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WO2009081792A1 - Procédé de production d'un copolymère d'éthylène/alpha-oléfine/polyène non conjugué - Google Patents

Procédé de production d'un copolymère d'éthylène/alpha-oléfine/polyène non conjugué Download PDF

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Publication number
WO2009081792A1
WO2009081792A1 PCT/JP2008/072826 JP2008072826W WO2009081792A1 WO 2009081792 A1 WO2009081792 A1 WO 2009081792A1 JP 2008072826 W JP2008072826 W JP 2008072826W WO 2009081792 A1 WO2009081792 A1 WO 2009081792A1
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Prior art keywords
ethylene
group
olefin
atom
polyene copolymer
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PCT/JP2008/072826
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English (en)
Japanese (ja)
Inventor
Sadahiko Matsuura
Haruka Saito
Mayumi Hiwara
Yasushi Tohi
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Mitsui Chemicals, Inc.
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Publication of WO2009081792A1 publication Critical patent/WO2009081792A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to a novel method for producing an ethylene / ⁇ -olefin / nonconjugated polyene copolymer using a transition metal compound having a specific structure.
  • Ethylene / ⁇ -olefin rubber represented by ethylene / propylene / non-conjugated diene copolymer (EPDM) does not have an unsaturated bond in the main chain of its molecular structure. Since it is superior in heat resistance and weather resistance compared to rubber, it is widely used in applications such as automotive parts, electric wire materials, building civil engineering materials, industrial material parts, and various resin modifiers.
  • EPDM non-conjugated diene copolymer
  • ethylene / ⁇ -olefin / non-conjugated polyene copolymers such as EPDM generally use a catalyst system (so-called Ziegler-Natta catalyst system) composed of a titanium catalyst or a combination of a vanadium catalyst and an organoaluminum compound.
  • a catalyst system so-called Ziegler-Natta catalyst system
  • the biggest disadvantage of this catalyst system is its productivity, and the polymerization activity is low and the catalyst life is short, so that the polymerization at a low temperature around 0 to 50 ° C. is forced.
  • the product concentration in the polymerization system is limited due to the viscosity bottleneck of the polymerization solution, and a process for decatalyzing and deashing the product is essential. Therefore, there is a problem that it is difficult to control polymerization, and this is extremely disadvantageous in terms of production and cost.
  • the metallocene catalyst system which has been actively researched since the 1980s, exhibits superior polymerization activity and ⁇ -olefin copolymerization ability compared to the Ziegler-Natta catalyst system. It has been reported that a novel olefin copolymer having a narrow composition distribution can be produced, and a novel production method has been made for an ethylene / ⁇ -olefin / non-conjugated polyene copolymer.
  • problems related to ethylene / ⁇ -olefin / non-conjugated polyene copolymer production include polymerization activity that can be applied to a deashing-free process, high molecular weight that can withstand high-temperature polymerization, and non-conjugated polyene that does not burden the monomer recovery process
  • problems in terms of production, cost, and physical properties such as copolymerization ability, high monomer alternate copolymerization ability for exhibiting good low-temperature characteristics, and moderately wide molecular weight distribution exhibiting good processability.
  • Patent Document 1 Patent Document 2, Patent Document 3, and Patent Document 4 disclose a production method using a geometrically constrained catalyst, but it has excellent ⁇ -olefin copolymerizability and produces a high molecular weight product.
  • the ethylene average chain length in the ethylene / ⁇ -olefin / nonconjugated polyene copolymer is long, resulting in poor low-temperature characteristics, which is one of the key physical properties. Remains.
  • the production method using a geometrically constrained catalyst there is a problem that it is difficult to control the polymerization heat because it often shows high polymerization activity in the initial stage of polymerization.
  • Patent Document 5 Patent Document 6, Patent Document 7 and the like disclose a bridged metallocene catalyst having a biscyclopentadienyl group or a bisindenyl group as a ligand. Although they are relatively high, both have low polymerization activity, and there is a problem that the molecular weight of the resulting ethylene / ⁇ -olefin / non-conjugated polyene copolymer is low.
  • the present inventors have achieved production costs and costs using a metallocene catalyst having a specific structure.
  • the present inventors have found a novel method for producing an ethylene / ⁇ -olefin / nonconjugated polyene copolymer excellent in surface and physical properties, and have completed the present invention.
  • the present invention relates to (A) a transition metal compound represented by the following general formula [I] (may be abbreviated as “bridged metallocene compound” in the following description), (B) (B-1) organic An olefin polymerization catalyst comprising: a metal compound, (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, and a silicon-containing group, and may be the same or different, and R 1 to R 16 may be bonded to adjacent substituents to form a ring.
  • n is an integer of 1 to 3
  • Y 1 and Y 2 are Group 14 atoms, which may be the same or different from each other.
  • n 1
  • Y 1 and Y 2 are both silicon atoms and R 1 to R 12 are simultaneously hydrogen atoms
  • R 13 to R 16 are not phenyl groups at the same time
  • Y 1 and Y 2 Are carbon atoms and R 1 to R 12 are simultaneously hydrogen atoms, R 13 to R 16 are not simultaneously hydrogen atoms.
  • M is selected from a titanium atom, a zirconium atom and a hafnium atom
  • Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand,
  • the neutral ligands that can be coordinated by a lone pair are selected in the same or different combinations.
  • j is an integer of 1 to 4. When j is 2 or more, Qs may be the same or different.
  • M is preferably a zirconium atom, and is preferably a hafnium atom.
  • Y 1 and Y 2 is a carbon atom, it is preferable Y 1 and Y 2 is silicon atom.
  • the ⁇ -olefin preferably has 3 to 20 carbon atoms, more preferably propylene.
  • the non-conjugated polyene is preferably a compound represented by the following general formula [II].
