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WO1997005143A1 - Nouveaux composes a base de metaux de transition du groupe 4 - Google Patents

Nouveaux composes a base de metaux de transition du groupe 4 Download PDF

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Publication number
WO1997005143A1
WO1997005143A1 PCT/JP1996/002100 JP9602100W WO9705143A1 WO 1997005143 A1 WO1997005143 A1 WO 1997005143A1 JP 9602100 W JP9602100 W JP 9602100W WO 9705143 A1 WO9705143 A1 WO 9705143A1
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group
formula
structural unit
atom
transition metal
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Japanese (ja)
Inventor
Terumasa Yamasaki
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—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

Definitions

  • the present invention relates to a novel transition metal compound having a ligand having a hetero 6-membered ring structure, which can be advantageously used for the polymerization of an olefin, a method for producing the same, and an olefin comprising the above transition metal compound. More particularly, the present invention relates to a monovalent anion having a six-membered ring structure and containing at least one boron atom and having six ⁇ electrons.
  • a transition metal compound comprising at least one of the sex ligands and a transition metal selected from Group 4 of the Periodic Table, a method for producing the same, a catalyst for olefin polymerization comprising the above transition metal compound, and
  • the present invention relates to a method for efficiently producing homopolymers and copolymers of olefins using the same.
  • the transition metal compound of the present invention is a novel compound.
  • an olefin is polymerized using an olefin polymerization catalyst containing the transition metal compound of the present invention, a homopolymer having a narrow molecular weight distribution or a copolymer having a narrow molecular weight distribution and a uniform composition distribution can be obtained. Coalescence can be produced, and the resulting polymer has physical properties such as impact strength, stress cracking resistance, transparency, low temperature heat sealing, blocking resistance, low stickiness, and low extractables. Is excellent.
  • transition metal complexes have been used as catalysts for olefin polymerization.
  • a polymerization method used as a soluble polymerization catalyst component has been proposed.
  • a typical example of these transition metal complexes is a cyclic pentadienyl skeleton, that is, a monovalent anionic ligand having a five-membered ring structure having six ⁇ electrons consisting of carbon atoms.
  • the method of using such a complex as an olefin polymerization catalyst component is described, for example, in Japanese Patent Application Laid-Open No. 58-19309, Japanese Patent Application Laid-Open No. 60-35000. No.
  • transition metal complexes as the olefin polymerization catalyst component and using aluminoxane or a cation generator as the cocatalyst component, the molecular weight distribution of the obtained polymer is narrow, and the copolymerization reaction is suppressed. It is known that a copolymer having a high copolymerization property and a uniform composition distribution can be obtained when the reaction is carried out.
  • Periodic Table 4 Group IV transition gold containing an azaboronyl group containing boron as a heteropentacyclic ring structure with a cyclopentagenenyl skeleton and six isoelectronic ⁇ electrons as a valence anionic ligand
  • a method using a genus complex as a catalyst for polymerization of a olefin is disclosed. However, this complex also tends to have low activity.
  • the present inventors have conducted intensive studies on transition metal complexes having high olefin polymerization activity in order to solve the above-mentioned problems.
  • a new type of transition metal complex which has not been known, was obtained, and the complex was found to have high activity as an olefin polymerization catalyst, and the present invention was completed. .
  • one object of the present invention is to provide a new type of transition metal compound which has not been known so far and which can be advantageously used for olefin polymerization.
  • Another object of the present invention is to provide a method for producing the above transition metal compound.
  • Still another object of the present invention is to provide an olefin polymerization catalyst capable of producing a homopolymer having a narrow molecular weight distribution or a copolymer having a narrow molecular weight distribution and a uniform composition distribution.
  • Still another object of the present invention is to provide excellent properties such as impact strength, stress cracking resistance, transparency, low-temperature heat sealability, blocking resistance, low stickiness, and low extractability.
  • An object of the present invention is to provide a catalyst for polymerization of an olefin capable of producing a polymer having characteristics.
  • Still another object of the present invention is to provide a method for (co) polymerization of olefins using the above-mentioned polymerization catalyst to obtain the above-mentioned various effects.
  • FIG. 1 is a configuration diagram of an olefin polymerization catalyst including the transition metal compound of the present invention.
  • the transition metal compound of the present invention is used in the production of olefins together with at least one cocatalyst selected from the group consisting of an organoaluminumoxy compound and a cation generator.
  • Alkyl aluminum may be further added as a promoter component.
