で該オレフィンの重合を行う製造方法である。
多段重合法(2)は、重合触媒(X)の存在下、オレフィンを重合する工程〈工程2X〉と、重合触媒(Y)の存在下、〈工程2X〉で用いたものと組成が等しいオレフィンを重合する工程〈工程2Y〉とを少なくとも含む。
該多段重合法(2)における〈工程2X〉で形成される重合触媒(X)および、〈工程2Y〉で形成される重合触媒(Y)は、いずれも重合槽内で形成させても、重合槽外で形成させた重合触媒を重合槽に添加して用いてもよい。
該多段重合法(2)において、〈工程2X〉で用いるオレフィンは、重合触媒(X)が重合槽内で形成される前に、もしくは重合槽外で形成された重合触媒(X)が重合槽内に添加される前に、あらかじめ重合槽内に添加されることが好ましく、〈工程2Y〉で用いるオレフィンは、重合触媒(Y)が重合槽内で形成される前に、もしくは重合槽外で形成された重合触媒(Y)が重合槽内に添加される前に、あらかじめ重合槽内に添加されることが好ましい。またオレフィンが1種類のオレフィンである場合には重合槽内のオレフィン濃度が、2種以上のオレフィンである場合には重合槽内の各オレフィン濃度および組成比が、重合中一定に保たれるように、オレフィンを重合槽に連続的に添加してもよい。
また各重合工程では1つ前の重合工程までに得られた重合体の存在下でオレフィンの重合が行われる。2番目以降の重合工程では、その一つ前の重合工程で製造された重合体の存在下でオレフィンを重合する。
さらに他の方法は、1種類以上の重合触媒(X)、1種類以上の重合触媒(Y)、1種類以上の有機金属化合物(C)、1種類以上のオレフィン、さらに必要に応じて有機化合物(E)を用いて、2つ以上の重合工程からなる多段重合を行うオレフィンブロックポリマーの製造方法であって、各重合工程は、隣り合う2つの重合工程でオレフィンの組成が互いに異なり、かつ、隣り合う2つの重合工程がそれぞれ1種類以上の重合触媒(X)を用いる重合工程と、1種類以上の重合触媒(Y)を用いる重合工程であり、1つ前の重合工程までに得られた重合体の存在下で該オレフィンの重合を行う製造方法である。
多段重合法(3)は、1種類以上の重合触媒(X)の存在下、オレフィン[X]を重合する工程〈工程3X〉と、重合触媒(Y)の存在下、〈工程3X〉で用いたものとは組成の異なるオレフィン[Y]を重合する工程〈工程3Y〉を少なくとも含む。
該多段重合法(3)における〈工程3X〉で形成される重合触媒(X)および、〈工程3Y〉で形成される重合触媒(Y)は、いずれも重合槽内で形成させても、重合槽外で形成させた重合触媒を重合槽に添加して用いてもよい。
該多段重合法(3)において、〈工程3X〉で用いるオレフィン[X]は、重合触媒(X)が重合槽内で形成される前に、もしくは重合槽外で形成された重合触媒(X)が重合槽内に添加される前に、あらかじめ重合槽内に添加されることが好ましく、〈工程3Y〉で用いるオレフィン[Y]は、重合触媒(Y)が重合槽内で形成される前に、もしくは重合槽外で形成された重合触媒(Y)が重合槽内に添加される前に、あらかじめ重合槽内に添加されることが好ましい。またオレフィンが1種類のオレフィンである場合には重合槽内のオレフィン濃度が、2種以上のオレフィンである場合には重合槽内の各オレフィン濃度および組成比が、重合中一定に保たれるように、オレフィンを重合槽に連続的に添加してもよい。
また各重合工程では1つ前の重合工程までに得られた重合体の存在下でオレフィンの重合が行われる。2番目以降の重合工程では、その一つ前の重合工程で製造された重合体の存在下でオレフィンを重合する。
さらに多段重合法(2)および(3)では、隣り合う2つの重合工程において形成されるセグメントの化学的または物理的性質が互いに異なるように、各工程で使用する重合触媒(X)および重合触媒(Y)を選択することが好ましい。
とくに多段重合法(3)では、隣り合う2つの重合工程において形成されるセグメントの化学的または物理的性質が互いに異なるように、各工程で使用する重合触媒(X)および重合触媒(Y)とオレフィンの組み合わせを選択することが好ましい。
有機金属化合物(C)は、遷移金属化合物(A-X)とのモル比〔(C)/(A-X)〕および遷移金属化合物(A-Y)とのモル比〔(C)/(A-Y)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる。さらに有機化合物(E)を用いる場合は、有機金属化合物(C)とのモル比〔(E)/(C)〕が、通常0.001~10、好ましくは0.005~2となるような量で用いられる。
〈工程2X〉では、重合触媒(X)の存在下、オレフィンを重合する。
〈工程2X〉で有機金属化合物(C)を用いる場合には、有機金属化合物(C)は、遷移金属化合物(A-X)とのモル比〔(C)/(A-X)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる。さらに有機化合物(E)を用いる場合は、有機金属化合物(C)とのモル比〔(E)/(C)〕が、通常0.001~10、好ましくは0.005~2となるような量で用いられる。
〈工程2Y〉では、〈工程2X〉に続いて、重合触媒(Y)の存在下、〈工程2X〉で用いたものと組成が等しいオレフィンを重合する。
〈工程2Y〉で有機金属化合物(C)を用いる場合には、有機金属化合物(C)は、遷移金属化合物(A-Y)とのモル比〔(C)/(A-Y)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる。さらに有機化合物(E)を用いる場合は、有機金属化合物(C)とのモル比〔(E)/(C)〕が、通常0.001~10、好ましくは0.005~2となるような量で用いられる。
〈工程3X〉では、1種類以上の重合触媒(X)の存在下、オレフィン[X]を重合する。
〈工程3X〉で有機金属化合物(C)を用いる場合には、有機金属化合物(C)は、遷移金属化合物(A-X)とのモル比〔(C)/(A-X)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる遷移金属化合物(A-X)とのモル比〔(C)/(A-X)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる。さらに有機化合物(E)を用いる場合は、有機金属化合物(C)とのモル比〔(E)/(C)〕が、通常0.001~10、好ましくは0.005~2となるような量で用いられる。
〈工程3Y〉では、〈工程3X〉に続いて、重合触媒(Y)の存在下、〈工程3X〉で用いたものとは組成の異なるオレフィン[Y]を重合する。
〈工程3Y〉で有機金属化合物(C)を用いる場合には、有機金属化合物(C)は、遷移金属化合物(A―Y)とのモル比〔(C)/(A―Y)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる遷移金属化合物(A)とのモル比〔(C)/(A―Y)〕が、通常1~100000、好ましくは10~10000、より好ましくは20~5000となるような量で用いられる。さらに有機化合物(E)を用いる場合は、有機金属化合物(C)とのモル比〔(E)/(C)〕が、通常0.001~10、好ましくは0.005~2となるような量で用いられる。
本発明の方法で製造するオレフィンブロックポリマーは、炭素原子数2~20のオレフィンから選ばれる1種類以上のオレフィンが重合触媒(X)により重合して形成されるポリマーセグメント(X)と、炭素原子数2~20のオレフィンから選ばれる1種類以上のオレフィンが重合触媒(Y)により重合して形成され、かつ、前記ポリマーセグメント(X)とは化学的または物理的性質の異なるポリマーセグメント(Y)とを、それぞれ1つ以上含むオレフィンブロックポリマーである。
プロピレンの単独重合体セグメントとしては、アイソタクチックポリプロピレンセグメント、アタクチックポリプロピレンセグメント、シンジオタクチックポリプロピレンセグメントであってもよいが、好ましくはアイソタクチックポリプロピレンセグメントおよびアタクチックポリプロピレンセグメントである。
エチレンと炭素数3~20のα-オレフィンとの共重合体セグメント、具体的にはエチレンと、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセンなどとの共重合体セグメント、
プロピレンと炭素数4~20のα-オレフィンとの共重合体セグメント、具体的にはプロピレンと1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセンなどとの共重合体セグメント、
エチレンまたはプロピレンと炭素数5~20の環状オレフィンとの共重合体セグメント、具体的にはテトラシクロドデセン、ノルボルネン、メチルノルボルネンなどとの共重合体セグメント、
エチレンまたはプロピレンと炭素数8~20のアルケニル脂環式化合物との共重合体セグメント、具体的にはビニルシクロヘキサンなどとの共重合体セグメント、などが挙げられ、
直鎖ポリエチレンセグメントと分岐ポリエチレンセグメントとを有するブロックポリマー、ポリエチレンセグメントとポリプロピレンセグメントとを有するブロックポリマー、ポリエチレンセグメントとポリブテンセグメントとを有するブロックポリマー、ポリエチレンセグメントとポリヘキセンセグメントとを有するブロックポリマー、ポリエチレンセグメントとポリオクテンセグメントとを有するブロックポリマー、
アイソタクチックポリプロピレンセグメントとシンジオタクチックポリプロピレンセグメントとを有するブロックポリマー、アイソタクチックポリプロピレンセグメントとアタクチックポリプロピレンセグメントとを有するブロックポリマー、アタクチックポリプロピレンセグメントとシンジオタクチックポリプロピレンセグメントとを有するブロックポリマー、ポリプロピレンセグメントとポリブテンセグメントとを有するブロックポリマー、ポリプロピレンセグメントとポリヘキセンセグメントとを有するブロックポリマー、ポリプロピレンセグメントとポリオクテンセグメントとを有するブロックポリマー、
ポリエチレンセグメントとエチレン/プロピレン共重合体セグメントとを有するブロックポリマー、ポリエチレンセグメントとエチレン/ブテン共重合体セグメントとを有するブロックポリマー、ポリエチレンセグメントとエチレン/ヘキセン共重合体セグメントとを有するブロックポリマー、ポリエチレンセグメントとエチレン/オクテン共重合体セグメントとを有するブロックポリマー、
ポリプロピレンセグメントとエチレン/プロピレン共重合体セグメントとを有するブロックポリマー、ポリプロピレンセグメントとプロピレン/ブテン共重合体セグメントとを有するブロックポリマー、ポリプロピレンセグメントとプロピレン/ヘキセン共重合体セグメントとを有するブロックポリマー、ポリプロピレンセグメントとプロピレン/オクテン共重合体セグメントとを有するブロックポリマーなどであり、