  • m is an integer of 0 to 2
  • R 17 , R 18 , R 19 and R 20 are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group or The hydrocarbon group may have a double bond, and any two of R 17 to R 20 may be bonded to each other to form a monocyclic or polycyclic ring.
  • the monocyclic or polycyclic ring may have a double bond, and R 17 and R 18 , or R 19 and R 20 may form an alkylidene group, and R 17 and R 19 Or R 18 and R 20 may be bonded to each other to form a double bond.
  • a monocyclic or polycyclic ring formed by bonding any two of R 17 to R 20 to each other has a double bond (ii) with R 17 and R 18 , or R 19 and R 20 form an alkylidene group (iii) R 17 and R 19 or R 18 and R 20 are bonded to each other to form a double bond (iv)
  • At least one of R 17 to R 20 is an unsaturated hydrocarbon group having one or more double bonds.
  • the polymerization temperature at the time of copolymerizing ethylene, ⁇ -olefin and non-conjugated polyene is preferably 80 ° C. or higher.
  • the copolymer obtained has a B value calculated by the following formula [III] based on the 13 C-NMR spectrum, usually 1.05 or more.
  • B value (c + d) / [2 ⁇ a ⁇ (e + f)] [III]
  • a is an ethylene mole fraction
  • c is an ethylene- ⁇ -olefin dyad mole fraction
  • d is an ethylene-nonconjugated polyene dyad mole fraction
  • e is an ⁇ -olefin mole fraction
  • f is (Mole fraction of non-conjugated polyene)
  • the molecular weight distribution of the copolymer can be controlled by a single catalyst system and single-stage polymerization, and good polymerization activity can be achieved.
  • the present production method can simultaneously solve the problems of existing metallocene catalyst systems in terms of productivity and physical properties.
  • the transition metal compound (bridged metallocene compound) represented by the general formula [I] an example of a preferred bridged metallocene compound, a method for producing the bridged metallocene compound used in the present invention, and the bridged metallocene compound used in the present invention as ethylene
  • a preferred embodiment for use in a catalyst for an / ⁇ -olefin / non-conjugated polyene copolymer, and finally a method for polymerizing monomers in the presence of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer catalyst are sequentially explained. To do.
  • Bridged metallocene compound used in the present invention is represented by the general formula [I].
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, and a silicon-containing group, which may be the same or different, and R 1 to R 16 may combine with adjacent substituents to form a ring.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • hydrocarbon group examples include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a substituted aryl group.
  • Oxygen-containing groups such as methoxy group, ethoxy group, and phenoxy group, nitrogen-containing groups such as nitro group, cyano group, N-methylamino group, N, N-dimethylamino group, and N-phenylamino group, boranetriyl group, diboranyl group
  • the hydrocarbon group include those containing a sulfur-containing group such as a boron-containing group such as sulfonyl group and sulfenyl group.
  • the hydrocarbon group may have a hydrogen atom substituted with a halogen atom.
  • Examples of such a hydrocarbon group include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group. be able to.
  • Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group.
  • a silyl group dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl)
  • a silyl group etc. can be mentioned.
  • the cyclopentadienyl group having substituents R 1 to R 4 in the general formula [I] includes an unsubstituted cyclopentadienyl group in which R 1 to R 4 are hydrogen atoms, 3-t-butylcyclopentadi Enyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group, 3- 3-position 1-substituted cyclopentadienyl group such as cyclohexylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl group, 3- Phenyl-5-methylcyclopentadienyl group, 3,5-di-t-butyl
  • Examples of the fluorenyl group having the substituents R 5 to R 12 in the general formula [I] include an unsubstituted fluorenyl group, a 2-methylfluorenyl group, and a 2-t-butylfluorine group in which R 5 to R 12 are hydrogen atoms.
  • 2-position 1-substituted fluorenyl group such as oleenyl group and 2-phenylfluorenyl group
  • 4-position 1 such as 4-methylfluorenyl group, 4-t-butylfluorenyl group and 4-phenylfluorenyl group A substituted fluorenyl group, or a 2,7- or 3,6-position 2-substituted fluorenyl group such as a 2,7-di-t-butylfluorenyl group or a 3,6-di-t-butylfluorenyl group
  • 2,3,6,7-position 4-substituted fluorenyl such as 7-dimethyl-3,6-di-t-butylfluorenyl group, 2,7-diphenyl-3,6-di-t-butylfluorenyl group Group or the following general formula [IV-I] [IV-II] binding R 6 and R 7 as represented each other in to form a ring, R 10
  • R 5 , R 8 , R 9 and R 12 are the same as defined in the general formula [I]
  • R a , R b , R c , R d , R e , R f , R g and R h are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be bonded to adjacent substituents to form a ring. Specific examples include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, amyl group, and n-pentyl group.
  • R x and R y are each independently a hydrocarbon group which may have an unsaturated bond having 1 to 3 carbon atoms, and R x is a bond to R a or R c. R y may form a double bond in combination with the carbon to which R e or R g is bonded, and R x and R y may form a double bond. Both are preferably saturated or unsaturated hydrocarbon groups having 1 or 2 carbon atoms.
  • Specific examples of the compounds represented by the general formulas [IV-I] and [IV-II] include an octamethyloctahydrodibenzofluorenyl group represented by the formula [IV-III], a compound represented by the formula [IV- IV] tetramethyldodecahydrodibenzofluorenyl group represented by formula [IV-V], octamethyltetrahydrodicyclopentafluorenyl group represented by formula [IV-V], hexamethyldihydro represented by formula [IV-VI] Examples thereof include a dicyclopentafluorenyl group and a b, h-dibenzofluorenyl group represented by the formula [IV-VII].
  • All of the transition metal compounds represented by the above general formula [I] containing these fluorenyl groups are excellent in the copolymerization ability of the nonconjugated polyene.