  • M 1 is a transition metal of Group 4A in the periodic table
  • the cyclic structural unit ( ⁇ ) represented by is a ligand
  • ⁇ 1 ⁇ ! ⁇ 6 each independently represents a hydrogen atom, C b Gen atom, a hydroxyl group, C i C ⁇ alkyl group, C 5 ⁇ C 2. Sik Roaru kill group, C 2 ⁇ C 2. Alkenyl, unsubstituted or C i to C 2. Hydrocarbon-substituted Li Le group, C 6 ⁇ C 2. ⁇ Li Lumpur group, C 7 ⁇ C 2. ⁇ Li Ruarukiru group, unsubstituted or Ji-Ji ⁇ hydrocarbon substituent A Mi amino group, C i C ⁇ sills group, or d-C 2. With an alkoxy group! ⁇ 1 ⁇ ! ⁇ Adjacent in 6
  • the two groups may form a 6-membered ring by bonding to each other.
  • L 7 is a ligand, and the cyclic structural unit ( ⁇ ) represented by the above formula (2) [however, the structural unit ( ⁇ ) and the structural unit (/ 3) may be the same or different]
  • ⁇ 1 ⁇ ! ⁇ 6 is substituted with one substituent selected from the group consisting of a bridging group or one bonding end of a bridging atom.
  • R 7 is a hydrogen atom, a halogen atom or a C i C hydrocarbon
  • the hydrogen atoms included in this hydrocarbon group include halogen atoms and the like.
  • An alkoxy group or a C 6 ⁇ C 2. May be substituted with aryloxy group o
  • Y 1 and Y 2 each independently represent a hydrogen atom, a halo gen atom, CC ⁇ alkyl group, C 6 ⁇ C 2.
  • ⁇ Li Lumpur group, c 7 to c 20 ⁇ Li Ruarukiru group. ! ⁇ . ⁇ Alkoxy group! ⁇ thio alkoxy group, C 6 -C 2 .
  • a transition metal compound represented by the following formula (1) 1. A transition metal compound represented by the following formula (1).
  • M 1 is a transition metal of Group 4A in the periodic table
  • the cyclic structural unit ( ⁇ ) represented by is a ligand
  • R: to R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C! C alkyl group, or C 5 to C 2 .
  • L 7 is a ligand and has a cyclic structure represented by the above formula (2).
  • Structural unit ( ⁇ ) (provided that the structural unit ( ⁇ ) and the structural unit ( ⁇ ) may be the same or different), a halogen atom, a ligand having an unsubstituted or substituted cyclic pentagenenyl skeleton, C i C so ⁇ Turkey alkoxy group, C i C zo Chioaruko alkoxy group, c 6 ⁇ c 2.
  • Thiophosphorous Li Ruokishi group, or a non-location ⁇ is C I ⁇ C 20 hydrocarbon substituent A Mi amino group.
  • Y 1 and Y 2 each independently represent a hydrogen atom, a hydrogen atom, a halogen atom, or a CiCs.
  • M 1 is a transition metal of Group 4A in the periodic table
  • the cyclic structural unit ( ⁇ ) represented by is a ligand
  • B is a boron atom
  • C is a carbon atom
  • N is a nitrogen atom
  • i is an integer of 1-3
  • j is an integer of 1-5.
  • R 1 to R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C! C alkyl group, or C 5 to C 2 . Cycloalkyl groups, C2-C2. Alkenyl group, unsubstituted or Ci-
  • L 7 is a ligand, and a cyclic structural unit (/ 3) represented by the above formula (2) [however, the structural unit (H) and the structural unit ( ⁇ ) may be the same or different] A halogen atom, a ligand having an unsubstituted or substituted cyclic pentagenenyl skeleton, a CC zoanoloxy group. ! ⁇ thioalkoxy group, C 6 -C 2 . Aryloxy group, C 6 -C 2 . A thioaryloxy group or a non-substituted or substituted;
  • Y 1 and Y 2 are each independently a hydrogen atom, a halogen atom, a C i C alkyl group, or C 6 -C 2 .
  • M 1 is a bond defined in the formula (1) and X 1 is a halogen atom] and a compound represented by the formula (5) Four
  • M 2 is an alkaline metal,! ⁇ ⁇ ! ⁇ And! ⁇ ⁇ ! ⁇ Is the same as defined in formula (2)] or L 7 in formula (1) is other than the cyclic structural unit (
  • MX 1 is as defined above, and L 7 is as defined in formula (1), except for the cyclic structural unit (/ 3) represented by formula (2). And a compound represented by the formula
  • each of Y 1 and Y 2 is a halogen atom
  • L 7 is a cyclic structural unit (/ 3) or a cyclic structural unit ( ⁇ )) other than a transition metal compound
  • M 2 is calculated by the above formula ( 5) and at least one halogen atom of Y 1 and Y 2 is substituted with Y 3 .
  • ⁇ 1 is a Group 4 transition metal of the Periodic Table 4
  • the cyclic structural unit (H) represented by is a ligand
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, C 1 to C 2 .
  • To (: 2. is an alkoxy group, and two adjacent groups among R 1 to R 6 may be bonded to each other to form a 6-membered ring.
