WO1997005143A1

WO1997005143A1 - Novel group 4 transition metal compounds

Info

Publication number: WO1997005143A1
Application number: PCT/JP1996/002100
Authority: WO
Inventors: Terumasa Yamasaki
Original assignee: Asahi Kasei Kogyo Kabushiki Kaisha
Priority date: 1995-07-25
Filing date: 1996-07-25
Publication date: 1997-02-13

Abstract

Novel transition metal compounds comprising at least one monovalent anionic ligand having a six-membered ring structure wherein six π-electrons and at least one boron atom are contained and a transition metal selected from among Group 4A elements of the periodic table; a process for the preparation of the compound; a polymerization catalyst for olefins comprising the above transition metal compound; and a process for efficiently producing olefin homopolymers or copolymers by the use of the compound. The polymerization of one or more olefins with the catalyst comprising the transition metal compound gives homopolymers having a narrow molecular weight distribution or copolymers having a narrow molecular weight distribution and a uniform composition, and the obtained homopolymers and copolymers are excellent in impact strength, stress cracking resistance, transparency, blocking resistance and so on and exhibit a low stickiness and a low extractible content.

Description

Specification

New group 4 transition metal compounds

Technical field

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 π 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. When 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.

Conventional technology

In recent years, 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 π electrons consisting of carbon atoms. Is a complex of a transition metal of Group 4 of the Periodic Table having at least one 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. 7, Japanese Patent Application Laid-Open No. 61-130303, Japanese Patent Application No. Hei 131-176, Japanese Patent Application Laid-Open No. Heisei 2-4-1303, Japanese Unexamined Patent Publication No. Hei 3 — 163 088, Japanese Unexamined Patent Publication No. Hei 5 — 194 641, Japanese Unexamined Patent Publication No. Hei 5 — 2301 23, Japanese Patent It is described in, for example, Japanese Laid-Open Publication No. 6-3060612. By using these 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.

On the other hand, a method using a Group A transition metal complex containing a ligand other than a cyclic pentagenenyl skeleton as the catalyst for polymerization of olefins has been attempted, but the polymerization activity of the cyclic pentagenenyl catalyst is high. It has not reached the point where a practical active region is obtained. Among them, Japanese Patent Application Laid-Open No. 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 π 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.

Therefore, among the Group 4 transition metal complexes containing ligands other than cyclopentagenenyl skeleton, a new type of catalyst having high activity as a catalyst for olefin polymerization has not been developed.

Summary of the Invention

Under these circumstances, the present inventors have conducted intensive studies on transition metal complexes having high olefin polymerization activity in order to solve the above-mentioned problems. As a result, surprisingly, 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. .

Accordingly, 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. In You.

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.

The above and other objects, features, and advantages of the present invention will become apparent from the following detailed description and the appended claims, which refer to the accompanying drawings.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a configuration diagram of an olefin polymerization catalyst including the transition metal compound of the present invention. As shown in the figure, 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. Can be. Alkyl aluminum may be further added as a promoter component.

Detailed description of the invention

According to the present invention, there is provided a transition metal compound represented by the following formula (1). (1)

[In equation (1):

M ¹ is a transition metal of Group 4A in the periodic table

The following equation (2)

The cyclic structural unit ( _α ) represented by is a ligand,

In equation (2),

Next formula

Is the formula B i C j! SU (where B is a boron atom, C is a carbon atom, N is a nitrogen atom, i is an integer of 1 to 3, j is an integer of 1 to 5, k is an integer from 0 to 2, where i + j + k = 6 and i — k = l), which is a 6-membered ring having six π electrons.

! ^ 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 (β) represented by the above formula (2) [however, the structural unit (α) and the structural unit (/ 3) may be the same or different] A halogen atom, a ligand having an unsubstituted or substituted cyclic pentagenenyl skeleton, a C i C alkoxy group, a ^ thioalkoxy group, and a C ₆ -C ₂ . Ary Ruokishi group, C ₆ ~ C _2. Thioaryloxy group, or unsubstituted or C! Cz. It is a hydrocarbon-substituted amino group.