  • a substituted fluorenyl group is more preferable, and in particular, the 2,7-position or 3,6-position 2-substituted fluorenyl group, the 2,3,6,7-position 4-substituted fluorenyl group, represented by the above general formula [IV-I]
  • the transition metal compound represented by the above general formula [I] having a 2,3,6,7-positioned 4-substituted fluorenyl group is excellent in non-conjugated polyene copolymerization ability.
  • the polymerization activity all exhibit high polymerization activity, but the transition metal compound represented by the above general formula [I] having a 2,7-substituted 2-fluorenyl group is particularly excellent.
  • the transition metal compound represented by the above general formula [I] having a 2,7-substituted 2-fluorenyl group is particularly excellent.
  • the ethylene / ⁇ -olefin / non-conjugated polyene copolymer produced exhibits a high molecular weight, it is suitable for polymerization at higher temperatures, has a wide molecular weight distribution, and can control the molecular weight distribution. .
  • R 13 , R 14 , R 15 and R 16 may be the same or different from each other, but are preferably a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, more preferably a hydrogen atom or a methyl group. And particularly preferably a hydrogen atom.
  • Y 1 and Y 2 which are bridging portions are Group 14 atoms and may be the same or different from each other.
  • the Group 14 hydrocarbon atom include a carbon atom, a silicon atom, a germanium atom, and a tin atom, and a carbon atom or a silicon atom is preferable. It is more preferable Y 1 and Y 2 for ease of synthesis are identical atoms, particularly preferably, Y 1 and Y 2 are carbon atoms.
  • n 1
  • Y 1 and Y 2 are both silicon atoms and R 1 to R 12 are simultaneously hydrogen atoms
  • R 13 to R 16 are not simultaneously phenyl groups
  • Y 1 and Y 2 Are carbon atoms and R 1 to R 12 are simultaneously hydrogen atoms, R 13 to R 16 are not simultaneously hydrogen atoms.
  • R 15 and R 16 existing in two or three, respectively, may be the same or different, and R 15 and R 16 may be bonded to each other to form a ring.
  • R 13 and R 15 may be bonded to each other to form a ring, and R 13 and R 15 may be bonded to each other to form a ring, and at the same time, R 14 and R 16 may be bonded to each other to form a ring.
  • R 14 and R 16 form a ring
  • R 14 and R 16 on Y 2 adjacent to Y 1 (position ⁇ ) form a ring.
  • M is a titanium atom, a zirconium atom or a hafnium atom.
  • An ethylene / ⁇ -olefin / non-conjugated polyene copolymer which is preferably a zirconium atom or a hafnium atom and exhibits a wide molecular weight distribution can be obtained. Further, when it is desired to obtain a higher molecular weight ethylene / ⁇ -olefin / non-conjugated polyene copolymer, or when polymerization is desired at a higher temperature, a hafnium atom is more preferable.
  • Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral group having 10 or less carbon atoms, a conjugated or nonconjugated diene, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. Chosen from.
  • J is an integer of 1 to 4, and when j is 2 or more, Q may be the same or different from each other.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom.
  • hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl.
  • anionic ligand examples include alkoxy groups such as methoxy, t-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.
  • organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane.
  • transition metal compound represented by the above general formula [I] in the present invention examples include ethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, ethylene (cyclopenta Dienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride, Ethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, Ethylene (cyclopentadienyl) (tetramethyldodeca
  • hafnium atoms zirconium atoms, and titanium atoms
  • zirconium atoms and hafnium atoms are preferable, and compounds having hafnium atoms generally generate a high molecular weight, so that polymerization at higher temperatures is possible. Therefore, it is preferable from the viewpoint of improving productivity.
  • Hafnium atoms produce higher molecular weight than zirconium atoms and titanium atoms because (1) the Lewis acidity of hafnium atoms is low and the reactivity is low compared to zirconium atoms and titanium atoms, (2) zirconium atoms
  • the bond energy between hafnium atom and carbon atom is larger than that of titanium atom and titanium atom. This is thought to be due to the suppression of the chain transfer reaction.
  • these compounds may be used independently and may be combined 2 or more types.
  • the molecular weight distribution of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer produced using the above catalyst depends on the polymerization time, and the molecular weight distribution becomes wider by extending the polymerization time. This is because a new polymerization active species (alkyl hafnium cation) (at least one) is generated in the polymerization system as the polymerization progresses, and the ethylene / ⁇ -olefin / nonconjugated polyene copolymer generated by this polymerization active species is generated.
  • the above phenomenon is a phenomenon peculiar to a transition metal compound in which two or more Group 14 atoms connecting the cyclopentadienyl group and the fluorenyl group are present. This is because the active species can take various conformational isomerism in a catalyst with two or more groups compared to a catalyst with one group 14 atom connecting the cyclopentadienyl group and the fluorenyl group. This is thought to be due to the fact that
  • the polymerization time is extended, two or more of the above catalysts are used, or these two methods are used. What is necessary is just to use in combination.
  • the above-described catalyst may be used and the polymerization time may be shortened and adjusted.
  • the aforementioned bridged metallocene compound can be produced by a known method, and the production method is not particularly limited.
  • a manufacturing method for example, J. Org. Organomet. Chem. 37, 561 (1998), and the method described in Japanese Patent Application Laid-Open No. 2004-175707 by the present applicant.
  • the catalyst is: (A) a bridged metallocene compound represented by the general formula [I], (B) at least one selected from (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the bridged metallocene compound (A) to form an ion pair. Species of compounds, If necessary, (C) particulate carrier, Consists of
  • (B-1) Organometallic Compound As the (B-1) organometallic compound used in the present invention, specifically, groups 1 and 2 and 12 of the periodic tables as shown in the following general formulas [V] to [VII] , Group 13 organometallic compounds are used.