  • L 7 ′ is a ligand, and a cyclic structural unit (/ 3) represented by the above formula (2) (provided that the structural unit ( ⁇ ) and the structural unit ( ⁇ ) may be the same or different)
  • R 7 is a hydrogen atom, a halogen atom, or C, to C 2 .
  • a hydrocarbon group is included in this hydrocarbon group.
  • the hydrogen atom may be substituted by a halogen atom, a CLC alkoxy group or a C 6 -C 20 aryloxy group.
  • Y 1 and Y 2 are each independently a hydrogen atom, a halogen atom,
  • M 2 is an alkali metal
  • L 1 to L 6 and R 1 to R 6 are as defined in the formula (2)
  • L 7 ′ is a ligand having a cyclopentagenenyl skeleton, the other bonding end of A is bonded to a carbon atom of the cyclopentagenenyl skeleton).
  • M 1 is as defined in formula (1 ′)
  • X 1 is a halogen atom, and is reacted with a compound represented by formula (1 ′); and its; give the transition metal compound formula (1 ') a cyclic structural unit (shed) in the L 7' is crosslinked
  • the transition metal compound obtained in the step ( ⁇ ) is converted into the compound represented by the formula (1).
  • ⁇ 3 ⁇ 2 [wherein ⁇ 3 has the same meaning as defined for ⁇ 1 and ⁇ 2 above, except for halogen atoms.
  • Micromax 2 is reacted with a compound represented by the formula (5) in Ri through defined it is in] ⁇ Substitution of one halogen atom Upsilon 3 and also 1 and less of Y 2, the manufacturing method characterized by and this encompasses and this.
  • a catalyst for polymerization of olefins comprising the transition metal compound described in 1 above.
  • the catalyst for polymerization of olefins according to the above item 4 further comprising at least one cocatalyst selected from the group consisting of an organic aluminum oxy compound and a cation generator.
  • the transition metal compound of the present invention a method for producing the same, a catalyst for polymerization of an olefin containing the compound, and a method for polymerizing the olefin using the catalyst will be specifically described.
  • polymerization is used to mean not only homopolymerization but also copolymerization, and the term “polymer” means not only homopolymer but also copolymer. It is used in the meaning including.
  • hydrocarbon group is used to include an alkyl, a cycloalkyl, an anorecenyl, an alkynyl, an arylalkynole, an aryl and an alkylaryl.
  • cyclopentagenenyl skeleton refers to a group having a c- cyclopentagenyl skeleton meaning a five-membered ring structure having six ⁇ electrons composed of a carbon atom.
  • -Pen mouth penta-genenyl group dimethyl penta-gen group, trimethyl-cyclopenta-genenyl group, tetramethyl-penta-geninole group, penta-methyl phenol group, penta-dienyl group Group, indul group, 1-methylindenyl group, 1,3-dimethylindyl group, 1,4,7—trimethylindenyl group, 4,5,6,7—tetramethylindenyl 1,2,4,5,6,7 —hexamethylindenyl group, 1,2,3,4,5,6,7_heptamethylindenyl group, tetrahydroindenyl group, 2 — Le one 4, 5, 6, 7 - Te DOO La inhibit mud Lee Ndeniru group, 1, 2, 3 - Application Benefits main Chinore one 4, 5, 6, 7 - Examples thereof include a tetrahydroindenyl group, a fluorenyl group, a 1-methylthiolenol
  • the transition metal compound of the present invention comprises a ligand having a hetero 6-membered ring structure containing boron, and a transition metal belonging to Group 4A of the Periodic Table. Characterized in that it may be bonded to any of the above ligands.
  • the above ligand having a 6-membered heterocyclic ring structure has 6 ⁇ -electrons, which are isoelectronic with the cyclopentapentaenyl group, and contains at least one boron, and is a monovalent anionic coordination. I am a child.
  • transition metal compound of the present invention wherein L 7 in the above formula (1) is a cyclic structural unit ( ⁇ ) represented by the above formula (2), specifically, the following compound Is mentioned.
  • the compounds of the present invention are not limited by these examples.
  • transition metal compound of the present invention wherein L 7 in the formula (1) is a compound other than the cyclic structural unit ( ⁇ ) represented by the formula (2), specifically, Such compounds are mentioned.
  • the compounds of the present invention are not limited by these examples.
  • the cyclopentapentagenenyl group is a methylcyclopentapentaenyl group, a dimethylcyclopentapentaenyl group, a trimethyltinolpentapentagenyl group, and a tetramethylphenol group is a tetrapentaenyl group.
  • the compound of the formula (1) in the present invention can be produced by several methods, for example, by the above-mentioned first method of the present invention.
  • This production method is carried out in a solvent that has been degassed and dried under an inert gas such as nitrogen or argon.
  • the compound represented by the formula (5) is mixed with the compound represented by the formula (3) or (4) in a solution under stirring or without stirring, and further under reflux or without reflux.
  • Solvents may be toluene or n-hexane, dichloromethane, getyl ether, tetrahydroxyfuran, n-pentane or benzene, alone or in a mixture, preferably It is one tell.