より好ましくは、ポリエチレンセグメントとポリプロピレンセグメントとを有するブロックポリマー、ポリエチレンセグメントとエチレン/プロピレン共重合体セグメントとを有するブロックポリマー、ポリプロピレンセグメントとエチレン/プロピレン共重合体セグメントとを有するブロックポリマーなどであり、
さらに好ましくは、ポリエチレンセグメントとエチレン/プロピレン共重合体セグメントとを有するブロックポリマー、ポリプロピレンセグメントとエチレン/プロピレン共重合体セグメントとを有するブロックポリマーである。
本発明の製造方法に従って得られたオレフィンブロック共重合体組成物は、ポリマーセグメント(X)とポリマーセグメント(Y)とが化学的に結合したオレフィンブロックポリマーに加えて、ポリマーセグメント(X)と同等の構造のブロック化されていないポリマー(X)および/またはポリマーセグメント(Y)と同等の構造のブロック化されていないポリマー(Y)から構成される。
したがって上記の沸騰ヘキサン抽出において、エチレン含量が0.1mol%以上9.0mol%以下である低エチレン含量のエチレン/プロピレン共重合体(以下、LEP)セグメントはBHIS成分に、エチレン含量が80.0mol%以上94.5mol%以下である高エチレン含量のエチレン/プロピレン共重合体(以下、HEP)セグメントはBHS成分へと分別される。一方、LEP、HEPおよびLEPとHEPが化学的に結合したブロックポリマー(以下、LEP-b-HEP)から構成されるエチレン/プロピレンブロック共重合体組成物について、上記の沸騰へキサン抽出を実施すると、LEPセグメントの性質によって、LEPおよびLEP-b-HEPの一部がBHIS成分に存在することになる。
HEPBHIS =(EEE+EEP+EPE)/(PPP+PPE+PEP+EPE+EEP+EEE)×100
HC2’BHIS = (EEE+EEP)/(EEE+EEP+EPE)×100
LEPBHIS =(PPP+PPE+PEP)/(PPP+PPE+PEP+EPE+EEP+EEE)×100
LC2’BHIS = PEP/(PPP+PPE+PEP) ×100
本発明におけるエチレン/プロピレンブロック共重合体組成物中のLEPセグメントの融点も同様に、LC2’およびLEPセグメント中のプロピレン連鎖の立体規則性に依存しており、それらは用いる触媒のエチレンとプロピレンの反応性比およびプロピレン重合における立体規則性に依存する。
本発明のエチレン/プロピレンブロック共重合体組成物は、耐熱性や機械物性の面から融点が高いことが好ましく、ポリエチレンよりも高い耐熱性示すために、好ましくは、130℃以上の融点を一つ以上有し、より好ましくは135℃以上の融点を一つ以上有し、さらに好ましくは140℃以上の融点を一つ以上有し、特に好ましくは145℃以上の融点を一つ以上有する。
12000≦ヤング率(MPa)×テンサイルインパクト(kJ/m2)・・(M-1)
17000≦ヤング率(MPa)×テンサイルインパクト(kJ/m2)・・(M-2)
25000≦ヤング率(MPa)×テンサイルインパクト(kJ/m2)・・(M-3)
33000≦ヤング率(MPa)×テンサイルインパクト(kJ/m2)・・(M-4)
42000≦ヤング率(MPa)×テンサイルインパクト(kJ/m2)・・(M-5)
(1)130℃以上の融点を一つ以上有する
(2)HEPBHISの含量が2.0wt%以上である
(3)HC2’BHISが80.0mol%以上94.5mol%以下である
(4)LC2’BHISが0.1mol%以上9.0mol%以下である
(5)HC2’BHISとHC2’BHSの差の絶対値が5.0mol%以下である
(6)12000 ≦ ヤング率(MPa)×テンサイルインパクト(kJ/m2)
(7)ヘイズの値が18%以下である
(i)6-(1-アダマンチル)-2-ヒドロキシメチル-p-クレゾールの合成
窒素置換した1 L四口フラスコに2-(1-アダマンチル)-p-クレゾール 20.9 g(86.1 mmol)、 塩化マグネシウム 16.4 g(172 mmol)、パラホルムアルデヒド 13.0 g(433 mmol)およびテトラヒドロフラン 400 mLを加えた。ここにトリエチルアミン 24 mL(172 mmol)を加え、2.5時間加熱還流した。反応溶液を室温まで放冷した後、不溶物を濾過した。濾液から減圧下揮発成分を留去した後、残渣に酢酸エチルを加え、1M HCl、飽和食塩水の順で洗浄した。有機層を無水硫酸マグネシウムにより乾燥した後、減圧下溶媒を留去することで、2-(1-アダマンチル)-5-メチルサリチルアルデヒドを含む混合物19.2 gを得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
1.78 ~ 2.25 (15H), 2.32(s, 3H), 6.98 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H), 9.82 (s, 1H), 11.64 (s, 1H).
窒素置換した500 mL四口フラスコに上記混合物 19.2 gとテトラヒドロフラン 135 mLおよびメタノール 80 mLを加え、氷冷した。ここに水素化ホウ素ナトリウム 1.60 g(42.5 mmol)をゆっくり加え、室温まで昇温後、14.5時間撹拌した。減圧下揮発成分を留去した後、酢酸エチルを加え、1 M HCl、飽和食塩水の順で洗浄した。有機層を無水硫酸マグネシウムにより乾燥した後、減圧下溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 クロロホルム:へキサン=1:3~1:0)で精製することで、6-(1-アダマンチル)-2-ヒドロキシメチル-p-クレゾール 8.80 g(収率 38%)を白色固体として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
1.78 (m, 6H), 2.01 (br, 1H), 2.07 (m, 3H), 2.15 (m, 6H), 2.25 (s, 3H), 4.81 (d, J = 4 Hz, 2H), 6.70 (d, J = 2 HJz, 1H), 6.99 (d, J = 2 HJz, 1H), 7.50 (s, 1H).
(ii)臭化 3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジルの合成
窒素置換した200 mL四口フラスコに6-(1-アダマンチル)-2-ヒドロキシメチル-p-クレゾール 8.80 g(32.3 mmol)とジクロロメタン 132 mLを加えた。ここに、三臭化リン 15 mL(1.23 M ジクロロメタン溶液, 18.5 mmol)を加え室温で、3.5時間撹拌した。反応溶液を氷水に加え、有機層を水、飽和食塩水で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下揮発成分を留去することで、臭化 3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジル 11.1 g(粗収率 103%)を淡黄色固体として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
1.78 (m, 6H), 2.09 (m, 3H), 2.12 (m, 6H), 2.26 (s, 3H), 4.54 (s, 2H), 6.92 (d, J = 2 HJz, 1H), 7.04 (d, J = 2 HJz, 1H).
(iii)trans-1,2-ビス(3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジルスルファニル)シクロオクタンの合成
窒素置換した200 mL四口フラスコに臭化 3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジル 7.04 g(21.0 mmol)とtrans-シクロオクタン-1,2-ジチオール 1.83 g(10.4 mmol)とテトラヒドロフラン100 mLを加えた。ここに、トリエチルアミン 4.3 mL(31 mmol)を加え、室温で21.5時間撹拌した。反応溶液を濾過し、濾液から減圧下揮発成分を留去した。得られた残渣に酢酸エチルと塩化アンモニウム水溶液を加えた。有機層をさらに塩化アンモニウム水溶液、飽和食塩水の順で洗浄後、無水硫酸マグネシウムで乾燥した。減圧下溶媒を留去した後、シリカゲルカラムクロマトグラフィー(展開溶媒 酢酸エチル:へキサン=20:1)で精製することで、trans-1,2-ビス(3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジルスルファニル)シクロオクタンとtrans-1-(3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジルスルファニル)-2-スルファニルシクロオクタンの6:1混合物6.61 gを得た。この混合物および臭化 3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジル1.36 g(3.98 mmol)をテトラヒドロフラン100 mLに溶解し、氷冷した。ここに、トリエチルアミン0.74 mL(5.31 mmol)を加え、15.5時間撹拌した。反応溶液を濾過し、濾液から減圧下揮発成分を留去した。得られた残渣に酢酸エチルと塩化アンモニウム水溶液を加え、有機層をさらに塩化アンモニウム水溶液、飽和食塩水の順で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 酢酸エチル:へキサン=20:1)で精製し、得られた固体をさらにヘキサンにて室温でリパルプ洗浄することで、trans-1,2-ビス(3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジルスルファニル)シクロオクタン 6.08 g(収率 85%)を白色固体として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
1.2~2.0 (m, 12H), 1.77 (m, 12H), 2.05 (m, 6H), 2.13 (12H), 2.24 (s, 6H), 2.67 (m, 2H), 3.73 (d, J = 13 Hz, 2H), 3.82 (d, J = 13 Hz, 2H), 6.71 (d, J = 2 Hz, 2H), 6.83 (s, 2H), 6.97 (d, J = 2 Hz, 2H).