  • Such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl. Examples thereof include aluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.
  • B-1b General formula: M 2 AlR a 4 ...
  • M 2 represents Li, Na or K
  • R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
  • R a and R b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 represents Mg, Zn or Cd.
  • a dialkyl compound of a Group 2 or Group 12 metal represented by the following periodic table.
  • organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum are preferable.
  • organometallic compounds (B-1) may be used alone or in combination of two or more.
  • B-2) Organoaluminum Oxy Compound
  • the organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.
  • a conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon 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 suspension of the hydrocarbon.
  • the aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.
  • organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a).
  • trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable.
  • the above organoaluminum compounds are used singly or in combination of two or more.
  • the benzene-insoluble organoaluminum oxy compound is usually 10% by weight or less, preferably 5% by weight or less, particularly preferably 2% by weight, based on 100% by weight of benzene, in terms of Al atoms.
  • the following are preferred, that is, those which are insoluble or hardly soluble in benzene.
  • organoaluminum oxy compound used in the present invention examples include an organoaluminum oxy compound containing boron represented by the following general formula [VIII].
  • R 1 represents a hydrocarbon group having 1 to 10 carbon atoms
  • R 2 to R 5 may be the same or different from each other, and have a hydrogen atom, a halogen atom, or a carbon atom number. 1 to 10 hydrocarbon groups are shown].
  • the organoaluminumoxy compound containing boron represented by the general formula [VIII] includes an alkyl boronic acid represented by the following general formula [IX], R 1 -B (OH) 2 ... [IX] [Wherein, R 1 represents the same group as in the general formula [VIII]. ] It can be produced by reacting an organoaluminum compound with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of ⁇ 80 ° C. to room temperature for 1 minute to 24 hours.
  • alkyl boronic acid represented by the general formula [IX] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boron.
  • Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid and the like.
  • methyl boronic acid n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.
  • organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a).
  • trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
  • the (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.
  • (B-3) Compound that reacts with transition metal compound to form ion pair Compound (B-3) that reacts with bridged metallocene compound (A) to form ion pair used in the present invention (hereinafter referred to as “ionization”)
  • Examples of the ionic compound include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207704, USP-5321106 and the like.
  • heteropoly compounds and isopoly compounds can also be mentioned.
  • Such ionized ionic compounds (B-3) are used singly or in combination of two or more.
  • a compound represented by BR 3 (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned.
  • R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group
  • trifluoroboron triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( and p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
  • Examples of the ionic compound include compounds represented by the following general formula [X].
  • R 1+ examples include H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.
  • R 2 to R 5 may be the same or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
  • carbonium cation examples include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.
  • ammonium cation examples include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N, 2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.
  • phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
  • R 1+ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.
  • Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
  • trialkyl-substituted ammonium salt examples include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl).
  • N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.
  • dialkylammonium salt examples include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.
  • triphenylcarbenium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl
  • Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula [XI] or [XII].
  • Et shows an ethyl group.
  • the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Metal borane anion salts such as -butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.
  • carborane compound examples include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonarborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1-carbadecarborate, tri ( n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carba Decaborate, tri (n-butyl) ammonium-1-trimethylsilyl
  • the heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
  • ionized ionic compounds the above-mentioned ionic compounds are preferable.
  • triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable. More preferred.
  • an organometallic compound (B-1) such as triisobutylaluminum
  • an organoaluminum oxy compound (B-2) such as methylaluminoxane
  • triphenyl an organometallic compound (B-3) such as carbenium tetrakis (pentafluorophenyl) borate
  • B-3 such as carbenium tetrakis (pentafluorophenyl) borate
  • the olefin polymerization catalyst used in the present invention includes the transition metal compound (A), the (B-1) organometallic compound, the (B-2) organoaluminum oxy compound, and the (B-3) ionized ionic compound.
  • a carrier (C) may be used as necessary together with at least one compound (B) selected from (C) Carrier
  • the carrier (C) used as necessary in the present invention is an inorganic compound or an organic compound, and is a granular or particulate solid.
  • the inorganic compound a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable.
  • porous oxide specifically, SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 or the like, or a composite or mixture containing these is used.
  • natural or synthetic zeolite SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 , SiO 2 —TiO 2 —MgO, etc.
  • those containing SiO 2 and / or Al 2 O 3 as main components are preferred.
  • the carrier preferably used in the present invention has a particle size of 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m, and a specific surface area of 50 to 1000 m. 2 / g, preferably in the range of 100 to 700 m 2 / g, and the pore volume is in the range of 0.3 to 3.0 cm 3 / g.
  • a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
  • 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. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.
  • Clay is usually composed mainly of clay minerals.
  • the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein can be exchanged.
  • Most clay minerals are ion-exchangeable layered compounds.
  • these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.
  • clay clay mineral, or ion-exchangeable layered compound
  • clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl 2 type, CdI 2 type, etc. It can be illustrated.
  • clays and clay minerals examples include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite
  • ion-exchangeable layered compounds include ⁇ -Zr (HAsO 4 ) 2 .H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Zr (KPO 4 ) 2 .3H 2 O, ⁇ -Ti (HPO 4 ) 2 , ⁇ -Ti (HAsO 4 ) 2 .H 2 O, ⁇ -Sn (HPO 4 ) 2 .H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Ti (HPO 4 ) 2 and crystalline acidic salts of polyvalent metals such as ⁇ -T
  • Such a clay, clay mineral or ion exchange layered compound preferably has a pore volume of not less than 0.1 cc / g having a radius of 20 mm or more as measured by a mercury intrusion method, and is preferably from 0.3 to 5 cc / g. Particularly preferred.
  • the pore volume is measured in a pore radius range of 20 to 30000 mm by a mercury intrusion method using a mercury porosimeter.