  • the reaction temperature can range from 100 ° C. to 25 ° C.
  • the reaction time can range from 1 hour to 24 hours.
  • the molar ratio of the compound of the formula (3) to the compound of the formula (5) is 1: (1 or more and less than 3); Preferably, the reaction is performed in a 1: 2 ratio.
  • the molar ratio of the compound of the formula (3), the compound of the formula (5) and the other compound of the formula (5) is 1: (0.5 or more and less than 2): (0.5).
  • the reaction is performed so that the ratio is less than 2), preferably 1: 1: 1.
  • the compound represented by the formula (4) and the compound represented by the formula (5) are reacted.
  • the reaction is carried out in a molar ratio of 1: (0.5 or more and less than 2), preferably 1: 1.
  • the compound of the above formula (5) can be produced by a known synthesis method.
  • transition metal compounds of the present invention in the case of a compound having a crosslinking group, it can be produced particularly by the following method.
  • the method is as follows: a compound represented by the formula (5) and a compound represented by the formula XAX [wherein A represents a bridge group or a bridging atom connecting the above-mentioned cyclic structural unit ( ⁇ ) and L 7 ′, and X represents a halogen atom in a] in reacting a compound I Table, the reaction mixture is L 7 'M 2 [L 7' is passing Li der Li defined in formula (1 '), M 2 in the formula (5) RM 2 [where R is an alkyl group having 1 to 10 carbon atoms, and M 2 is a compound represented by the formula (5)].
  • Equation (5) the ligand moiety one AX + L 7 'M 2
  • the reaction temperature is in the range of 20 ° C to 100 ° C, preferably 0 ° C to 80 ° C, and the reaction time is 10 minutes to 50 hours, preferably 30 minutes to 24 hours. Time range.
  • the molar ratio of the compound represented by the formula XAX to the compound represented by the formula (5) is 1: (0.5 or more and less than 2) ), favored properly 1: Ni Let 's become 1, the amount of L 7 next added is 1 amount of the compound and L 7 of the formula XAX is in a molar ratio: (less than 0.5 or 2), the preferred properly 1: 1, the amount of further compounds of the formula RM 2 added is in molar ratio of 1: (less than 1 or 3), is favored properly 1: Ni Let 's become 2, each compound reaction Add to
  • M 1 is as defined in formula (1 ′), and X 1 is a halogen atom, and is reacted with a compound represented by formula (1), and A transition metal compound in which the cyclic structural unit ( ⁇ ) in the formula (1) is crosslinked with L 7 ′ is obtained.
  • the reaction for obtaining the transition metal compound is carried out according to the method for producing the compound of the above formula (1).
  • transition metal compounds of the present invention when at least one selected from Y 1 and Y 2 is other than a halogen atom, for example, the transition metal compound of the present invention wherein Y 1 and Y 2 are a halogen atom and this produced by the this replacing Y 1 and Y 2 compounds Ru can.
  • a desired transition metal compound can be produced.
  • the transition metal compound produced by these methods can be purified by several methods. For example,
  • the filtrate is concentrated, pentane is added, the insolubles are removed by filtration, and pentane is distilled off from the filtrate, and the residue obtained is recrystallized with toluene.
  • the solvent in the filtrate of the reaction solution is distilled off, and the residue is dissolved in the minimum amount of toluene, and n-hexane is added thereto.
  • the insoluble material is filtered off, and the filtrate is cooled. How to get,
  • the solvent obtained by evaporating the solvent in the filtrate of the reaction solution is extracted with pentane or n-hexane, and the solvent is distilled off from the extract under reduced pressure.
  • the compound produced by the above method can be used as a catalyst for efficiently polymerizing olefins.
  • the catalyst for polymerization of an olefin according to the present invention may further comprise at least one cocatalyst selected from the group consisting of an organic aluminum oxy compound and a cation generator, in addition to the above-mentioned specific transition metal compound.
  • a compound conventionally known in the art can be used.
  • the organoaluminumoxy compound is an aluminoxane represented by either formula (6) or formula (7).
  • R 9 represents a hydrogen atom, a halogen atom, or an alkyl group having 0 carbon atoms, and p is an integer of 1 to 40.
  • R 9 examples include a hydrogen atom; a halogen atom such as chlorine and bromine; a methylenol group, an ethyl group, an ⁇ -propyl group, an iso-propyl group n-butyl group, an iso-butynole group, a sec-butynole group, Alkyl groups such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; or a mixture thereof, particularly a methyl group or a mixture of a methyl group and another group. Is preferred.
  • the number of repetitions p is preferably selected from the range of 2 to 40, more preferably 5 or more.