窒素雰囲気下のグローブボックス中、50 mLシュレンク管でtrans-1,2-ビス(3-(1-アダマンチル)-5-メチル-2-ヒドロキシベンジルスルファニル)シクロオクタン 200 mg(0.29 mmol)のトルエン(6 mL)溶液に、テトラベンジルハフニウム159 mg(0.29 mmol)のトルエン(6 mL)溶液を室温で滴下した。1.5時間後、反応溶液を濾過し、濾液から減圧下揮発成分を留去した。得られた残渣をペンタンで洗浄し、減圧下乾燥することで、[シクロオクタンジイル-trans-1,2-ビス(3-(1-アダマンチル)-5-メチル-2-オキソイルベンジルスルファニル)]ジベンジルハフニウム 249 mg (収率 82%)を白色粉末として得た。
1H-NMR (400 MHz,δ, ppm, トルエン-d8)
0.6~1.4 (m, 12H), 1.84 (m, 6 H), 2.1~2.2 (16H), 2.17 (s, 6H), 2.41 (m, 12H),
2.66 (d, J = 12 Hz, 2H), 2.83 (d, J = 12 Hz, 2H), 3.11 (d, J = 14 Hz, 2H), 3.51 (d, J = 14 Hz, 2H), 6.27 (s, 2H), 6.78 (t, J = 7 Hz, 2H), 7.1~7.2 (10H).
(i)4-tert-ブチル-2-(3, 5-ジメチル-1-アダマンチル)フェノールの合成
窒素置換した50 mLシュレンクに、4-tert-ブチルフェノール3.3 g(22 mmol)、3,5-ジメチル-1-アダマンタノール 4.0 g(22 mmol)およびジクロロメタン20 mLを加え、氷浴で0℃まで冷却した。ここに硫酸 1.2 mL(22 mmol)を加え、室温で1時間撹拌した。反応溶液を炭酸水素ナトリウム水溶液に注いだ。有機層を無水硫酸マグネシウムで乾燥した後、減圧下で揮発成分を留去した。得られた白色固体をシリカゲルカラムクロマトグラフィー(展開溶媒 酢酸エチル:ヘキサン=1:10)で精製することで4-tert-ブチル-2-(3, 5-ジメチル-1-アダマンチル)フェノール 4.0 g(収率 59%)を白色固体として得た。1H-NMR (400 MHz,δ, ppm, CDCl3)
0.874 (s, 6H), 1.20 (s, 2H), 1.29 (s, 9H), 1.35~1.45 (m, 4H), 1.70~1.78 (m, 4H), 1.95 (m,2H), 2.17 (m, 1H), 4.56 (s, 1H), 6.56 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.2~7.3 (5H), 7.24 (d, J = 2 Hz, 1H).
窒素置換した100 mL二口フラスコに、4-tert-ブチル-2-(3, 5-ジメチル-1-アダマンチル)フェノール4.0 g(13 mmol)、塩化マグネシウム4.8 g(50 mmol)、パラホルムアルデヒド2.1 g(70 mmol)およびテトラヒドロフラン50 mLを加えた。ここにトリエチルアミン6.7 mL(48 mmol)を加え、3時間加熱還流した。反応溶液を室温まで放冷した後、不溶物を濾過した。濾液から減圧下で揮発成分を留去した後、残渣に酢酸エチルおよび水を加えた。有機層を1 M HCl、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順に洗浄し、無水硫酸マグネシウムにより乾燥した。減圧下で溶媒を留去することで、5-tert-ブチル-3-(3, 5-ジメチル-1-アダマンチル)サリチルアルデヒド(収率96%)を含む混合物4.2 gを得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
0.874 (s, 6H), 1.2~2.2 (m, 22H), 7.32 (d, J = 2 Hz, 1H), 7.53 (d, J = 2 Hz, 1H), 9.85 (s, 1H), 11.7 (s, 1H).
窒素置換した100 mLフラスコに、上記混合物 4.2 gとテトラヒドロフラン20 mLおよびメタノール20 mLとを加え、氷冷した。ここに水素化ホウ素ナトリウム 490 mg(13 mmol)をゆっくり加え、室温まで昇温後、1時間撹拌した。反応溶液から減圧下で揮発成分を留去した後、水および酢酸エチルを加えた。有機層を1 M HCl、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順に洗浄し、無水硫酸マグネシウムにより乾燥した。減圧下、溶媒を留去した後、得られた無色オイルをシリカゲルカラムクロマトグラフィー(展開溶媒 酢酸エチル:へキサン=1:10~1:5)で精製することで4-tert-ブチル-6-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシメチルフェノール3.4 g(収率81%)を白色固体として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
0.875 (s, 6H), 1.2~2.2 (m, 23H), 4.85 (d, J = 5 Hz, 2H), 6.88 (d, J = 2 Hz, 1H), 7.22 (d, J = 2 Hz, 1H), 7.55 (s, 1H).
窒素置換した200 mLフラスコに、4-tert-ブチル-6-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシメチルフェノール3.4 g(9.9 mmol)とジクロロメタン20 mLを加えた。ここに、三臭化リン6.6 mL(1.0 M ジクロロメタン溶液, 6.6 mmol)を加え、室温で1時間撹拌した。反応溶液に水を加え、有機層をさらに水で2回洗浄した後、飽和食塩水で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後、減圧下で揮発成分を留去することで、臭化 5-tert-ブチル-3-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシベンジル3.95 g(収率98%)を白色固体として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
0.882 (s, 6H), 1.22 (s, 2H), 1.28 (s, 9H), 1.35~1.45 (m, 4H), 1.70~1.78 (m, 4H), 1.96 (m,2H), 2.19 (m, 1H), 4.57 (s, 1H), 7.08 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H).
窒素置換した50 mLシュレンクに、臭化 5-tert-ブチル-3-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシベンジル1.0 g(2.5 mmol)、trans-シクロオクタン-1,2-ジチオール 0.18 g(1.0 mmol)およびテトラヒドロフラン 7 mLを加え、氷冷した。ここに、トリエチルアミン 0.7 mL(5.0 mmol)を加え、0℃で1時間、室温で2時間撹拌した。さらに臭化 5-tert-ブチル-3-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシベンジル0.05 g(0.013 mmol)を加え、室温で1時間攪拌した。反応溶液から減圧下で揮発成分を留去した後、酢酸エチルおよび塩化アンモニウム水溶液を加えた。有機層を水、飽和食塩水の順で洗浄した後、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去した後、シリカゲルカラムクロマトグラフィー(展開溶媒 酢酸エチル:へキサン=1:10)で精製することで、trans-1,2-ビス[5-tert-ブチル-3-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシベンジルスルファニル]シクロオクタン1.0 g(収率>99%)を白色固体として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
0.88 (s, 12H), 1.2~2.2 (m, 56H), 2.59 (m, 2H), 3.77 (d, J = 14 Hz, 2H), 3.87 (d, J = 14 Hz, 2H), 6.89 (d, J = 2 Hz, 2H), 7.19 (d, J = 2 Hz, 2H).
窒素雰囲気下のグローブボックス中、50 mLシュレンク管でtrans-1,2-ビス[5-tert-ブチル-3-(3, 5-ジメチル-1-アダマンチル)-2-ヒドロキシベンジルスルファニル]シクロオクタン 83 mg(0.10 mmol)のトルエン(1 mL)溶液に、ジクロロ{1,1’-オキシビス[エタン][ビス(フェニルメチル)ハフニウム]}51 mg(0.10 mmol)のトルエン(1 mL)溶液を室温で滴下した。1.5時間後、減圧下で揮発成分を留去した。得られた残渣をペンタンで洗浄し、減圧下で乾燥することで、{シクロオクタンジイル-trans-1,2-ビス[5-tert-ブチル-3- (3, 5-ジメチル-1-アダマンチル) -2-オキソイルベンジルスルファニル]}ジクロロハフニウム 55 mg (収率51%)を白色粉末として得た。
1H-NMR (400 MHz,δ, ppm, CDCl3)
0.901 (s, 12H), 1.0~2.4 (m, 56H), 2.58 (brs, 2H), 3.88 (d, J = 14 Hz, 2H), 4.54 (d, J = 14 Hz, 2H), 6.85 (d, J = 2 Hz, 2H), 7.37 (d, J = 2 Hz, 2H).