  • any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used.
  • Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.
  • the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure.
  • Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
  • an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.
  • the ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability.
  • Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars.
  • introducing another substance between the layers of the layered compound in this way is called intercalation.
  • guest compounds to be intercalated include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , metal alkoxides such as Ti (OR) 4 , Zr (OR) 4 , PO (OR) 3 , and B (OR) 3 ( R is a hydrocarbon group), metal hydroxide ions such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2+ , [Fe 3 O (OCOCH 3 ) 6 ] + Etc. These compounds are used alone or in combination of two or more.
  • these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) 4 , Al (OR) 3 , Ge (OR) 4 (R is a hydrocarbon group, etc.).
  • metal alkoxides such as Si (OR) 4 , Al (OR) 3 , Ge (OR) 4 (R is a hydrocarbon group, etc.
  • Polymers, colloidal inorganic compounds such as SiO 2, and the like can also coexist.
  • the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
  • Clay, clay mineral, and ion-exchange layered compound may be used as they are, or may be used after treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.
  • clay or clay mineral is preferable, and montmorillonite, vermiculite, hectorite, teniolite, and synthetic mica are particularly preferable.
  • Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 ⁇ m.
  • a (co) polymer produced mainly from an ⁇ -olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.
  • the olefin polymerization catalyst used in the present invention includes the bridged metallocene compound (A), (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) ionized ionic compound of the present invention.
  • a specific organic compound component (D) as described later may be included as necessary together with at least one compound (B) selected from the above, and optionally the carrier (C).
  • (D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.
  • ethylene / ⁇ -olefin and non-conjugated polyene are copolymerized in the presence of the olefin polymerization catalyst as described above to produce ethylene / ⁇ -olefin / non-conjugated polyene copolymer.
  • An ⁇ -olefin / non-conjugated polyene copolymer is obtained.
  • the ⁇ -olefin that can be used in the present invention is not particularly limited, but an ⁇ -olefin having 3 to 20 carbon atoms can be used.
  • an ⁇ -olefin having 3 to 20 carbon atoms can be used.
  • propylene 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 -Pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl -1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4
  • ⁇ -olefins having 3 to 8 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene are particularly preferable. Furthermore, these ⁇ -olefins can be used singly or in combination of two or more.
  • the ⁇ -olefin can be appropriately selected so as to be most desirable in terms of the properties of the copolymer to be produced. As an example of selection, the physical properties when the copolymer or a mixture containing the copolymer is vulcanized are desirable.
  • non-conjugated polyene that can be used in the present invention
  • a compound having two or more non-conjugated unsaturated bonds can be used without limitation, and examples thereof include the following non-conjugated cyclic polyene and non-conjugated chain polyene. It can be used alone or in combination of two or more.
  • non-conjugated cyclic polyene examples include compounds represented by the following general formula [II].
  • m is an integer of 0 to 2
  • R 17 , R 18 , R 19 and R 20 are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group or Represents a group.
  • Examples of the halogen atom represented by R 17 to R 20 in the general formula [II] include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms and a double group. And an unsaturated hydrocarbon group having one or more bonds. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.
  • Examples of the halogenated alkyl group include groups in which at least a part of the hydrogen atoms forming the alkyl group as described above are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • Examples of the cycloalkyl group include a cyclohexyl group.
  • Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
  • Examples of the unsaturated hydrocarbon group include a vinyl group and an allyl group.
  • any two of R 17 to R 20 that is, R 17 and R 18 , R 19 and R 20 , R 17 and R 19, and R 18 R 20 may be combined with R 17 and R 20 or R 18 and R 19 (in cooperation with each other) to form a monocycle or polycycle, and in this way The formed monocycle or polycycle may have a double bond.
  • R 17 and R 18 , or R 19 and R 20 may form an alkylidene group.
  • R 17 and R 19 or R 18 and R 20 may be bonded to each other to form a double bond.
  • the non-conjugated cyclic polyene represented by the general formula [II] satisfies any one or more of the following (i) to (iv): (I) a monocyclic or polycyclic ring formed by bonding any two of R 17 to R 20 to each other has a double bond (ii) with R 17 and R 18 , or R 19 and R 20 form an alkylidene group (iii) R 17 and R 19 or R 18 and R 20 are bonded to each other to form a double bond (iv) At least one of R 17 to R 20 is an unsaturated hydrocarbon group having one or more double bonds.
  • non-conjugated cyclic polyene represented by the general formula [II] include an alkylidene group having an alkylidene group formed by R 17 and R 18 or R 19 and R 20.
  • alkylidene group-containing non-conjugated cyclic polyene examples include compounds represented by the following general formula [II-I].
  • R 21 is an alkylidene group
  • R 22 and R 23 are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Alternatively, the group represents a group, and R 22 and R 23 may form an alkylidene group.
  • Specific examples of the alkylidene group represented by R 21 in the general formula [II-I] include alkylidene groups having 1 to 20 carbon atoms such as a methylene group, an ethylidene group, a propylidene group, and an isopropylidene group.
  • s is preferably 0.
  • the halogen atom represented by R 22 and R 23 are the same as those described above.
  • the hydrocarbon group include the same alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbons having 6 to 20 carbon atoms. Groups and the like.
  • alkylidene group-containing non-conjugated cyclic polyene represented by the general formula [II-I] include 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB), and 5-isopropylidene. Examples thereof include lidene-2-norbornene and the following compounds. Of these, 5-ethylidene-2-norbornene (ENB) is preferred.
  • polycyclic non-conjugated cyclic polyene examples include dicyclopentadiene (DCPD), dimethyldicyclopentadiene, and the following compounds.