The structural unit (shed) and ⁷ (except halogen atoms), but one CR ⁷ ₂ - one CR ⁷ ₂ CR ⁷ ₂ - one CR ⁷ = CR ⁷ -, one S i R ⁷ ₂ - , One S i R ⁷ ₂ S i R ⁷ _2- , one G R ⁷ ₂ —, — BR ⁷ —, — A 1 R ⁷ —, — PR ⁷ —, — P (O) R ⁷ —, — NR ⁷ —, one S 0 ₂ —, one SO—, — O—, one S—, one Ge—, — S n—, — C〇— for each of the also rather good [At that time, the cyclic structural unit _(α) and L ⁷ of the cyclic structure unit (] 3),! ^ ¹ ~! ^ ⁶ is substituted with one substituent selected from the group consisting of a bridging group or one bonding end of a bridging atom.) Where 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!チ thio alkoxy group, C ₆ -C ₂ . Aryloxy group, C ₆ -C ₂ . Chio § Li Ruokishi group, an unsubstituted or C, ~ C _2. It is a hydrocarbon-substituted amino group or an unsubstituted or C i Cso hydrocarbon-substituted phosphino group. ] Next, in order to facilitate understanding of the present invention, first, basic features and preferred embodiments of the present invention will be listed.

1. A transition metal compound represented by the following formula (1).

[In equation (1):

M ¹ is a transition metal of Group 4A in the periodic table

The following equation (2

(2)

Four The cyclic structural unit (α) represented by is a ligand,

In equation (2),

Next formula

Is the formula B i C j Nk (where 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, k Is an integer of 0 to 2, where i is 10; j + k = 6, i 1 k = l), and is a 6-membered ring having 6 π electrons.

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 . Sik b Al Kill group, C ₂ ~ C _2. Alkenyl group, unsubstituted or Ci-

C _2. Hydrocarbon-substituted silyl groups, C ₆ -C ₂ . § Li Lumpur group, C _r ~ C _2. Arylalkyl group, unsubstituted or. ! - Ji ^ hydrocarbon-substituted A Mi amino group, C! C so § sill group, or a C i ~ C _2,. Two groups adjacent to each other in R ′ to R ^{6 by} an alkoxy group may be bonded to each other to form a 6-membered ring.

L ⁷ is a ligand and has a cyclic structure represented by the above formula (2). Structural unit (β) (provided that the structural unit ( _α ) and the structural unit (β) 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. Aryloxy group, C ₆ -C 2. Thiophosphorous Li Ruokishi group, or a non-location換又is C _I ~ C ₂₀ hydrocarbon substituent A Mi amino group.

The structural units (alpha) and ⁷ (except halogen atoms), but one ^{_{^{CR 7 2 -, - CR 7}}} 2 CR 7 2 -, - CR 7 = CR 7 -, - S i R 7 2 -, One SiR ⁷ 2 SiR ⁷ ₂ —, — Ge R ⁷ ₂ —, one BR ⁷ —, — AIR ⁷ —, — PR ⁷ —, — P (O) R ⁷ —, one NR ⁷ —, — S 0 ₂ —, 1 SO—, 110-1, 1 S—, — Ge 1, 1 Sn—, 1 C〇, may be bonded via a bridging group or bridging atom selected from [in this case, for each of the cyclic structural units (alpha) and L ⁷ of the ring structure units (beta), conjoining ends of replacing one substituent selected from R i R ⁶ bridging group or bridging atom R ⁷ is a hydrogen atom, a halogen atom or CI to C ₂ . § hydrocarbon group Li, hydrogen atoms contained in the hydrocarbon group, halogen atom, C i to C _2. Alkoxy group or C ₆ -C ₂ . May be substituted with an aryloxy group.

Y ¹ and Y ² each independently represent a hydrogen atom, a hydrogen atom, a halogen atom, or a CiCs. Alkyl group, C ₆ ~ C _2. § Li Lumpur group, c ₇ ~c _2. § Li Ruarukiru group, C t~ C _2. Alkoxy group, C! C zo Alkoxy group, c ₆ ~c _2. § Li Ruokishi group, c ₆ ~c _2. It is a thioaryloxy group, an unsubstituted or C i C hydrocarbon-substituted amino group, or an unsubstituted or C ^ C ao hydrocarbon-substituted phosphino group. ]

2. A method for producing a transition metal compound represented by the following formula (1),

[In equation (1)

M ¹ is a transition metal of Group 4A in the periodic table

The following equation (2)

The cyclic structural unit (α) represented by is a ligand,

In equation (2),

Next formula

Is the formula B i C j N _k (where B is a boron atom, C is a carbon atom, N is a nitrogen atom, i is an integer of 1-3, and j is an integer of 1-5. , K is an integer of 0 to 2, where i + j + k = 6, and i−1k = l), and is a 6-membered ring having six π electrons.