  • Known methods for synthesizing this aluminoxane for example, dissolving a trialkylaluminum in a hydrocarbon solvent, A method in which water is gradually added to the alkyl aluminum to hydrolyze it; copper sulfate hydrate or aluminum sulfate hydrate is suspended in a hydrocarbon solvent; and the hydrate crystal water in this suspension is suspended.
  • Trialkyl aluminum by contacting it with trialkyl aluminum and then slowly hydrolyze the trialkyl aluminum, or by using trialkyl aluminum against the adsorbed water of silica gel suspended in a hydrocarbon solvent. It can be produced by a method in which the trialkylaluminum is brought into contact and slowly hydrolyzed.
  • examples of the cation generator include a neutral type and an ion-to-type type
  • examples of the neutral type include an organic boron compound represented by the following formula (8).
  • R 1 . Is a hydrocarbon group having 1 to 20 carbon atoms.
  • the compound is a boron compound in which a hydrocarbon group is bonded to boron as a substituent, and any compound can be used.
  • a hydrogen atom may be replaced by a halogen atom.
  • R 1 Q examples include an alkynole group such as a methyl group, an ethyl group, an n-propyl group, an amino group, an iso-amino group, an iso-butinole group, and an n-octynole group; or a phenyl group; And aryl groups such as fluorophenyl group, tolyl group, and xylyl group. Note that the three R 1 ° may be the same or different from each other.
  • a specific example of the organoboron compound represented by the formula (8) is ⁇ o
  • Tri-Feninoleborone Tri- (Pentaf / Leo-Feninole) Boron, Tri- (2,3,4,5—Tetra-Fenoleolophenyl) Boron, Tri- (2,4) , 6—trifnorololo phenylene boron, tri (2,3—difluorophenyl) boron, tri (2—phenylolerophenyl) boron, tri (3,5—di (trifluorene) Methinole) Feninole) Boron, Tri ((4— (Trifluoromethyl) phenyl) Boron, Trimethylborone, Trietinole Boron, Tri (Trifluoromethyl) Boron And diphenylphenylphenol, di (pentaphenylolenophenyl) chloroborone, etc. Among them, tri (pentaphenyloleolophenyl) borone is particularly desirable.
  • the ion-pair type cation generator is a cation generator represented by the following formula (9).
  • [On] + is a metal cation such as a 1B group, 2B group, or 8 group metal ion; or carbonylation ⁇ beam, Shironiu arm, Okiso - ⁇ beam, sulfonyl ⁇ beam, Anmoniumu, and Ri Oniumu der such e Suhoniumu, [BR 1 1 4] - is was non-coordinating or the coordinating It is a scarce anion.
  • R 1 1 is R 1 in the formula (8). Same as.
  • An example of a preferred compound represented by the formula (9) is
  • Organoaluminumoxy compound as catalyst.
  • an alkylene represented by the formula (10) may be used as a further cocatalyst. Aluminum can coexist.
  • R 1 2 represents a hydrogen atom, a halogen group or an alkyl group having from 1 to 1 0 carbon atoms. q is 1 or 2.
  • Hydrogen atom as an example of R 1 2; chlorine, halogen atom such as bromine; methylation group, Echiru group, n - propyl group, IS 0 - propyl group n - Buchinore group, IS 0 - Buchinore group, sec —Alkyl groups such as butyl group, pentyl group, hexyl group, octyl group and decyl group, and mixtures thereof.
  • the catalyst for the polymerization of the olefin is selected from the group consisting of the main catalyst component which is the above-mentioned specific transition metal compound, the organic aluminum oxy compound and the cation generator. At least one co-catalyst component selected and a co-catalyst component which is an alkylaluminum are added and dissolved in an inert hydrocarbon solvent or an olefin medium to be subjected to polymerization. And can be prepared by using.
  • the order of addition at this time is arbitrarily selected, and the main catalyst component and the co-catalyst component may be mixed and used before the polymerization, or may be used by independently adding them to the polymerization reaction system.
  • the catalyst of the present invention may contain other components effective for olefin polymerization in addition to the above components. Further, when performing multimodal polymerization or the like to improve the polymer properties, it is possible to use a combination of two or more transition metal compounds, which are the main components of the catalyst of the present invention. It can be used in combination with other main catalyst components known in the art.
  • Transition metal compounds of the present invention for use in Orefu fin polymerization is usually 1 CI- 8 ⁇ 1 0- 1 mol / Orefu I Nmono mer capacity (Li Tsu preparative Honoré), favored by rather is 1 0 ⁇ : L CI- Used at catalyst concentrations in the range of 3 moles / olefin monomer capacity (liters).
  • the volume of the oligomer monomer generally means the volume of the raw monomer as a raw material, but when a solvent is used in slurry polymerization or solution polymerization, the volume of the oligomer monomer and the solvent
  • a gaseous olefin monomer and a diluent gas that is an inert gas such as nitrogen or argon in gas phase polymerization the volume of the olefin monomer And the volume of the dilution gas.
  • the volume of inert gas existing in the space other than the liquid phase in the polymerization vessel is excluded.