  • unsaturated hydrocarbon group-containing nonconjugated cyclic polyene examples include 5-vinyl-2-norbornene (VNB) and the following compounds. Of these, 5-vinyl-2-norbornene (VNB) is preferred.
  • ring-symmetric non-conjugated cyclic polyene examples include the following compounds.
  • non-conjugated cyclic polyene represented by the general formula [II] a non-conjugated cyclic polyene having m of 0 is preferable.
  • an alkylidene group-containing non-conjugated cyclic polyene having m of 0 An alkylidene group-containing non-conjugated cyclic polyene in which s is 0 in the general formula [II-I], or a polycyclic non-conjugated cyclic polyene in which m is 0 in the general formula [II], an unsaturated hydrocarbon group in which m is 0
  • Nonconjugated cyclic polyenes are preferred. Specifically, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB) are most preferable.
  • non-conjugated chain polyene examples include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, and 1,12-tetradecadiene.
  • 3-methyl-1,4-hexadiene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4 -Hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5 -Heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5- Til-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1
  • non-conjugated chain polyenes examples include ⁇ , ⁇ -dienes such as 1,7-octadiene and 1,9-decadiene.
  • non-conjugated chain polyene for example, non-conjugated triene or tetraene represented by the following general formula [II-II] can be mentioned.
  • f is an integer of 0 to 5 (provided that when both p and q are 1, f is G is an integer of 1 to 6
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 8 is an alkyl group having 1 to 3 carbon atoms
  • R 9 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by — (CH 2 ) n —CR 10 ⁇ C (R 11 ) R 12 (
  • n is an integer of 1 to 5
  • R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 12 is an alkyl group having 1 to 3 carbon atoms).
  • R 9 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a non-conjugated triene represented by the following general formula (II-III) is preferable.
  • R 3 , R 4 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a methyl group or an ethyl group. However, R 8 and R 9 are not hydrogen atoms at the same time.
  • the non-conjugated triene represented by the general formula [II-III] is a non-conjugated triene or tetraene represented by the general formula [II-II], wherein f is 0, g is 2, p is 0, and q is 1 , R 5 and R 6 are non-conjugated trienes which are hydrogen atoms. Further, among the non-conjugated trienes represented by the above general formula [II-III], compounds in which R 7 and R 9 are both methyl groups are preferred.
  • non-conjugated triene or tetraene represented by the general formula [II-II] include the following compounds.
  • non-conjugated triene represented by the general formula [II-III] include the following compounds.
  • the non-conjugated triene or tetraene represented by the above general formula [II-II] can be produced by a known method, for example, Japanese Patent Application Laid-Open Nos. 9-235327 and 2001-114837 by the present applicant. Are described in detail.
  • the ethylene / ⁇ -olefin / non-conjugated polyene copolymer obtained by the production method of the present invention comprises (i) a structural unit derived from ethylene (ethylene unit) and (ii) an ⁇ -olefin having 3 to 20 carbon atoms.
  • the structural unit ( ⁇ -olefin unit) derived from is usually in the range of 99/1 to 1/99 in terms of molar ratio [(i) / (ii)], but is not particularly limited.
  • the structural unit derived from the non-conjugated polyene compound of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is not particularly limited, but is generally 0.1 to 50 mol%, preferably 0.2 to It is in the range of 8 mol%, more preferably 0.3-5 mol%.
  • the intrinsic viscosity [ ⁇ ] of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer obtained by the production method of the present invention measured in decalin at 135 ° C. is not particularly limited, but is usually 0.02 to 20 dl / g, Preferably, it is in the range of 0.05 to 10 dl / g.
  • the iodine value (IV) is not particularly limited, but is usually 55 g / 100 g or less, preferably 1 to 40 g / 100 g.
  • the ethylene / ⁇ -olefin / non-conjugated polyene copolymer obtained by the production method of the present invention has a content of structural units derived from ethylene of 50 mol% or more, and the B value calculated by the following formula [III] is:
  • the B value ⁇ 1.05 and the ethylene / ⁇ -olefin / nonconjugated polyene copolymer exhibiting a B value ⁇ 1.05 is an ethylene / ⁇ -olefin / nonconjugated having a B value ⁇ 1.05.
  • the alternating copolymerization property of the monomer is strong, and as a result, the ethylene average chain length is shortened, and the low temperature property, which is one of the important physical properties, exhibits good characteristics.
  • B value (c + d) / [2 ⁇ a ⁇ (e + f)] [III]
  • a is an ethylene mole fraction
  • c is an ethylene- ⁇ -olefin dyad mole fraction
  • d is an ethylene-nonconjugated polyene dyad mole fraction
  • e is an ⁇ -olefin mole fraction
  • f is Non-conjugated polyene mole fraction.
  • the B value is an index indicating the randomness of the copolymer monomer chain distribution in the copolymer
  • a, c, d, e, and f in the above formula [III] measure the 13 C-NMR spectrum, JC Randall (Macromolecules, 15, 353 (1982)), J. Ray (Macromolecules, 10, 773 (1977)) et al.
  • the length of this block chain affects the physical properties of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer.
  • the larger the B value the shorter the block chain and the better low-temperature properties. Indicates. Further, as the B value becomes smaller than 1.00, the composition distribution in the polymer chain of the ethylene / ⁇ -olefin / nonconjugated polyene copolymer becomes wider, and such a copolymer is a copolymer having a narrow composition distribution. In contrast, for example, when vulcanized, physical properties such as strength may not be sufficiently exhibited.
  • the molecular weight distribution of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer can be controlled by a single catalyst system and single-stage polymerization.
  • the molecular weight and molecular weight distribution of the copolymer are appropriately selected according to the purpose of use, but the number average molecular weight (Mn) is usually from 2,000 to 2,500,000, preferably from 5,000 to 1,500,000.