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-

C _2. Hydrocarbon-substituted Li Le group, C _s ~ C _{2 Q} § Li Lumpur group, C ₇ ~ C _2. § Li one Ruarukiru group, an unsubstituted or C! C hydrocarbon substituent A Mi amino group, C i to C ₂₀ § sills group, or a C, ~ C _2. An alkoxy group, adjacent to R ¹ to R ⁶ The two groups may form a 6-membered ring by bonding to each other.

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 (β) may be the same or different] A halogen atom, a ligand having an unsubstituted or substituted cyclic pentagenenyl skeleton, a CC zoanoloxy group. !じ 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 . § Li Lumpur group, C ₇ ~ C ₂₀ § Li Ruarukiru group, C ₁ ~ C _2. An alkoxy group, a C i C thioalkoxy group, C ₆ -C ₂ . Aryloxy group, C ₆ -C ₂ . A thioaryloxy group, an unsubstituted or C i C ^ hydrocarbon-substituted amino group, or an unsubstituted or C i C ^ hydrocarbon-substituted phosphino group. ]

(a) When producing a compound in which L ⁷ is a cyclic structural unit () represented by the formula (2) in the formula (1), the compound represented by the formula (3)

M ¹ X ¹ (3)

[Wherein, 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

[In the formula, 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 (| 3) represented by formula (2) When manufacturing compounds,

Equation (4)

M ¹ X ¹ 3 L ⁷ (4)

[Wherein, 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

By reacting with the compound represented by (5), in formula (1), each of Y ¹ and Y ^{2 is} a halogen atom, and L ⁷ is a cyclic structural unit (/ 3) or a cyclic structural unit ( β)) other than a transition metal compound; and

(b) When at least one of the transition metal compounds selected from Y ¹ and Y ² in the formula (1) other than a halogen atom is desired, the transition metal compound obtained in the step (a) is converted to a compound of the formula Y ³ M ²

[Where Y ³ has the same meaning as defined above for Y ¹ and Y ² , except for the halogen atom. 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 .

A manufacturing method characterized by including the above.

3. The manufacturing method of the formula (1 ') in the represented and the formula (1') below the annular structural units (shed) and the following L ⁷ 'and the transition metal compound are crosslinked in,

(1,)

[Formula (1 ':

Μ ¹ is a Group 4 transition metal of the Periodic Table 4

The following equation (2)

The cyclic structural unit (H) represented by is a ligand,

Formula (2) Hey

Next formula

Is the formula B i C j N _k (where 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, k is an integer from 0 to 2, where

+ j + k = 6, k = l) 6-membered ring with 6 π electrons

R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, C 1 to C ₂ . Alkyl group, C ₅ ~ C _2. Sik b Al Kill group, C _₂ ~ C _2. Alkenyl group, unsubstituted or Ci-

C _2. Hydrocarbon-substituted silyl groups, C ₆ -C ₂ . Aryl group C ₇ ~ C _2. § Li one Ruarukiru group, an unsubstituted or C! C hydrocarbon substituent A Mi amino group, C, ~ C ₂ Ashiru group, or C,

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 ( _α ) and the structural unit (β) may be the same or different) A ligand having an unsubstituted or substituted cyclopentagenyl skeleton, _{C 1} to C ₂ . Alkoxy group, C! ~ C _2. Chioarukokishi group, C ₆ ~ C _2. Aryloxy group, C ₆ -C ₂ . Thioaryloxy group, or unsubstituted or. ! ^ ^ Is a hydrocarbon-substituted amino group.