下記に示される遷移金属化合物(A-Y2)は、Small, B. L.; Brookhart, M.; Bennett, A. M. A. J. Am. Chem. Soc. 1998, 120, 4049-4050.に記載の方法により合成した。
d-MAOの合成
3方コックを取り付けた撹拌子入りの200mL二口フラスコを窒素置換し、東ソー・ファインケム社製PMAO-Sトルエン溶液(アルミニウム含量6.1wt%)100mLをシリンジで測り取り、フラスコに投入した。この溶液を減圧し揮発成分を除去した。得られた白色固体を脱水トルエン100mLに再溶解した後、揮発成分を減圧除去した。この操作を更に2回繰り返し、白色粉末14.1gを得た。
ウベローデ型粘度計を用いて、テトラリン溶媒および温度135℃の条件で、濃度0.1、0.2、および0.5g/dlの3点について還元粘度を測定した。次に、参考文献:「高分子溶液、高分子実験学11」(1982年共立出版会社刊)第491頁に記載の計算法に従い、還元粘度を濃度に対しプロットし、濃度をゼロに外挿する外挿法によって極限粘度を求めた。
ゲルパーミエーションクロマトグラフィー(GPC)により、下記の条件で測定した。検量線は標準ポリスチレンを用いて作成した。
機種: ミリポアウオーターズ社製 150C型
カラム: TSK-GEL GMH-HT 7.5×600×2本
測定温度:140℃,152℃
溶媒: オルトジクロロベンゼン
測定濃度:5mg/5mL
DSC測定条件(1):熱分析装置 示差走査熱量計(TA Instruments社製 Q100)を用い下記の方法で測定した。
1)等温保持 220℃ 5分間
2)測定 220℃~-90℃(10℃/分)・・・(Tc)
3)測定 -90℃~220℃(10℃/分)・・・(Tm)、(ΔH)
4)冷却 220℃~-90℃(10℃/分)
5)等温保持 -90℃ 5分間
6)測定 -90℃~60℃(2℃/分)・・・(Tg)
(変調振幅±0.16℃、変調周期30秒)
DSC測定条件(2):熱分析装置 示差走査熱量計(Perkin Elmer社製 Diamond DSC)を用い下記の方法で測定した。
1)等温保持 220℃ 5分間
2)測定 220℃~20℃(5℃/分)・・・(Tc)
3)等温保持 20℃ 2分間
4)測定 20℃~220℃(5℃/分)・・・(Tm)、(ΔH)
核磁気共鳴分光器(NMR)を用い、以下のように測定したポリマーの13C-NMRスペクトルの結果を用い、Kakugoらの報告(参考文献:Macromolecules、1982年、15号、1150ページ~1152ページ)に記載の方法に準拠して求めた。また、EP含量を、上述の算出法を用いて求めた。
装置 :Bruker社製 AVANCE600 10mmクライオプローブ
測定溶媒:1,2-ジクロロベンゼン/1,2-ジクロロベンゼン-d4=75/25(容積比)の混合液
測定温度:130℃
測定方法:プロトンデカップリング法
パルス幅:45度
パルス繰り返し時間:4秒
化学シフト値基準:テトラメチルシラン
TREF分別については、次のように実施した。
装置 PREPmc2 PolymerChar社製
溶媒 1,2ジクロロベンゼン
溶媒量 各フラクションについて、100mlで溶解。
ポリマー量 500mg
TREF分別条件(1)
溶解ステップ 130℃、90分
安定化温度 120℃、45分
結晶化温度 0.2℃/分の降温速度で40℃まで冷却
分別温度 50℃、60℃、70℃、80℃、90℃、100℃、110℃、130℃の8フラクションとした。
TREF分別条件(2)
溶解ステップ 130℃、90分
安定化温度 120℃、45分
結晶化温度 0.2℃/分の降温速度で40℃まで冷却
分別温度 30℃、40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃の11フラクションとした。
TREF分別で得られた各ポリマー溶液について、アセトンを1リットル加え、ポリマーを沈殿させたのち、減圧濾過にてポリマーを回収した。回収したポリマーを70℃真空乾燥を12時間以上実施することで、分析用サンプルとした。
得られた重合パウダーをアルミ板、更に鋼製平板に挟んで230℃の熱プレス機にて5分間予熱し、重合体粒子が融着するのに十分な圧力で5分間プレス、次に30℃の冷却プレス機にて冷却し、測定に供した。この際、鋼製スペーサーを用いることで所望の厚みのプレスシートに調整した。
得られた重合パウダーをアルミ板、更に鋼製平板に挟んで190℃の熱プレス機にて5分間予熱し、重合体粒子が融着するのに十分な圧力で5分間プレス、次に30℃の冷却プレス機にて冷却し、測定に供した。この際、鋼製スペーサーを用いることで所望の厚みのプレスシートに調整した。
ヘイズ(曇価)をJIS K7136に準拠した方法で測定した。上記の方法で0.1ミリメートルの厚みのプレスシートを作製し、ヘイズメーター(日本電色工業製NDH2000)を用いて測定した。
テンサイルインパクト(引張衝撃強度)を上記0.3mmtプレスシートより JIS K6251-7号試験片を作製し、引張衝撃試験機(オリエンテック社製CIT-150T-20)を用いて測定した。ハンマーの振り上げ角度を110°、チャック間距離は20mmとした。
ヤング率(剛性)を上記0.3mmtプレスシートより JIS K6251-7号試験片を作製し、引張試験機(オリエンテック社製STA-1225)を用いて5.0mm/分の速度で引張り試験を行い、引張-応力カーブのゼロ点での接線の傾きから初期弾性率を求めた。
降伏強度、引張強度および伸びをJIS K6251に準拠した方法で測定した。上記0.3mmtプレスシートよりJIS K6251-7号試験片を作製し、引張試験機(オリエンテック社製STA-1225)を用いて50mm/分の引張速度で測定した。
(1)エチレン/プロピレン共重合の単段重合
内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン40mL、プロピレン80gを加え50℃に昇温し、さらにエチレンを分圧で0.05MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))0.50mmolとジエチル亜鉛(有機金属化合物(C))0.05mmolの混合溶液、遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(0.40mM、0.80μmol)の混合溶液、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.25mL(4.0mM、5.0μmol)の順にオートクレーブに加え、50℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、単段重合ポリマーを8.5g得た。
内容積300mLのナス型フラスコにヘキサン250mLを加え、実施例1(1)で合成した単段重合ポリマー2.00gを充填した円筒濾紙(ADVANTECH社製 R86 )をソックスレー抽出器内に設置し、還流管を取り付けた後5時間加熱還流し、円筒濾紙上の不溶成分(BHIS)および下部フラスコ中の溶出成分(BHS)へと分別した。減圧乾燥によりそれぞれ十分に溶媒を留去し、BHIS成分を0.89g、BHS成分を1.11g得た。
(1)エチレン/プロピレン共重合の単段重合
内容積1リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン100mL、プロピレン200gを加え50℃に昇温し、さらにエチレンを分圧で0.05MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))0.50mmolとジエチル亜鉛(有機金属化合物(C))0.05mmolの混合溶液、遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液2.50mL(4.0mM、10.0μmol)の順にオートクレーブに加え、50℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、単段重合ポリマーを21.0g得た。
実施例2(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.13g、BHS成分を0.87g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-X2)のトルエン溶液1.00mL(2.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(2.0mM、4.0μmol)の混合溶液としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを22.1g得た。
実施例3(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.81g、BHS成分を1.19g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-X2)のトルエン溶液3.00mL(1.0mM、3.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液3.00mL(1.0mM、3.0μmol)の混合溶液としたこと、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液2.50mL(4.0mM、10.0μmol)の添加量を3.75mL(4.0mM、15.0μmol)としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを22.6g得た。
実施例4(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.10g、BHS成分を0.90g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-X2)のトルエン溶液1.00mL(5.0mM、5.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液1.00mL(5.0mM、5.0μmol)の混合溶液としたこと、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液2.50mL(4.0mM、10.0μmol)の添加量を5.00mL(4.0mM、20.0μmol)としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを29.8g得た。
実施例5(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.24g、BHS成分を0.76g得た。
(1)エチレン/プロピレン共重合の単段重合
ジエチル亜鉛(有機金属化合物(C))0.05mmolを0.10mmolとしたこと、遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-X2)のトルエン溶液3.00mL(1.0mM、3.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液3.00mL(1.0mM、3.0μmol)の混合溶液としたこと、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液2.50mL(4.0mM、10.0μmol)の添加量を3.75mL(4.0mM、15.0μmol)としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを29.2g得た。
実施例6(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.79g、BHS成分を1.21g得た。
(1)エチレン/プロピレン共重合の単段重合
重合温度を40℃に変更し、遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-X2)のトルエン溶液3.00mL(1.0mM、3.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液3.00mL(1.0mM、3.0μmol)の混合溶液としたこと、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液2.50mL(4.0mM、10.0μmol)の添加量を3.75mL(4.0mM、15.0μmol)としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを29.2g得た。
実施例7(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.89g、BHS成分を1.11g得た。
(1)エチレン/プロピレン共重合の単段重合
トリイソブチルアルミニウム(有機金属化合物(C))0.50mmolを0.25mmolとし、遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-X2)のトルエン溶液3.00mL(1.0mM、3.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液3.00mL(1.0mM、3.0μmol)の混合溶液としたこと、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液2.50mL(4.0mM、10.0μmol)の添加量を3.75mL(4.0mM、15.0μmol)としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを41.0g得た。
実施例8(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.88g、BHS成分を1.12g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-Y5)のトルエン溶液0.10mL(0.20mM、0.020μmol)と遷移金属化合物(A-Y1)のトルエン溶液1.00mL(1.0mM、1.0μmol)の混合溶液としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを14.0g得た。
比較例1(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.00g、BHS成分を1.00g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(2.0mM、4.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液を、遷移金属化合物(A-Y5)のトルエン溶液0.10mL(0.20mM、0.020μmol)と遷移金属化合物(A-Y1)のトルエン溶液2.00mL(1.0mM、2.0μmol)の混合溶液としたこと以外は実施例2(1)に記載の方法に従って行い、単段重合ポリマーを13.7g得た。
比較例2(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.05g、BHS成分を1.95g得た。
(1)エチレン/プロピレン共重合の単段重合