  • the molecular weight (Mw) is usually 10,000 to 5,000,000, preferably 20,000 to 3,000,000, and the molecular weight distribution (Mw / Mn) can be controlled in the range of usually 1.5 to 20, When it is desired to further improve the properties (easiness of winding of the roll, etc.), the molecular weight distribution (Mw / Mn) is preferably in the range of 3.5 to 20, more preferably 5 to 20, and further preferably 6 to 20. To be prepared. In the present invention, these molecular weights, molecular weight distributions, and the like are measured under the conditions described in the examples described later.
  • An ethylene / ⁇ -olefin / nonconjugated polyene copolymer having a B value ⁇ 1.05 can be obtained by the method for producing an ethylene / ⁇ -olefin / nonconjugated polyene copolymer of the present invention.
  • the B value of the resulting ethylene / ⁇ -olefin / nonconjugated polyene copolymer is less than 1.05. Show.
  • At least two or more of the catalyst components (A), (B), and (C) may be contacted in advance.
  • the unsupported component (B) may be added in any order as necessary.
  • the components (B) may be the same or different.
  • the solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are prepolymerized with olefin.
  • a catalyst component may be further supported on the prepolymerized solid catalyst component.
  • ethylene / ⁇ -olefin and non-conjugated polyene are copolymerized in the presence of the olefin polymerization catalyst as described above to produce ethylene / ⁇ -olefin / non-conjugated polyene copolymer.
  • An ⁇ -olefin / non-conjugated polyene copolymer is obtained.
  • any of a liquid phase polymerization method such as solution (dissolution) polymerization and suspension polymerization or a gas phase polymerization method can be used.
  • the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methylcyclopentane.
  • Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons, ethylene chloride, chlorobenzene, dichloromethane and other halogenated hydrocarbons are mentioned, and these may be used alone or in combination of two or more. Can do.
  • olefin itself can also be used as a solvent.
  • the component (A) is usually 10 ⁇ 12 to 10 ⁇ 2 mol, preferably 10 ⁇ 10 to 10 ⁇ 8 mol, per liter of reaction volume. Used in such an amount.
  • Component (B-1) generally has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of 0.01 to 50000, The amount is preferably 0.05 to 10,000.
  • Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atoms in component (B-2) to the total transition metals (M) in component (A) usually from 10 to The amount used is 50000, preferably 20 to 10,000.
  • Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 20, preferably The amount used is 1 to 15.
  • the olefin polymerization temperature using such an olefin polymerization catalyst is usually in the range of ⁇ 50 to + 200 ° C., preferably in the range of 0 to + 200 ° C., more preferably in the range of +80 to + 200 ° C.
  • a higher temperature (+ 80 ° C. or higher) is desirable from the viewpoint of productivity.
  • the polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
  • the molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. Specific examples include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.
  • the physical properties and properties of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer are measured as follows.
  • B value (c + d) / [2 ⁇ a ⁇ (e + f)] [III]
  • a is an ethylene mole fraction
  • c is an ethylene- ⁇ -olefin dyad mole fraction
  • d is an ethylene-nonconjugated polyene dyad mole fraction
  • e is an ⁇ -olefin mole fraction
  • f is Non-conjugated polyene mole fraction.
  • the catalysts used in Examples 1 to 21 and Comparative Examples 4 to 8 are disclosed in JP-A-2004-175707 and J.P. Organomet. Chem. , 37.561 (1998), and the structure of the synthesized compound is 270 MHz 1 H-NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A), etc. Were determined.
  • Example 1 Into a stainless steel (SUS) autoclave with an internal volume of 1 L sufficiently purged with nitrogen, 470 ml of n-heptane from which impurities were removed by activated alumina and 4.0 ml of 5-ethylidene-2-norbornene (hereinafter abbreviated as “ENB”) at 25 ° C. The liquid phase and gas phase were saturated for 15 minutes at an ethylene feed rate of 100 L / hr, sealed, and maintained at 80 ° C. Propylene was charged at a partial pressure of 0.30 MPa, and then increased to 0.80 MPaG with ethylene.
  • SUS stainless steel
  • 0.1 ml of a toluene solution of 1 mmol / ml triisobutylaluminum was injected, and then 0.0005 mmol / ml ethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride.
  • 0.1 ml of toluene solution was injected under pressure.
  • 0.125 ml of a toluene solution of 0.004 mmol / ml triphenylcarbenium tetrakis (pentafluorophenyl) borate was injected and polymerization reaction was performed for 15 minutes.
  • the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.
  • the obtained polymerization solution was mixed in 1 L of a methanol / acetone mixed solution (1/1 [vol / vol%]) containing 5 ml of concentrated hydrochloric acid, and then stirred for 1 hour at room temperature to deash.
  • the precipitated ethylene / propylene / ENB copolymer was collected by filtration and dried for 10 hours under the conditions of 130 ° C. and ⁇ 600 mmHg.
  • the ethylene content was 73.7 mol%
  • the propylene content was 24.2 mol%
  • the ENB content was 2.1 mol.
  • Example 1 was carried out in the same manner as Example 1 except that the catalysts and promoters listed in Table 1 were used and the propylene partial pressure and polymerization time listed in Table 1 were set. The polymerization results are shown in Table 1.
  • the obtained polymerization solution was mixed in 1 L of a methanol / acetone mixed solution (1/1 [vol / vol%]) containing 5 ml of concentrated hydrochloric acid, and then stirred for 1 hour at room temperature to deash.
  • the precipitated ethylene / propylene / ENB copolymer was collected by filtration and dried for 10 hours under the conditions of 130 ° C. and ⁇ 600 mmHg.
  • the ethylene content was 73.3 mol%
  • the propylene content was 25.3 mol%
  • the ENB content was 1.4 mol.
  • the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.