The structural units (alpha) and L ^7, and the, _ CR ⁷ ₂ -,

- CR ^⁷ CR ⁷ -, one CR ^⁷ = CR ^7, one ^{_{S i R 7 2 -, -}} S i R 7 2 S i R 7 2 -, one G e R ⁷ ₂ -, one BR ⁷ -,

A 1 R ⁷ —, — PR ⁷ —, one P (0) R ⁷ —, one NR ⁷ —, one S 0 ₂ —, one SO—, one O—, one S—, one Ge—,

One S n -, when [the coupled via a bridging group or a bridging atom selected from a CO-, for each of the cyclic structural units of the cyclic structure units _(alpha) and L ⁷ (β), RLR ⁶ And one of the bonding ends of a bridging group or a bridging atom is bonded to one of the substituents selected from the above). Here, 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,

CC alkyl group, c _s ~c _2. § Li Lumpur group, c ₇ to c ₂₀ § Li Ruarukiru group, ~. ^ Alkoxy group, C t C ao Chio alkoxy group, c ₆ ~c _2. § Li Ruokishi group, c ₆ ~c _2. Thiaryloxy group, unsubstituted or CtC ^ hydrocarbon-substituted amino group, or unsubstituted or substituted. ^ A hydrocarbon-substituted phosphino group. ]

(i) Equation (5)

Wherein M ² is an alkali metal, L ¹ to L ⁶ and R ¹ to R ⁶ are as defined in the formula (2), and a compound represented by the formula XAX wherein A is as defined above. Represents a bridging group or a bridging atom for linking the cyclic structural unit (h) and L ⁷ ′, and X is a halogen atom).

⁷ ′ M ² [L ⁷ is the same as defined in equation (1 ′). Is the same as defined in formula (5)], and the reaction is further carried out. Further, RM ² [where R is an alkyl group having 1 to 10 carbon atoms, and M ² is defined in formula (5)] is reacted represented by the addition of compound a is] as described, [cyclic structural unit (α) - Α- L ⁷ '] M ² ₂ becomes formula wherein one coupling end of the a cyclic structural unit

(Shed) scale ¹ to be substituted with one substituent of R ⁶ bind, the other coupling end of A are linked by substituted with one substituent of L ⁷ '

(However, when 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).

(Y) obtained in Step (i) [cyclic structural unit ^{(α) - Α- L 7 '} ) M 2 2 becomes a compound represented by formula and formula (3)

M ¹ X ¹ (3)

Wherein 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

(iii) In the case where at least one of the transition metal compounds selected from Y ¹ and Y ² in the formula (1 ′) is other than a halogen atom, the transition metal compound obtained in the step (ϋ) is converted into the compound represented by the formula (1). Υ ³ Μ ² [wherein Υ ³ has the same meaning as defined for Υ ¹ and Υ 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] Υ 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.

4. A catalyst for polymerization of olefins comprising the transition metal compound described in 1 above.

5. 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.

6. The catalyst for olefin polymerization according to the above item 5, further comprising an alkylaluminum.

7. A method of homopolymerizing orefin or copolymerizing orefin with a comonomer other than the orefin using the catalyst according to any one of the above items 4 to 6.

8. The Orefu Lee emissions is Ri ethylene Ren der, the small-mer, wherein Eta 2 C = CHR ⁸ (wherein, R ⁸ is C 1 -C 1 8-alkyl or number of .6 to 2 0 carbon carbon And the alkyl group is linear, branched, or cyclic.), A cyclic olefin having 3 to 20 carbon atoms, and a compound having 4 to 20 carbon atoms. 8. The method according to the above item 7, wherein at least one member is selected from the group consisting of linear, branched, and cyclic gens. Hereinafter, 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.

In the present invention, the term "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.

In the present invention, the term "hydrocarbon group" is used to include an alkyl, a cycloalkyl, an anorecenyl, an alkynyl, an arylalkynole, an aryl and an alkylaryl. In the present invention, the term “cyclopentagenenyl skeleton” refers to a group having a _c- cyclopentagenyl skeleton meaning a five-membered ring structure having six π 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-methylthiolenolenyl group, and a 9-t-butylfluorenyl group.

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 π-electrons, which are isoelectronic with the cyclopentapentaenyl group, and contains at least one boron, and is a monovalent anionic coordination. I am a child.

The transition metal compound of the present invention, wherein L ⁷ in the above formula (1) is a cyclic structural unit (β) represented by the above formula (2), specifically, the following compound Is mentioned. However, the compounds of the present invention are not limited by these examples.