内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン40mL、プロピレン80gを加え40℃に昇温し、さらにエチレンを分圧で0.05MPa分加えた。次いで、加圧投入器からMMAO-3A(有機金属化合物(C))2.0mmolとジエチル亜鉛(有機金属化合物(C))0.05mmolの混合溶液、遷移金属化合物(A-X2)のトルエン溶液0.40mL(1.0mM、0.40μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(0.50mM、0.10μmol)の混合溶液の順にオートクレーブに加え、40℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、単段重合ポリマーを9.4g得た。
実施例9(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.62g、BHS成分を0.38g得た。
(1)エチレン/プロピレン共重合の単段重合
内容積1リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン100mL、プロピレン200gを加え40℃に昇温し、さらにエチレンを分圧で0.05MPa分加えた。次いで、加圧投入器からMMAO-3A(有機金属化合物(C))2.0mmol、ジエチル亜鉛(有機金属化合物(C))0.05mmol、遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液の順にオートクレーブに加え、40℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、単段重合ポリマーを14.0g得た。
実施例10(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.22g、BHS成分を0.78g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを8.2g得た。
実施例11(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.48g、BHS成分を0.52g得た。
(1)エチレン/プロピレン共重合の単段重合
トルエン100mLを300mLとし、プロピレン200gを100gとし、遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを4.8g得た。
実施例12(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.77g、BHS成分を0.23g得た。
(1)エチレン/プロピレン共重合の単段重合
ジエチル亜鉛(有機金属化合物(C))0.05mmolを0.10mmolとし、遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを8.0g得た。
実施例13(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.10g、BHS成分を0.90g得た。
(1)エチレン/プロピレン共重合の単段重合
ジエチル亜鉛(有機金属化合物(C))0.05mmolを0.30mmolとし、遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを14.3g得た。
実施例14(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.79g、BHS成分を1.21g得た。
(1)エチレン/プロピレン共重合の単段重合
ジエチル亜鉛(有機金属化合物(C))0.05mmolを0.02mmolとしたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを16.5g得た。
実施例15(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.05g、BHS成分を0.95g得た。
(1)エチレン/プロピレン共重合の単段重合
ジエチル亜鉛(有機金属化合物(C))0.05mmolを0.01mmolとしたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを14.7g得た。
実施例16(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.04g、BHS成分を0.96g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を、遷移金属化合物(A-Y5)のトルエン溶液0.10mL(0.060mM、0.0060μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを7.0g得た。
比較例3(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を1.13g、BHS成分を0.87g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を、遷移金属化合物(A-Y5)のトルエン溶液0.10mL(0.060mM、0.0060μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.40mL(1.0mM、0.40μmol)の混合溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを7.9g得た。
比較例4(1)で合成した2段重合ポリマーを使用すること以外は、実施例1(2)に記載の方法に従って行い、BHIS成分を0.45g、BHS成分を1.55g得た。
(1)エチレン/プロピレン共重合の単段重合(HEPの合成)
遷移金属化合物(A-X2)のトルエン溶液3.00mL(1.0mM、3.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液3.00mL(1.0mM、3.0μmol)の混合溶液を、遷移金属化合物(A-Y1)のトルエン溶液3.00mL(1.0mM、3.0μmol)の溶液としたこと以外は実施例4(1)に記載の方法に従って行い、単段重合ポリマーを19.0g得た。
90~110℃で溶出する成分のNMR解析結果から、HEP成分が9.7~23.0%確認された。観測されたHEP成分は参考例11とほぼ等しい組成を有しており、50℃以下で溶出するべき成分であるにもかかわらず、90~110℃で溶出する成分に存在している。すなわち、これは単独では50℃以下で溶出するべきHEP成分が、HEP成分に対して化学的に連結したLEP成分の性質によって、90~110℃で溶出したことを表しており、実施例4で得られたエチレン/プロピレンブロック共重合体組成物において、オレフィンブロックポリマーが存在していることを強く示唆する結果である。
さらに実施例10と同一の重合条件にて重合触媒(Y)のみを用いてエチレン/プロピレン共重合を実施した参考例12より得られたHEP、および実施例10と同一の重合条件にて重合触媒(X)のみを用いてエチレン/プロピレン共重合を実施した参考例13より得られたLEP、以上の2成分を3種類の混合比にてそれぞれ溶媒ブレンドを実施した参考例14~16にて得られたブロックポリマーを含まないHEPとLEPのブレンドポリマーについても、同様に各種機械的強度および透明性測定を実施した。結果を、表5、表6および図3に示す。
(1)エチレン/プロピレン共重合の単段重合(HEPの合成)
遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の混合溶液を遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.20μmol)の溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを5.7g得た。
(1)エチレン/プロピレン共重合の単段重合(LEPの合成)
遷移金属化合物(A-X2)のトルエン溶液2.00mL(1.0mM、2.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.20mL(1.0mM、0.2μmol)の混合溶液を遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)の溶液としたこと以外は実施例10(1)に記載の方法に従って行い、単段重合ポリマーを12.5g得た。
(1)LEPおよびHEPの溶媒ブレンド
内容積1Lのナス型フラスコに参考例12(1)で合成した単段重合ポリマー1.0g、参考例13(1)で合成した単段重合ポリマー4.0gと、キシレン500mLを加え、還流管を取り付けた後1時間加熱還流した。得られた均一溶液を、氷冷したエタノール2000mL中へと攪拌しながら一度に加えてさらに15分間攪拌した。次いで、析出物を濾過した後に減圧乾燥することで、溶媒ブレンドポリマーを5.0g得た。
(1)LEPおよびHEPの溶媒ブレンド
参考例12(1)で合成した単段重合ポリマー1.0g、参考例13(1)で合成した単段重合ポリマー4.0gを、参考例12(1)で合成した単段重合ポリマー2.5g、参考例13(1)で合成した単段重合ポリマー2.5gとしたこと以外は、参考例14(1)に記載の方法に従って行い、溶媒ブレンドポリマーを5.0g得た。
(1)LEPおよびHEPの溶媒ブレンド
参考例12(1)で合成した単段重合ポリマー1.0g、参考例13(1)で合成した単段重合ポリマー4.0gを、参考例12(1)で合成した単段重合ポリマー4.0g、参考例13(1)で合成した単段重合ポリマー1.0gとしたこと以外は、参考例15(1)に記載の方法に従って行い、溶媒ブレンドポリマーを5.0g得た。
(1)エチレン/プロピレン共重合の単段重合
内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン100mL、プロピレン50gを加え70℃に昇温し、さらにエチレンを分圧で0.6MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))0.50mmol、ジエチル亜鉛(有機金属化合物(C))0.05mmol、遷移金属化合物(A-X1)のトルエン溶液1.00mL(1.0mM、1.0μmol)と遷移金属化合物(A-Y1)のトルエン溶液0.10mL(1.0mM、0.1μmol)の混合溶液、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、70℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、単段重合ポリマーを13.5g得た。
内容積1リットルのナス型フラスコに実施例17(1)で合成した単段重合ポリマー2.00gと、キシレン1.00Lを加え、還流管を取り付けた後、オイルバス中140℃で3時間攪拌した。得られた均一溶液を氷冷した後、室温で2時間攪拌した。次いで、析出物を濾過、濾液を濃縮乾固した後に、各々減圧乾燥することで、CXIS成分を1.05g、CXS成分を0.95g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X1)の替わりに遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)を加え、重合時間を15分としたこと以外は実施例17(1)に記載の方法に従って行い、単段重合ポリマーを7.8g得た。
実施例18(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を1.55g、CXS成分を0.45g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X1)を加えなかったこと以外は実施例17(1)に記載の方法に従って行い、単段重合ポリマーを10.0g得た。
比較例5(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を2.00g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X1)の替わりに遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)を加え、トリチルテトラキス(ペンタフルオロフェニル)ボレートの替りにd-MAO(活性化用助触媒成分(B))31.0mgを加え、トリイソブチルアルミニウムを加えなかったこと以外は実施例17(1)に記載の方法に従って行い、単段重合ポリマーを15.1g得た。
実施例19(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を0.87g、CXS成分を1.13g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X2)を加えなかったこと以外は実施例19(1)に記載の方法に従って行い、単段重合ポリマーを9.4g得た。
比較例6(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を2.00g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-Y1)の替わりに遷移金属化合物(A-Y2)のトルエン溶液0.50mL(1.0mM、0.5μmol)を加えたこと以外は実施例17(1)に記載の方法に従って行い、単段重合ポリマーを8.9g得た。
実施例20(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を0.47g、CXS成分を1.53g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X1)の替わりに遷移金属化合物(A-X2)のトルエン溶液1.00mL(1.0mM、1.0μmol)を加え、重合時間を15分としたこと以外は実施例20(1)に記載の方法に従って行い、単段重合ポリマーを4.5g得た。
実施例21(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を1.19g、CXS成分を0.81g得た。
(1)エチレン/プロピレン共重合の単段重合
遷移金属化合物(A-X1)を加えなかったこと以外は実施例20(1)に記載の方法に従って行い、単段重合ポリマーを2.5g得た。
比較例7(1)で得られた単段重合ポリマーを用いたこと以外は、実施例17(2)と同様に行い、CXIS成分を2.00g得た。
このことは、CXIS成分中に重合触媒(X)由来の非晶性のエチレン/プロピレン共重合体セグメント(X)が存在することを示している。しかし、該セグメント(X)はそのTgの値から、通常ではすべてCXS成分に分別される組成である。したがってこのことは、単独ではCXS成分として分別されるべき非晶性のエチレン/プロピレン共重合体セグメント(X)が、該セグメント(X)に対して化学的に連結した結晶性のエチレン/プロピレン共重合体セグメント(Y)の性質によって、不溶成分としてCXIS成分中に存在していることを示しており、実施例17~21で得られた単段重合ポリマーにおいて、オレフィンブロックポリマーが生成していることが示唆される。
(1)エチレンの単段重合