  • the obtained polymerization solution was mixed with 500 ml of water containing 5 ml of concentrated hydrochloric acid and washed. Thereafter, liquid separation was performed, and the organic layer was further washed with 500 ml of water three times, and the solvent of the obtained organic layer was distilled off.
  • the obtained ethylene / propylene / ENB copolymer was dried at 130 ° C.
  • the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.
  • the obtained polymerization solution was mixed with 500 ml of water containing 5 ml of concentrated hydrochloric acid and washed. Thereafter, liquid separation was performed, and the organic layer was further washed with 500 ml of water three times, and the solvent of the obtained organic layer was distilled off.
  • the obtained ethylene / propylene / ENB copolymer was dried at 130 ° C.
  • Example 1 In Example 1, it carried out like Example 1 except having set to the propylene partial pressure and polymerization time of Table 1 which used the catalyst and co-catalyst of Table 1 which were described. The polymerization results are shown in Table 1.
  • Example 21 In Example 1, using the catalysts and cocatalysts described in Table 2, instead of ENB 4.0 ml, which is a non-conjugated polyene, 4.0 ml ENB and 5-vinyl-2-norbornene (hereinafter abbreviated as “VNB”) The same procedure as in Example 1 was performed except that 0 ml was used and the propylene partial pressure and polymerization time described in Table 2 were set. The polymerization results are shown in Table 2.
  • the molecular weight distribution of the copolymer can be controlled by a single catalyst system and single-stage polymerization, and good polymerization activity can be achieved.

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Abstract

La présente invention concerne un procédé permettant de produire de façon efficace et économique un copolymère d'éthylène/α-oléfine/polyène non conjugué ayant d'excellentes caractéristiques. Dans le procédé de production d'un copolymère d'éthylène/α-oléfine/polyène non conjugué, de l'éthylène, une α-oléfine et un polyène non conjugué sont copolymérisés en présence d'un catalyseur de polymérisation d'oléfine qui est composé (A) d'un composé métallique de transition représenté par la formule générale [I] ci-dessous et (B) d'au moins un composé choisi parmi (B-1) des composés métalliques organiques, (B-2) des composés organiques d'oxy-aluminium et (B-3) des composés qui forment une paire ionique par réaction avec le composé métallique de transition (A). [formule chimique 1] [I] (Dans la formule [I], R1-R16 représentent respectivement un atome d'hydrogène, un atome d'halogène, un groupe hydrocarbure à substitution halogène facultative ayant 1 à 20 atomes de carbone ou similaires ; n représente un nombre entier valant 1 à 3, à condition que lorsque n vaut 1, Y1 et Y2 soient tous les deux des atomes de silicium et R1-R12 soient des atomes d'hydrogène en même temps, et que R13-R16 ne soient pas des groupes phényle en même temps, et lorsque n vaut 1, Y1 et Y2 soient tous les deux des atomes de carbone et R1-R12 soient des atomes d'hydrogène en même temps, et que R13-R16 ne soient pas des atomes d'hydrogène en même temps ; M représente Zr, Hf ou similaire ; Q représente un atome d'halogène ou similaire ; et j représente un nombre entier allant de 1 à 4.)
PCT/JP2008/072826 2007-12-21 2008-12-16 Procédé de production d'un copolymère d'éthylène/alpha-oléfine/polyène non conjugué WO2009081792A1 (fr)

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WO2013054882A1 (fr) * 2011-10-13 2013-04-18 三井化学株式会社 Copolymère à base d'éthylène, composition contenant celui-ci, et article moulé ainsi que film ou feuille constitués de ce copolymère ou de cette composition
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WO2016152711A1 (fr) * 2015-03-20 2016-09-29 三井化学株式会社 COMPOSITION D'ÉLASTOMÈRE THERMOPLASTIQUE, SON UTILISATION ET PROCÉDÉ DE PRODUCTION, COPOLYMÈRE D'ÉTHYLÈNE/α-OLÉFINE/POLYÈNE NON CONJUGUÉ ET SON UTILISATION
WO2018180362A1 (fr) 2017-03-31 2018-10-04 三井化学株式会社 Composition élastomère thermoplastique et son utilisation
KR20190137308A (ko) 2018-06-01 2019-12-11 에스케이이노베이션 주식회사 에틸렌-알파 올레핀-디엔 공중합체 및 이의 제조방법
KR20190137309A (ko) 2018-06-01 2019-12-11 에스케이이노베이션 주식회사 에틸렌-알파 올레핀-디엔 공중합체 및 에틸렌-알파 올레핀-디엔 공중합체 컴파운드
WO2020171019A1 (fr) 2019-02-22 2020-08-27 三井化学株式会社 Composition de polymère oléfinique et son corps moulé
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WO2013054882A1 (fr) * 2011-10-13 2013-04-18 三井化学株式会社 Copolymère à base d'éthylène, composition contenant celui-ci, et article moulé ainsi que film ou feuille constitués de ce copolymère ou de cette composition
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JPWO2013054882A1 (ja) * 2011-10-13 2015-03-30 三井化学株式会社 エチレン系共重合体、当該共重合体を含む組成物、及びエチレン系共重合体あるいは組成物からなる成形品並びにフィルム又はシート
US9109065B2 (en) 2011-10-13 2015-08-18 Mitsui Chemicals, Inc. Ethylene copolymer, composition including the copolymer, and shaped article and film or sheet formed from the ethylene copolymer or the composition
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KR20160103042A (ko) 2014-02-13 2016-08-31 미쓰이 가가쿠 가부시키가이샤 에틸렌·α-올레핀·비공액 폴리엔 공중합체 및 그의 용도, 및 그의 제조 방법
US10919997B2 (en) 2014-02-13 2021-02-16 Mitsui Chemicals, Inc. Ethylene α-olefin non-conjugated polyene copolymer, use thereof, and manufacturing method thereof
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