Bis (boratabenzene) zirconium dichloride, bis (1-methylboratabenzene) zirconium dichloride, bis (1_t butinoreboratabenzene) dinorecodium dichloride, bis (1 — Bromobora tabenzene) Zirconium dichloride, bis (1—hydroxyboratabenzene) zirconium dichloride, bis (1—methoxyboratabenzene) zirconium dichloride, bis ( 1-Methoxy 2-, 4-t-butyl-boratabenzene) Zirconium dichloride. Bis (1-methyl-1-2-acetylpropyltabenzene) zirconium chloride, bis (1-phenylborabenzene) dichloride, magnesium chloride, bis (1-methylbutylamine-boratabenzene) zirconium zirconium Dichloride, bis (2-diisopropilamino 1-2-boratanaftaren) zirconium jig mouth ride, bis (2-methoxy2-boratanaphtaren) jirconi dimolo chloride , Bis (9-mesityl-1 9—borata anthracene) zirconium dichloride, bis (dimethyltin 2-bromoboratabenzene) zirconium dichloride bis (1 Chill 4-bromoboratabenzene Zirconium chloride, ethylene bis (boratabenzene one) Ginoleconi dichloride, ethylene bis (1-methylborabenzene-41-yl) Ginoleconi dichloride, ethylene bis (1-ethylenepola tabenzene-4-yl) ) Zirconium dichloride, ethylene bis (1-dimethyl amino borotabenzene) 1-zircone Numium dichloride, dimethylborabenzene (1-yl) 4-dimethyl zirconium Dichloride dimethylboranebenzene (1-phenylboratabenzene) 4-zirconium zirconium Umm Zikroride

(1 — dimethylaminobutylabenzene) 4-zirconium dichloride, A compound in which zirconium is replaced by titanium or hafnium in the above, and

In the above, a compound in which a chloro group is replaced by a methyl group or a benzyl group is exemplified.

Similarly, the transition metal compound of the present invention, wherein L ^{7 in the} formula (1) is a compound other than the cyclic structural unit (β) represented by the formula (2), specifically, Such compounds are mentioned. However, the compounds of the present invention are not limited by these examples.

(1-methylboratabenzene) zirconium trichloride mouth, (1-phenylboratabenzene) zirconium trichloride, (1-dimethylaminoboratabenzene) zirconium trichloride, (1—methylportabenzene) (cyclopentene pentagenenyl) zirconium dichloride, (1—phenyleneboratabenzene) (cyclopentageneline) dinoreconidium chloride, (1—dimethylaluminolatabenzene) (Cyclopentagenenyl) zirconium dichloride, (1-t-butylinolebotarabenzene) (cyclopentageninole) dinorcone dimethoxy chloride, (1-methyl-2-bromoborata benzene) (cyclopentagenenyl) di / reconidium dichloride, (1 1-methyl-1-4-bromoboratabenzene (cyclopentagenenyl) zirconium dichloride, (1—methylboratabenzene) (methoxy) zirconium dichloride, (1-phenylboratabenzene) (methoxy) zirconium dichloride, (1-dimethylaminoboratabenzene)

(Methoxy) zirconium dichloride, (1—methylboratabenzene) (1—isopropyl-1,2,6—jib mouth Monafso [1,8—cd] [1,2,6] azadibo Linine) Zirconium dichloride, {1 — (boratabenzene 1 1 -yl)-2-(cyclopentagenenyl) ethane) Zirconium zinc chloride, {1 — (1 ーMethylpora tabenzene 1-4 —yl) -2 — (cyclopentageninole) ethane) dinoreco ゥジ口、、、 {{{1 1 1 1 1 1 1 1 1 1 — — — Jenyl) Ethane) Zirconium Mouth Mouth Mouth Ride, {1- (1 -dimethylaminoboratabenzene- 1-4-yl) 1 2 — (cyclopentagenenyl) ethane} Zirconium , {( Ratabenzene (11-yl) (cyclopentagenenyl) dimethylsilyl) Zirconium dichloride, {(1—methylboratabenzene 1-4-inole) (cyclopentenyl) dimethinoresylane} Zirconium music chloride, {(1 phenylboratabenzene-14-yl) (six-opening pentagel) dimethyl silane} Zirconium music chloride, {(1 dimethylalumino) -Boratabenzene (4-yl)