内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン200mLを加え40℃に昇温し、さらにエチレンを分圧で0.6MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))0.25mmol、遷移金属化合物(A-X1)のトルエン溶液1.00mL(1.0mM、1.0μmol)と遷移金属化合物(A-Y3)のトルエン溶液1.00mL(1.0mM、1.0μmol)の混合溶液、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、40℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、単段重合ポリマーを4.4g得た。
(1)エチレンの単段重合
遷移金属化合物(A-X1)を加えなかったこと以外は実施例22(1)に記載の方法に従って行い、単段重合ポリマーを1.2g得た。
(1)エチレン/プロピレン共重合(前段)とプロピレン単独重合(後段)の2段重合
前段:内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン160mL、プロピレン20gを加え50℃に昇温し、さらにエチレンを分圧で0.4MPa分加えた。次いで、加圧投入器からdーMAO(活性化用助触媒成分(B))31.8mg、ジエチル亜鉛(有機金属化合物(C))0.05mmol、遷移金属化合物(A-Y4)のトルエン溶液0.10mL(1.0mM、0.1μmol)の順にオートクレーブに加え、50℃で30分重合を行った。重合反応終了後、未反応モノマーをパージし、アルゴン2.0MPaを加え、再びパージする操作を2回繰り返した。
後段:オートクレーブ内をアルゴン雰囲気に保ったまま室温に冷却した後、再びプロピレン20gを加え50℃に昇温した。次いで、加圧投入器から遷移金属化合物(A-X1)のトルエン溶液4.00mL(1.0mM、4.0μmol)の順にオートクレーブに加え、50℃で60分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、2段重合ポリマーを4.3g得た。
実施例23(1)で合成した2段重合ポリマーを使用すること以外は、実施例17(2)に記載の方法に従って行い、CXIS成分を1.19g、CXS成分を0.81g得た。
(1)エチレン/プロピレン共重合(前段)とプロピレン単独重合(後段)の2段重合
前段:内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン160mL、プロピレン20gを加え50℃に昇温し、さらにエチレンを分圧で0.2MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))0.50mmol、ジエチル亜鉛(有機金属化合物(C))0.05mmol、遷移金属化合物(A-Y4)のトルエン溶液0.20mL(1.0mM、0.2μmol)、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、50℃で15分重合を行った。重合反応終了後、未反応モノマーをパージし、アルゴン2.0MPaを加え、再びパージする操作を2回繰り返した。
後段:オートクレーブ内をアルゴン雰囲気に保ったまま室温に冷却した後、再びプロピレン20gを加え50℃に昇温した。次いで、加圧投入器から遷移金属化合物(A-X1)のトルエン溶液4.00mL(1.0mM、4.0μmol)、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、50℃で120分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、2段重合ポリマーを16.7g得た。
実施例24(1)で合成した2段重合ポリマーを使用すること以外は、実施例17(2)に記載の方法に従って行い、CXIS成分を0.91g、CXS成分を1.09g得た。
(1)エチレン/プロピレン共重合(前段)とプロピレン単独重合(後段)の2段重合
前段:内容積0.4リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン160mL、プロピレン20gを加え50℃に昇温し、さらにエチレンを分圧で0.2MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))0.50mmol、ジエチル亜鉛(有機金属化合物(C))0.01mmol、遷移金属化合物(A-Y4)のトルエン溶液0.10mL(1.0mM、0.1μmol)、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、50℃で15分重合を行った。重合反応終了後、未反応モノマーをパージし、アルゴン2.0MPaを加え、再びパージする操作を2回繰り返した。
後段:オートクレーブ内をアルゴン雰囲気に保ったまま室温に冷却した後、再びプロピレン20gを加え50℃に昇温した。次いで、加圧投入器から遷移金属化合物(A-X2)のトルエン溶液4.00mL(1.0mM、4.0μmol)、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、50℃で60分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール500mLおよび1N塩酸水溶液5mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、2段重合ポリマーを15.3g得た。
実施例25(1)で合成した2段重合ポリマーを使用すること以外は、実施例17(2)に記載の方法に従って行い、CXIS成分を1.09g、CXS成分を0.91g得た。
(1)エチレン/プロピレン共重合(前段)とプロピレン単独重合(後段)の2段重合
前段:内容積3.0リットルの撹拌機付きオートクレーブを十分乾燥した後、トルエン800mL、プロピレン100gを加え50℃に昇温し、さらにエチレンを分圧で0.2MPa分加えた。次いで、加圧投入器からトリイソブチルアルミニウム(有機金属化合物(C))1.00mmol、ジエチル亜鉛(有機金属化合物(C))0.15mmol、遷移金属化合物(A-Y4)のトルエン溶液0.80mL(1.0mM、0.8μmol)、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、50℃で30分重合を行った。重合反応終了後、未反応モノマーをパージし、アルゴン2.0MPaを加え、再びパージする操作を2回繰り返した。
後段:オートクレーブ内をアルゴン雰囲気に保ったまま室温に冷却した後、再びプロピレン100gを加え80℃に昇温した。次いで、加圧投入器から遷移金属化合物(A-Y4)のトルエン溶液2.00mL(1.0mM、2.0μmol)、トリチルテトラキス(ペンタフルオロフェニル)ボレート(活性化用助触媒成分(B))のトルエン溶液1.00mL(4.0mM、4.0μmol)の順にオートクレーブに加え、80℃で30分重合を行った。少量のエタノールを加えて反応を停止させ、未反応モノマーをパージして、オートクレーブを開放した後、エタノール2000mLおよび1N塩酸水溶液20mLを加え、室温で30分攪拌した。析出したポリマーを吸引濾過した後、真空乾燥機にて十分に減圧乾燥し、2段重合ポリマーを53.8g得た。
比較例9(1)で合成した2段重合ポリマーを使用すること以外は、実施例17(2)に記載の方法に従って行い、CXIS成分を1.40g、CXS成分を0.60g得た。
このことは、CXIS成分中に重合触媒(Y)由来のエチレン/プロピレン共重合体セグメント(Y)が存在することを示している。しかし、該セグメント(Y)はそのTgの値から、通常ではすべてCXS成分に分別される組成である。したがってこのことは、単独ではCXS成分として分別されるべき非晶性のエチレン/プロピレン共重合体セグメント(Y)が、該セグメント(Y)に対して化学的に連結した結晶性のプロピレン単独重合体セグメント(X)の性質によって、不溶成分としてCXIS成分中に存在していることを示しており、実施例23~25で得られた2段重合ポリマーにおいて、オレフィンブロックポリマーが生成していることが示唆される。
さらに上記の実施例23~25では、重合触媒(Y)のみを用いた比較例9に比べて、CXIS成分中のEP含量の値が大きく、オレフィンブロックポリマーの生成効率が高い。
Claims (21)
- 重合触媒(X)と、重合触媒(Y)と、
元素周期律表第2族、12族および13族から選ばれる原子を含む有機金属化合物(C)(活性化用助触媒成分(B)を除く)とを用いて、オレフィンを重合するオレフィンブロックポリマーの製造方法であって、
重合触媒(X)は、下記一般式(1-X)で表される遷移金属化合物(A-X)と、有機アルミニウムオキシ化合物(B-1)、有機ホウ素化合物(B-2)、亜鉛助触媒成分(B-3)およびイオン交換性層状珪酸塩(B-4)から選ばれる活性化用助触媒成分(B)とを接触させて形成され、
重合触媒(Y)は、下記一般式(1-Y)(但し、下記一般式(1-X)で表される遷移金属化合物を除く)から選ばれる遷移金属化合物(A-Y)と、有機アルミニウムオキシ化合物(B-1)、有機ホウ素化合物(B-2)、亜鉛助触媒成分(B-3)およびイオン交換性層状珪酸塩(B-4)から選ばれる活性化用助触媒成分(B)とを接触させて形成される、製造方法。
MXは、チタン原子、ジルコニウム原子またはハフニウム原子を表す。
RX1~RX8は、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数2~20のアルケニル基、
炭素原子数2~20のアルキニル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基を表す。
RX1~RX8における上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アルキニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記へテロ環式化合物残基はそれぞれ置換基を有していてもよい。
上記RX1~RX8の定義に関わらず、RX1とRX2、RX2とRX3、RX3とRX4、RX5とRX6、RX6とRX7、RX7とRX8はそれぞれ相互に連結して環を形成してもよく、これらの環は置換基を有していてもよい。
XXは、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数2~20のアルケニル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
炭素原子数1~20のアルコキシ基、
炭素原子数7~30のアラルキルオキシ基、
炭素原子数6~30のアリールオキシ基、
炭素原子数1~20の置換シリル基、
炭素原子数1~20の置換アミノ基、
炭素原子数1~20の置換チオラート基、または
炭素原子数1~20のカルボキシラート基を表す。
XXにおける上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記カルボキシラート基はそれぞれ置換基を有していてもよい。
XX同士は、相互に連結して環を形成してもよい。
EXは中性のルイス塩基を表す。EXが複数ある場合は、複数のEXは同一でも異なっていてもよい。EXの個数を示す下付のxは、0、1、または2である。)
Lは、水素原子を除いて70個までの原子を含有し、共役系π電子を介してMに結合するπ電子共役系アニオン性基であり、aが2以上の場合、Lは互いに同一でも異なっていてもよい。
Xは、水素原子を除いて70個までの原子を含有する非共役系アニオン性基であり、bが2以上の場合、Xは互いに同一でも異なっていてもよい。
Eは、水素原子を除いて70個までの原子を含有し、1つ以上の非共有電子対を介してMに結合する中性ルイス塩基性配位子であり、cが2以上の場合、Eは互いに同一でも異なっていてもよい。
aは0~6の整数であり、bは0~8の整数であり、cは0~9の整数であり、nは1~4の整数である。また、M、L、Xの価数がそれぞれme、le、xeのとき、me=le×a+xe×bの関係を満たす。また、L、X、Eは、これらのうち2個以上が互いに連結して環を形成していてもよく、さらにaが2以上の場合、L同士が、bが2以上の場合、X同士が、cが2以上の場合、E同士が、nが2以上の場合、L同士、X同士、E同士が互いに連結して環を形成していてもよい。) - 重合触媒(Y)を形成する遷移金属化合物(A-Y)として、式(1-Y-1)~(1-Y-8)に示す化合物を用いる、請求項1に記載のオレフィンブロックポリマーの製造方法。
R1は水素原子以外に1~30個の原子を含有するハイドロカルビル基を表す。
T1は水素原子以外に1~40個の原子を含有する二価の架橋基を表す。
E1はルイス塩基性を有する炭素原子数5~40の複素環式化合物残基を表す。)
Gは酸素原子、硫黄原子、セレン原子または置換基Rdを有する窒素含有基(-NRd-)を表す。また、aが2以上の場合、G同士は互いに同一でも異なっていてもよい。
T2は窒素原子または置換基Reを有する炭素含有基(-CRe=)である。また、aが2以上の場合、T2同士は互いに同一でも異なっていてもよい。
R9~R11、Gに含まれるRd、T2に含まれるReは、前記一般式(1-Y)中のXと同様のものを表す。R9~R11、Rd、Reは、互いに同一でも異なっていてもよく、aが2以上の場合、R9同士、R10同士、R11同士、Rd同士、Re同士は互いに同一でも異なっていてもよい。また、R10、R11、Rd、Reは、これらのうち2個以上が互いに連結して環を形成していてもよく、aが2以上の場合、R9~R11、Rd、Reのうちの1個の基と、他の配位子に含まれるR9~R11、Rd、Reのうちの1個の基とが連結されていてもよい。)
T4は、-CRg 2-、-C6Rg 4-、-SiRg 2-、-NRg-、-PRg-、-P(O)Rg-、-S-、-S(O)-または-SO2-を表す。T4がヘテロ原子を含む場合は、T4のヘテロ原子がMに直接配位結合していてもよい。
R10、R11、R16、Gに含まれるRd、T4に含まれるRgは、前記一般式(1-Y)中のXと同様のものを表す。R10、R11、R16、Rd、Rgは、互いに同一でも異なっていてもよく、R16同士は互いに同一でも異なっていてもよく、aが2以上の場合、R10同士、R11同士、Rd同士、Rg同士は互いに同一でも異なっていてもよい。また、R10、R11、Rd、Rgは、これらのうち2個以上が互いに連結して環を形成していてもよく、aが2以上の場合、R10、R11、R16、Rd、Rgのうちの1個の基と、他の配位子に含まれるR10、R11、R16、Rd、Rgのうちの1個の基とが連結されていてもよい。)
T3は、-CRf 2-、-SiRf 2-、-NRf-、-PRf-、-P(O)Rf-、-O-、-S-、-S(O)-または-SO2-を表す。T3がヘテロ原子を含む場合は、T3のヘテロ原子がMに直接配位結合していてもよい。gは、1~7の整数である。また、gが2以上の場合、T3同士は互いに同一でも異なっていてもよい。
T5は、-CRh 2-、-C6Rh 4-、-SiRh 2-、-NRh-、-PRh-、-P(O)Rh-、-S-、-S(O)-または-SO2-を表す。T5がヘテロ原子を含む場合は、T5のヘテロ原子がMに直接配位結合していてもよい。また、T5同士は互いに同一でも異なっていてもよい。