  • the ratio of the aluminum atom to the transition metal atom relative to the transition metal compound is usually 10 to 10 5 , preferably 50 to 5 XI. 0 used in the 3 range.
  • the molar ratio of the cation generator Z to the transition metal compound to the transition metal compound is usually from 0.5 to 10, preferably from 1 to 10. Used in the range of 3.
  • the ratio of the aluminum atom to the transition metal atom relative to the transition metal compound is usually 1 to 1 0 5, the preferred properly used in the range of 1 0-1 0 3.
  • the polymerization can be carried out by any polymerization method such as slurry polymerization, solution polymerization, and gas phase polymerization.
  • the main catalyst component and the cocatalyst component which are transition metal compounds
  • the carrier include inorganic oxide carriers such as silica, alumina, silica alumina, magnesia, titania, and zirconia; inorganic halide carriers such as magnesium chloride; polystyrene, and polyethylene.
  • Organic carriers such as ren and polypropylene carbon are exemplified.
  • the olefin may be prepolymerized in advance by a catalyst supported on a carrier, and then the olefin may be polymerized.
  • the amount of the obtained olefin prepolymer is 1 g per 1 g of the supported catalyst. It is preferable to apply so as to be about 100 g.
  • the main catalyst component and co-catalyst component are supported on a carrier and used for polymerization in order to improve the particle shape and bulk density of the polymer generated in slurry polymerization or gas phase polymerization. This is an effective method.
  • an inert hydrocarbon solvent or olefin itself to be used for polymerization can be used as a solvent.
  • inert hydrocarbon solvents include butane, iso-butane, pentane, hexane, octane, and decane.
  • Aliphatic hydrocarbons such as cyclohexane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, methynolecyclopentane, cyclohexane, and cyclohexane; benzene, Aromatic hydrocarbons such as toluene and xylene; and petroleum fractions such as naphtha, kerosene and light oil.
  • the polymerization temperature when slurry polymerization is carried out, is usually in the range of ⁇ 20 to 100 ° C., preferably 20 to 90 ° C. .
  • the polymerization temperature When carrying out the solution polymerization, is usually in the range of 0 to 300 ° C, preferably in the range of 100 to 250 ° C.
  • the polymerization temperature When performing the gas phase polymerization, is usually in the range of 0 to 120 ° C, preferably in the range of 20 to 100 ° C.
  • the polymerization pressure is not particularly limited, but usually, the conditions of normal pressure to 300 kg / cm 2 G, preferably normal pressure to 100 000 kg Z cmSG can be employed.
  • the polymerization can be performed in any of a batch system, a non-continuous system, and a continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.
  • the molecular weight of the obtained olefin polymer can be adjusted by changing the force of the presence of hydrogen in the polymerization reaction system or the polymerization temperature.
  • cyclic olefins having 3 to 20 carbon atoms include cyclopentene, cycloheptene, norbornane, 5-methyl-2-norbornane, tetracyclododecene, 2 — Methyl 1,4,5,8—dimethano 1,2,3,4,4a, 5,88a —octahydronaphthalene.
  • linear, branched or cyclic gens include vinylcyclohexene 1,5-hexadiene.
  • ethylene / propylene ethylene 1-butene, ethylene 1-hexene ethylene / 1-octene, ethylene / cyclopentene, ethylene / styrene, ethylene / propylene Z-ethyl It is possible to produce a copolymer having a uniform composition distribution or a low-density copolymer by performing copolymerization by combining two or more components such as lidenanolbornene.
  • transition metal compound of the present invention a commercially available product or one synthesized by a method known in the art was used as the starting transition metal compound and the alkali metal salt of the ligand precursor.
  • the molecular weight and molecular weight distribution of the homopolymer and copolymer obtained by the polymerization reaction were determined by the differential refractive index method using 150 CV gel permeation chromatography (GPC) manufactured by Waters, USA. It was measured.
  • the comonomer distribution of the copolymer obtained by the copolymerization reaction was measured using an M550 Fourier transform infrared spectrophotometer (FT-IR) manufactured by Nicole, USA, linked to the GPC. It was measured.
  • FT-IR Fourier transform infrared spectrophotometer
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • a solution obtained by adding lmmo 1 of zirconium tetrachloride to 20 ml of getyl ether is cooled to ⁇ 78 ° C., and the ligand precursor 1-methyl is added to getyl ether 10 m 1.
  • Borata benzene reamed salt (GE Harberic, eta 1., Chem. Ber., 105, 3413-3423 (1972), GE Harberich, eta Chem. Ber., 109, 2382-2388 (1976)) 2 mmo 1 was added, a solution cooled to 178 ° C. was added dropwise, and the mixture was slowly returned to room temperature and stirred for 15 hours.