(Cyclopentageninole) dimethylsilylane} dinoleco dichloride, {1— (boratabenzene 1 1-inole) (t—butylamino) dimethylsilylane} zirconium dichloride Do {(1—methylbortabenzene 1-4-inole) (t—butylamino) dimethylsilylane} zirconium dichloride, {(11-phenylporabenzene-14-inole) (t-butylamino) dimethyl Tilsilane} dinochloride dimethyl chloride, ((1-dimethylaminoboratabenzene) (t-butylamino) dimethylsilylane} zirconium chlorochloride,

A compound in which zirconium is replaced with titanium or hafnium in the above,

In the above description, the cyclopentapentagenenyl group is a methylcyclopentapentaenyl group, a dimethylcyclopentapentaenyl group, a trimethyltinolpentapentagenyl group, and a tetramethylphenol group is a tetrapentaenyl group. Group, pentamethylinolecyclopentageninole group, ethynolec mouth pentageninole group, _n— propynolecicle mouth pentadienyl group, isoprovircyclocyclopentagenenyl group, n—butinolecrine pentageninole group, Indeninole, 1-Methylinolidenenyl, 1,3—Dimethylindull, 1,4,7—Trimethylindull, 4,5,6,7—Tetramethylindenyl , 1,2,4,5,6,7 —hexamethylindenyl group, 1,2,3,4,5,6,7 —heptamethylindenyl group Tetrahydridoindenyl group, 2 — methinolay 4, 5, 6, 7 — Tetrahydridoindul group, 1, 2, 3 — Trimethylyl 1, 4, 5, 6, 7 — Te Trahydridoindenyl group, fluorenyl group, 1-methylphenylololeyl group, 9-t-butylphenylolenyl Compounds substituted with

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., and the reaction time can range from 1 hour to 24 hours.

In the reaction of the compound represented by the formula (3) with the compound represented by the formula (5), 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.

In this reaction, two different types of compounds represented by the formula (5) may exist. In this case, 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.

In the reaction between the compound represented by the formula (4) and the compound represented by the formula (5), 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. For example, (A) G. E. Harbe erich, et a, Chem. Be r., 105, 3413-3423 (1972), (B) G. E. Harber i ch, et a 1.,

Chem. Ber., 109, 2382-2388 (1976), (C) A. J. Ashe, eta, J. Am. Chem. Soc., 97, 6865-6866 (1975), (D) A. J Ashe, eta 1., J. Am. Chem. Soc, 101, 7066-7067 (1979), (E) G. E. Harberich, eta 1., Organome tal lies,

12, 2891-2893 (1993), (F) GE Harberich, eta 1., Organome talies, 14, 471-480 (1995), (G) AJ Ashe, et al., Organome tall ies, 15, 387-393 (1996).

Among the 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 ( _α ) 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)]. As defined) It is reacted by addition of I the compounds, [cyclic structural unit _{^{(α) - A - L 7}} '] in M consisting formula [wherein, ¹ ~ R of one coupling end of the A cyclic structure units (alpha) bonded substituted with one substituent in the ^6, other coupling end of Α is, L ⁷ 'are bonded substituted with one substituent (but, L ^7' is consequent Ropentajeniru backbone In the case of a ligand having the above formula, the other bonding end of A is bonded to a carbon atom of the cyclopentagenenyl skeleton)).

The above reaction is shown by the following reaction formula.

Equation (5) + X A X

— Formula (5) Ligand moiety — AX + M ² X

Equation (5) the ligand moiety one AX + L ⁷ 'M ²

→ Formula (5) Ligand part _ AX— L ⁷ '10 M ² X Formula (5) Ligand part— A— L ⁷ '+ 2 RM ²

-→ [Formula (5) Ligand moiety A-L ⁷ '] M ² ₂

Ten R— R u ⁶ + R-R '

(R 'is, L ^7' has the formula (5) when ¹ one substituent in the ~ R ^6, L ⁷ 'has the formula (5) except in the case one substituent thereof)

The [cyclic structural unit (shed) Single A- L ⁷ '] in the reaction for obtaining the M ² ₂ composed compounds I Table formula, in a solvent used in the reaction, hexane, decane, Jefferies chill ether, Tetrahydrofuran, benzene, tonolen, xylene, chloro-honolem, Methylene chloride and the like can be mentioned, and such a reaction solvent is usually used in a range of 10 to 500 times by weight based on the compound. 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.