R12~R15は、前記一般式(1-Y)中のXと同様のものを表す。R12~R15、T3に含まれるRf、T5に含まれるRhは互いに同一でも異なっていてもよく、R12同士、R13同士、R14同士、R15同士、Rh同士は互いに同一でも異なっていてもよく、gが2以上の場合、Rf同士は互いに同一でも異なっていてもよい。また、R12~R15、Rf、Rh、は、これらのうち2個以上が互いに連結して環を形成していてもよく、gが2以上の場合、2個以上のRf同士が互いに連結して環を形成していてもよい。)
bは1~4の整数である。またbが2以上の場合、X同士は互いに同一でも異なっていてもよく、2つ以上のX同士が互いに連結して環を形成していてもよい。
また、R22はそれぞれ互いに同一でも異なっていてもよく、隣接する2つのR22同士が互いに連結して環を形成していてもよい。
シクロペンタジエニル環上の置換基R22同士の結合により形成される上記環上の水素原子の一部もしくは全てが、さらにR22によって置換されていてもよい。)
bは1~3の整数である。またbが2以上の場合、X同士は互いに同一でも異なっていてもよく、2つ以上のX同士が互いに連結して環を形成していてもよい。
Zは窒素原子、リン原子、酸素原子、硫黄原子、置換基Rmを有する窒素含有基(-NRm-)または、置換基Rmを有するリン含有基(-PRm-)である。
R23~R25、Zに含まれるRmは、前記一般式(1-Y)中のXと同様のものを表す。R23~R25、Rmは、互いに同一でも異なっていてもよく、R23同士、R24同士、R25同士は互いに同一でも異なっていてもよい。また、R23、R24、R25、Rmは、これらのうち2個以上が互いに連結して環を形成していてもよい。
R26、R27は、互いに独立に、前記一般式(1-Y)中のXと同様のものを表す。R26同士、R27同士は、互いに同一でも異なっていてもよい。また、2個のR26および2個のR27から選ばれる2個以上が互いに連結して環を形成していてもよい。 - 一般式(1-X)において、
RX1およびRX5が、それぞれ独立して、
ハロゲン原子、
炭素原子数1~20のアルキル基、
環を構成する炭素原子数が3~10のシクロアルキル基、
炭素原子数7~30のアラルキル基、
炭素原子数6~30のアリール基、
置換シリル基、または
環を構成する炭素原子数が3~20のヘテロ環式化合物残基
である請求項1または2に記載のオレフィンブロックポリマーの製造方法。 - 一般式(1-X)において、
nが3である請求項1~3のいずれか1項に記載のオレフィンブロックポリマーの製造方法。 - 有機金属化合物(C)が有機アルミニウム化合物および/または有機亜鉛化合物を含む、請求項1~4のいずれか1項に記載のオレフィンブロックポリマーの製造方法。
- 有機金属化合物(C)が炭素原子数3~24の有機アルミニウム化合物および/または炭素原子数2~16の有機亜鉛化合物を含む、請求項5に記載のオレフィンブロックポリマーの製造方法。
- オレフィンブロックポリマーの製造方法が、重合触媒(X)および重合触媒(Y)を単一の工程で形成させてオレフィンを重合する単段重合である、請求項1~6のいずれか1項に記載のオレフィンブロックポリマーの製造方法。
- 単段重合において2種類以上のオレフィンを重合する、請求項7に記載のオレフィンブロックポリマーの製造方法。
- オレフィンブロックポリマーの製造方法が、重合触媒(X)を形成させてオレフィンを重合する工程と重合触媒(Y)を形成させてオレフィンを重合する工程とを含む多段重合であり、隣り合う2つの工程で形成される重合触媒の種類が互いに異なり、かつ、一つ前の工程までに得られた重合体の存在下で該オレフィンを重合する、請求項1~6のいずれか1項に記載のオレフィンブロックポリマーの製造方法。
- 多段重合が2段重合である、請求項9に記載のオレフィンブロックポリマーの製造方法。
- 2段重合の前段と後段で、オレフィンの組成が互いに異なる、請求項10に記載のオレフィンブロックポリマーの製造方法。
- 2段重合の前段と後段の一方で2種以上のオレフィンの共重合を行い、当該前段と後段の他方で1種のオレフィンの単独重合を行う、請求項11に記載のオレフィンブロックポリマーの製造方法。
- オレフィンが、エチレン、炭素原子数が3~20のα-オレフィン、炭素原子数が3~20の環状オレフィン、および炭素原子数が5~20のアルケニル脂環式化合物から選ばれる、請求項1~12のいずれか1項に記載のオレフィンブロックポリマーの製造方法。
- オレフィンが、エチレンおよび炭素原子数が3~10のα-オレフィンからなる群より選ばれる、請求項13に記載のオレフィンブロックポリマーの製造方法。
- オレフィンが、エチレンおよびプロピレンからなる群より選ばれる、請求項14に記載のオレフィンブロックポリマーの製造方法。
- 単段重合において、エチレンおよび炭素原子数が3~10のα-オレフィンを重合する、請求項8に記載のオレフィンブロックポリマーの製造方法。
- 炭素原子数が3~10のα-オレフィンがプロピレンである請求項16に記載のオレフィンブロックポリマーの製造方法。
- 2段重合の前段と後段の一方でエチレンおよびプロピレンの共重合を行い、当該前段と後段の他方でプロピレンの単独重合を行う、請求項12に記載のオレフィンブロックポリマーの製造方法。
- 以下の要件(1)~(5)の全てを満たすエチレン/プロピレンブロック共重合体組成物。
(1)130℃以上の融点を一つ以上有する
(2)HEPBHISの含量が2.0wt%以上
(3)HC2’BHISが80.0mol%以上94.5mol%以下
(4)LC2’BHISが0.1mol%以上9.0mol%以下
(5)HC2’BHISとHC2’BHSの差の絶対値が5.0mol%以下 - 以下の要件(6)を満たす請求項19に記載のエチレン/プロピレンブロック共重合体組成物。
(6)12000 ≦ ヤング率(MPa)×テンサイルインパクト(kJ/m2) - 以下の要件(7)を満たす請求項20に記載のエチレン/プロピレンブロック共重合体組成物。
(7)ヘイズの値が18%以下
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170095036A (ko) * | 2016-02-12 | 2017-08-22 | 주식회사 엘지화학 | 신규한 리간드 화합물 및 전이금속 화합물의 제조방법 |
US10662322B2 (en) | 2017-04-27 | 2020-05-26 | Sumitomo Chemical Company, Limited | Propylene polymer composition |
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US10358397B2 (en) | 2017-06-29 | 2019-07-23 | Exxonmobil Chemical Patents Inc. | Production of olefin dimers |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007035485A1 (en) * | 2005-09-15 | 2007-03-29 | Dow Global Technologies Inc. | Catalytic olefin block copolymers with controlled block sequence distribution |
JP2007529616A (ja) * | 2004-03-17 | 2007-10-25 | ダウ グローバル テクノロジーズ インコーポレイティド | エチレンコポリマーを形成するためのシャトリング剤を含む触媒組成物 |
JP2010126557A (ja) * | 2008-11-25 | 2010-06-10 | Mitsui Chemicals Inc | オレフィンブロック重合体の製造方法 |
Family Cites Families (63)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5661416A (en) * | 1979-10-24 | 1981-05-26 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
US5391629A (en) | 1987-01-30 | 1995-02-21 | Exxon Chemical Patents Inc. | Block copolymers from ionic catalysts |
DE3942363A1 (de) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | Verfahren zur herstellung einer polypropylen-formmasse |
IT1256663B (it) * | 1992-12-15 | 1995-12-12 | Himont Inc | Composizioni polipropileniche aventi buona trasparenza e migliorata resistenza all'urto. |
US6288192B1 (en) * | 1998-01-14 | 2001-09-11 | Sumitomo Chemical Company, Ltd. | Olefin polymer, olefin polymerization catalyst and process for producing olefin polymer |
EP1829907B1 (en) | 1998-10-19 | 2012-04-11 | JNC Petrochemical Corporation | Propylene/ethylene block copolymer, blushing-resistant transparent polypropylene resin for molding, elastomer for molding, and molded article obtained therefrom |
US7022782B2 (en) | 2000-12-26 | 2006-04-04 | Sumitomo Chemical Company, Limited | Homogeneous type solid catalyst component or homogeneous type solid catalyst, process for production thereof and process for producing addition polymer with the same |
EP1275662A1 (en) * | 2000-12-26 | 2003-01-15 | Sumitomo Chemical Company, Limited | Modified particle, support, catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
US20030069127A1 (en) | 2000-12-26 | 2003-04-10 | Kazuo Takaoki | Modified particle,support, catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
JP4234005B2 (ja) | 2001-07-12 | 2009-03-04 | 出光興産株式会社 | ポリオレフィン系樹脂組成物 |
US6818703B2 (en) | 2002-03-29 | 2004-11-16 | Sumitomo Chemical Company, Limited | Propylene-based resin composition and film made of the same |
JP2004051801A (ja) * | 2002-07-19 | 2004-02-19 | Mitsui Chemicals Inc | ポリオレフィン樹脂組成物及びその用途 |
BRPI0508148B1 (pt) | 2004-03-17 | 2015-09-01 | Dow Global Technologies Inc | Interpolímero de etileno em multibloco, derivado reticulado e composição |
US7714071B2 (en) | 2004-03-17 | 2010-05-11 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom |
US7662881B2 (en) | 2004-03-17 | 2010-02-16 | Dow Global Technologies Inc. | Viscosity index improver for lubricant compositions |
US7504347B2 (en) | 2004-03-17 | 2009-03-17 | Dow Global Technologies Inc. | Fibers made from copolymers of propylene/α-olefins |
BRPI0508173B1 (pt) | 2004-03-17 | 2016-03-15 | Dow Global Technologies Inc | copolímeros em multibloco, polímero, copolímero, um derivado funcional, mistura homogênea de polímero, processo para a preparação de um copolímero em multibloco contendo propileno e processo para preparar um copolímero em multibloco contendo 4-metil-1-penteno |
US7582716B2 (en) | 2004-03-17 | 2009-09-01 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack |
US7671106B2 (en) | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Cap liners, closures and gaskets from multi-block polymers |
US7666918B2 (en) | 2004-03-17 | 2010-02-23 | Dow Global Technologies, Inc. | Foams made from interpolymers of ethylene/α-olefins |
US7863379B2 (en) | 2004-03-17 | 2011-01-04 | Dow Global Technologies Inc. | Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers |
US7795321B2 (en) | 2004-03-17 | 2010-09-14 | Dow Global Technologies Inc. | Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom |
US8273838B2 (en) | 2004-03-17 | 2012-09-25 | Dow Global Technologies Llc | Propylene/α-olefins block interpolymers |
US7622529B2 (en) | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility |
US7608668B2 (en) | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
US7687442B2 (en) | 2004-03-17 | 2010-03-30 | Dow Global Technologies Inc. | Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils |
US7514517B2 (en) | 2004-03-17 | 2009-04-07 | Dow Global Technologies Inc. | Anti-blocking compositions comprising interpolymers of ethylene/α-olefins |
US7579408B2 (en) | 2004-03-17 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins |
US7671131B2 (en) | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom |
US7355089B2 (en) | 2004-03-17 | 2008-04-08 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
US7622179B2 (en) | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof |
US7897689B2 (en) | 2004-03-17 | 2011-03-01 | Dow Global Technologies Inc. | Functionalized ethylene/α-olefin interpolymer compositions |
AR053693A1 (es) | 2004-03-17 | 2007-05-16 | Dow Global Technologies Inc | Composiciones de interpolimero de etileno/alfa-olefina multibloque adecuado para peliculas |
US7557147B2 (en) | 2004-03-17 | 2009-07-07 | Dow Global Technologies Inc. | Soft foams made from interpolymers of ethylene/alpha-olefins |
US7741397B2 (en) | 2004-03-17 | 2010-06-22 | Dow Global Technologies, Inc. | Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof |
US7524911B2 (en) | 2004-03-17 | 2009-04-28 | Dow Global Technologies Inc. | Adhesive and marking compositions made from interpolymers of ethylene/α-olefins |
US7803728B2 (en) | 2004-03-17 | 2010-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of ethylene/α-olefins |
US8273826B2 (en) | 2006-03-15 | 2012-09-25 | Dow Global Technologies Llc | Impact modification of thermoplastics with ethylene/α-olefin interpolymers |
JP5570115B2 (ja) | 2005-03-17 | 2014-08-13 | ダウ グローバル テクノロジーズ エルエルシー | 擬似ブロックコポリマーおよび可逆的連鎖移動剤(chainshuttlingagent)を用いる方法 |
US7786216B2 (en) | 2005-03-17 | 2010-08-31 | Dow Global Technologies Inc. | Oil based blends of interpolymers of ethylene/α-olefins |
US7910658B2 (en) | 2005-03-17 | 2011-03-22 | Dow Global Technologies Llc | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
US7737215B2 (en) | 2005-03-17 | 2010-06-15 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
KR101319131B1 (ko) | 2005-03-17 | 2013-10-17 | 다우 글로벌 테크놀로지스 엘엘씨 | 에틸렌/알파-올레핀 공중합체로부터 제조된 섬유 |
US7989543B2 (en) | 2005-03-17 | 2011-08-02 | Dow Global Technologies Llc | Adhesive and marking compositions made from interpolymers of ethylene/α-olefins |
US8084537B2 (en) | 2005-03-17 | 2011-12-27 | Dow Global Technologies Llc | Polymer blends from interpolymers of ethylene/α-olefin with improved compatibility |
AU2006227619A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Llc | Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates |
MX2007011334A (es) | 2005-03-17 | 2007-10-02 | Dow Global Technologies Inc | Revestimientos de tapas, cierres y juntas de polimeros de bloques multiples. |
US7906587B2 (en) | 2005-09-16 | 2011-03-15 | Dow Global Technologies Llc | Polymer blends from interpolymer of ethylene/α olefin with improved compatibility |
US7695812B2 (en) | 2005-09-16 | 2010-04-13 | Dow Global Technologies, Inc. | Fibers made from copolymers of ethylene/α-olefins |
US8071701B2 (en) | 2005-12-16 | 2011-12-06 | Dow Global Technologies Llc | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
WO2009012215A1 (en) * | 2007-07-13 | 2009-01-22 | Dow Global Technologies Inc. | Ethylene/a-olefin interpolymers containing low crystallinity hard blocks |
WO2009012153A1 (en) | 2007-07-13 | 2009-01-22 | Dow Global Technologies Inc. | Viscosity index improver for lubricant compositions |
JP5996162B2 (ja) | 2007-07-13 | 2016-09-21 | ダウ グローバル テクノロジーズ エルエルシー | 制御されたブロック配列分布及び少なくとも一つの低結晶性ハードブロックを有する触媒オレフィンブロックコポリマー |
US20120184676A1 (en) | 2007-08-31 | 2012-07-19 | Stichting Dutch Polymer Institute | Compatiblised polyolefin compositions |
BRPI0905778B1 (pt) | 2008-01-30 | 2019-04-30 | Dow Global Technologies Inc. | COMPOSIÇÃO DE INTERPOLÍMERO EM BLOCOS DE ETILENO/a-OLEFINA, INTERPOLÍMERO EM BLOCOS DE PROPILENO/a-OLEFINA, ARTIGO E PROCESSO PARA POLIMERIZAÇÃO DE UM OU MAIS MONÔMEROS POLIMERIZÁVEIS POR ADIÇÃO |
WO2009097560A1 (en) | 2008-01-30 | 2009-08-06 | Dow Global Technologies Inc. | ETHYLENE/α-OLEFIN BLOCK INTERPOLYMERS |
US8124709B2 (en) | 2008-01-30 | 2012-02-28 | Dow Global Technologies Llc | Ethylene/α-olefin block interpolymers |
KR101765964B1 (ko) * | 2009-10-13 | 2017-08-07 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | 프로필렌 중합체 조성물 |
DE112011100520T5 (de) * | 2010-02-12 | 2012-11-29 | National University Corporation Saitama University | Katalysator zur stereoselektiven Olefinpolymerisation und Verfahren zur Herstellung von stereoselektivem Polyolefin |
WO2012147995A1 (ja) | 2011-04-28 | 2012-11-01 | 住友化学株式会社 | オレフィンブロックポリマーの製造方法 |
WO2013022102A1 (ja) | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | エチレン系重合用触媒およびエチレン系重合体の製造方法 |
WO2013022103A1 (ja) | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | 4族遷移金属錯体を用いるオレフィンブロックポリマーの製造方法 |
JP2013166898A (ja) | 2012-02-16 | 2013-08-29 | Sumitomo Chemical Co Ltd | 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 |
-
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- 2012-11-29 WO PCT/JP2012/081003 patent/WO2013081080A1/ja active Application Filing
- 2012-11-29 DE DE112012005025.8T patent/DE112012005025T5/de not_active Withdrawn
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-
2014
- 2014-05-30 US US14/291,303 patent/US9695260B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007529616A (ja) * | 2004-03-17 | 2007-10-25 | ダウ グローバル テクノロジーズ インコーポレイティド | エチレンコポリマーを形成するためのシャトリング剤を含む触媒組成物 |
WO2007035485A1 (en) * | 2005-09-15 | 2007-03-29 | Dow Global Technologies Inc. | Catalytic olefin block copolymers with controlled block sequence distribution |
JP2010126557A (ja) * | 2008-11-25 | 2010-06-10 | Mitsui Chemicals Inc | オレフィンブロック重合体の製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170095036A (ko) * | 2016-02-12 | 2017-08-22 | 주식회사 엘지화학 | 신규한 리간드 화합물 및 전이금속 화합물의 제조방법 |
KR102095007B1 (ko) | 2016-02-12 | 2020-03-30 | 주식회사 엘지화학 | 신규한 리간드 화합물 및 전이금속 화합물의 제조방법 |
US10662322B2 (en) | 2017-04-27 | 2020-05-26 | Sumitomo Chemical Company, Limited | Propylene polymer composition |
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JPWO2013081080A1 (ja) | 2015-04-27 |
DE112012005025T5 (de) | 2014-10-16 |
JP6068754B2 (ja) | 2017-01-25 |
CN103958548A (zh) | 2014-07-30 |
US20140275429A1 (en) | 2014-09-18 |
CN103958548B (zh) | 2016-05-18 |
US9695260B2 (en) | 2017-07-04 |
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