  • Ligand precursors such as phenylboratabenzene sorbent (GE Harber ich, eta 1., Chem. Ber. 105, 3413-3423 (1972), GE Harbe rich, eta, Chem. Ber., 109, 238 2-2388 (1976)) 2 mlo 1, add 10 ml of getyl ether, cool to 140 ° C and add zirconium tetrachloride. 1 ml of getyl ether was added to mmo1, and the suspension cooled to 14 ° C. was slowly added dropwise, and the mixture was returned to room temperature and stirred for 15 hours.
  • phenylboratabenzene sorbent GE Harber ich, eta 1., Chem. Ber. 105, 3413-3423 (1972), GE Harbe rich, eta, Chem. Ber., 109, 238 2-2388 (1976)
  • the filtrate is concentrated to 1 O m 1, 50 m 1 of pentane is added, insoluble matter is removed by filtration, pentane is distilled off from the filtrate, and the residue is dissolved in a minimum amount of toluene necessary for dissolution.
  • the mixture was cooled to 178 ° C and recrystallized to obtain a yellow solid. Yield was 24.3%.
  • the solvent was distilled off, 50 ml of toluene was added to the residue, and insolubles were removed by filtration. Filtrate was concentrated to 10 ml, and 50 ml of pentane was added to dissolve insolubles, removed by filtration, pentane was distilled off from the filtrate, and the residue was dissolved using the minimum amount of toluene necessary for dissolution. The mixture was cooled to 178 ° C and recrystallized to obtain a yellow solid. The yield was 29.4%.
  • the filtrate was concentrated to 1 O ml, 5 O ml of pentane was added to remove insoluble matter by filtration, pentane was distilled off from the filtrate, and the residue was dissolved using the minimum amount of toluene necessary for dissolution. Recrystallization was performed by cooling to 78 ° C, and a yellow solid was obtained ( The yield was 30.1%.
  • Bis (n-butylcyclopentagenyl) zirconium magnesium chloride A ligand precursor added to a suspension of 1 mm 01 and 10 ml of getyl ether cooled to 180 ° C. 1 Lithium salt of dimethylaminoboratanebenzene (produced according to the method described in Organometa 11ics, 14, 471-480 (1995) in E. Harberich, eta) 1 Jethyl ether in 1 mmo 1 0 m 1 is added dropwise a solution cooled with an 7 8 e C was added, and the mixture was stirred for 1 2 hour to warm to room temperature and Yutsu Ku Ri.
  • the solvent was distilled off, 50 ml of toluene was added, and the insoluble matter was removed by filtration.
  • the filtrate is concentrated to 1 O ml, pentane (50 ml) is added, insoluble matter is removed by filtration, pentane is distilled off from the filtrate, and the residue is dissolved using the minimum amount of toluene necessary for dissolution.
  • the mixture was cooled to 178 ° C. and recrystallized to obtain a yellow solid. Yield was 25.2%.
  • the polymer Mw is 480, 00 Mw
  • Example 15 Polymerization was carried out in the same manner as in Example 15 except that catalyst 2 was used as the catalyst.
  • the resulting polymer weight was 59.5 g.
  • the Mw of the polymer was 511, 000, and Mw / Mn was 2.90.
  • Example 15 Polymerization was carried out in the same manner as in Example 15 except that catalyst 3 was used as the catalyst.
  • the resulting polymer weight was 54.1 g.
  • the Mw of the polymer was 541,000, and Mw / Mn was 2.80.
  • Example 19 Polymerization was carried out in the same manner as in Example 15 except that catalyst 4 was used as the catalyst. The resulting polymer weighed 49.8 g. The Mw of the polymer was 527,000, and the MwZMn was 3.01. Example 19
  • Polymerization was carried out in the same manner as in Example 19, except that catalyst 8 was used as the catalyst.
  • the obtained polymer weight was 18.3 g.
  • the Mw of the polymer was 366, 000, and Mw / Mn was 4.51.
  • Example 2 1 500 ml of dehydrated and deoxygenated toluene was placed in a 1.6 liter autoclave in which the inside was evacuated and purged with nitrogen (0.5 ml of methylaluminoxane in terms of aluminum atoms). (MMA O, manufactured by Tohoku Sozo Co., Ltd., Japan) 5 ml of toluene solution (0.5 lmol / liter in terms of aluminum atom) and 5 ml of toluene solution containing 0.5 ⁇ 1 of catalyst 9 Then 100 ml of xylene was added, the internal temperature of the autoclave was kept at 120 ° C, and ethylene was added at 20 kg / cm 2 G.
  • MMA O manufactured by Tohoku Sozo Co., Ltd., Japan
  • Mw / Mn was 3.65.
  • the density was 0.1 SS lg Z ci 3 , and it was confirmed by GPC-FTIR measurement that the hexene component was distributed almost uniformly from the low molecular weight region to the high molecular weight region.
  • Polymerization was carried out in the same manner as in Example 21 except that catalyst 10 was used as the catalyst.
  • the resulting polymer weight was 22.lg.
  • Poly Ma One Mw is 2 8 1 0, 0 0 0 , MwZM n is 2 6 6 and a density of 0. 9 2 3 g / cm 3 .
  • Example 2 3 Polymerization was carried out in the same manner as in Example 21 except that catalyst 11 was used as the catalyst. The resulting polymer weight was 19.4 g. Mw of the poly mer 3 1 1, 0 0 0, Mw / M n is 2.8 4 and a density of 0. 9 1 9 g / cm 3 .
  • Example 2 5 Polymerization was carried out in the same manner as in Example 21 except that catalyst 12 was used as the catalyst. The resulting polymer weighed 12.5 g of a polymer. Mw of the poly-mer is 4 8 0, 0 0 0, M Roh M n 3. 2 1, density of 0. 9 3 0 g Z cm 3 . Example 2 5
  • OOO MwZM n was 2.79 and the density was 0.914 g Z cm 3 .
  • Polymerization was carried out in the same manner as in Example 21 except that catalyst 2 was used as the catalyst and 1-hexene was changed to 1-octene.
  • the obtained polymer weight was 19.8 g.
  • the catalyst for olefin polymerization comprising the novel transition metal compound of the present invention is a conventional olefin polymerization catalyst comprising a transition metal compound having a ligand of a heteromultimembered ring structure having six ⁇ electrons. It shows superior catalytic activity compared to catalysts for use.
  • a homopolymer having a narrow molecular weight distribution or a copolymer having a narrow molecular weight distribution and a uniform composition distribution can be produced. Due to these catalytic performances, the resulting polymer has impact strength, stress cracking resistance, transparency, low temperature heat sealing, blocking resistance, low stickiness, low extractability, etc. Shows excellent physical properties.

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Abstract

Cette invention concerne de nouveaux composés à base de métaux de transition, lesquels composés comprennent au moins un ligand anionique monovalent ayant une structure de noyau à six membres dans laquelle sont présents six π-électrons et au moins un atome de bore, ainsi qu'un métal de transition choisi parmi les éléments du Groupe 4A de la table de classification périodique. Cette invention concerne également un procédé de préparation d'un tel composé, un catalyseur de polymérisation d'oléfines comprenant le composé à base de métaux de transition susmentionné, ainsi qu'un procédé efficace de production d'homopolymères ou de copolymères d'oléfines à l'aide dudit composé. La polymérisation d'une ou plusieurs oléfines à l'aide du catalyseur contenant ce composé à base de métaux de transition, permet d'obtenir des homopolymères ayant une répartition étroite du poids moléculaire, ou encore des copolymères ayant une répartition étroite du poids moléculaire ainsi qu'une composition uniforme. Les homopolymères et copolymères ainsi obtenus offrent d'excellentes qualités de résistance aux impacts et, à la fissuration, de transparence, et de résistance au blocage, entre autres, et possèdent une faible adhésivité ainsi qu'un faible contenu extractible.
PCT/JP1996/002100 1995-07-25 1996-07-25 Nouveaux composes a base de metaux de transition du groupe 4 Ceased WO1997005143A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997035867A1 (fr) * 1996-03-27 1997-10-02 The Dow Chemical Company Complexes metalliques heterocycliques et procedes de polymerisation d'olefines
KR100827898B1 (ko) * 2000-05-13 2008-05-07 스미스클라인비이참피이엘시이 클라불란산의 염의 정제 방법
US8158605B2 (en) 2007-09-26 2012-04-17 Mount Sinai School Of Medicine Azacytidine analogues and uses thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05507756A (ja) * 1990-06-22 1993-11-04 エクソン・ケミカル・パテンツ・インク オレフィン重合用のアルミニウムを含まないモノシクロペンタジエニルメタロセン触媒
JPH07258322A (ja) * 1994-03-23 1995-10-09 Idemitsu Kosan Co Ltd 重合用触媒及び重合体の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05507756A (ja) * 1990-06-22 1993-11-04 エクソン・ケミカル・パテンツ・インク オレフィン重合用のアルミニウムを含まないモノシクロペンタジエニルメタロセン触媒
JPH07258322A (ja) * 1994-03-23 1995-10-09 Idemitsu Kosan Co Ltd 重合用触媒及び重合体の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997035867A1 (fr) * 1996-03-27 1997-10-02 The Dow Chemical Company Complexes metalliques heterocycliques et procedes de polymerisation d'olefines
US6355818B1 (en) 1996-03-27 2002-03-12 The Dow Chemical Company Heterocyclic metal complexes and olefin polymerization process
KR100827898B1 (ko) * 2000-05-13 2008-05-07 스미스클라인비이참피이엘시이 클라불란산의 염의 정제 방법
US8158605B2 (en) 2007-09-26 2012-04-17 Mount Sinai School Of Medicine Azacytidine analogues and uses thereof

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