In the reaction between the compound represented by the formula XAX and the compound represented by the formula (5), 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 X ¹ ₄ (3)

Wherein 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 ( _α ) in the formula (1) is crosslinked with L ⁷ ′ is obtained.

The above reaction is shown by the following reaction formula.

[Formula (5) ligand moiety — ― — L ⁷ '] M ² ₂ + M ¹ X, → [Formula (5) ligand moiety-A — L ⁷ '] M ¹ X 2

+ 2 M ² X

The reaction for obtaining the transition metal compound is carried out according to the method for producing the compound of the above formula (1).

Among the 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.

For example, a method represented by the following reaction formula can be mentioned. The compound of the formula (1) (where Y ¹ and Y ² are halogen atoms and are represented by X) +2 Y ³ M ²

→ Compound of formula (1) (however, Y ¹ and Y ² are substituted by Y ³ ) + 2 M ² X

(Y ³ is here above Upsilon ', Upsilon have the same meaning of the ^second of defined, halogen atom are excluded. Micromax ² is a Tsuri was defined by the formula (5).). The substitution reaction can be performed under the same conditions as in the production of the precursor of the compound having a crosslinking group described above.

According to the production method of the present invention as described above, a desired transition metal compound can be produced. Note that the transition metal compound produced by these methods can be purified by several methods. For example,

A method in which the filtrate of the reaction solution is concentrated under reduced pressure, toluene is added to remove insolubles, the filtrate is concentrated and recrystallized with toluene,

After removing the insolubles by adding toluene as described above, 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. Advantageously, a compound conventionally known in the art can be used.

That is, the organoaluminumoxy compound is an aluminoxane represented by either formula (6) or formula (7).

In the formulas (6) and (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.

Examples of R ⁹ include a hydrogen atom; a halogen atom such as chlorine and bromine; a methylenol group, an ethyl group, an η-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.

On the other hand, examples of the cation generator include a neutral type and an ion-to-type type, and examples of the neutral type include an organic boron compound represented by the following formula (8).

BR ¹⁰ ₃

In equation (8), R ¹ . Is a hydrocarbon group having 1 to 20 carbon atoms. In other words, there is no particular limitation as long as the compound is a boron compound in which a hydrocarbon group is bonded to boron as a substituent, and any compound can be used. In these groups, a hydrogen atom may be replaced by a halogen atom.

Examples of R ^{1 Q} 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 ά 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] ⁺ [BR ¹ ^]-· (9) In the 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

(Pentafluorophenyl) borate, silver (I) tetra (pentafenoleolo phenylinole) borate, (I) tetra (penta) _w瞧 3 7 ™ ^6/0210 ° phnoreolophenyl) borate, mercury (Π) bis (tetra (ぺ tafnorolelophenyl) borate, palladium (Π) bis

(Tetra (pentaphnoleolopheninole) volat, Platinum (green) bis (tetra (pentaphneolelo phenyl) volate, dipheninole hydrocanoleboniumtetra (pentafrenoleolopheninole) volate, triphenylcarbine Pentra (Pentafnorole mouth) Volate, Triffeinole (vol.) Borate, Tricyclohexeneole power Bonitetra (Pentafenolero feninole) Bole (1) Triethyloxodimethyl tetra (pentafluorophenyl) volat, triethylsulfone dimethyl (pentafluorophenyl) volat, Jetylani dinitrotetra (pentafluorophenol) volat, Remethylammonium tetra (pentaphnoleno phenylene) volat, triethylammonium tetra (pentafluorophenyl) borate, tetra-η-butylammonium tetra (pentafluorophenyl) borate, trif Examples include salts of tetra (pentaphenylenolophenylinole) borate such as enylphosphonium tetra (pentafluoro phenyl) borate, etc. In the present invention, the purpose and assistance of stabilizing the catalyst during the polymerization of the olefins are described. Organoaluminumoxy compound as catalyst. For the purpose of stabilizing the cation generator and reducing the amount used, an alkylene represented by the formula (10) may be used as a further cocatalyst. Aluminum can coexist.

^{(R 1 2 3 A 1)} q · · · (1 0) (1 0) in, 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.

In the present invention, in carrying out the polymerization of the olefin, 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. Good. 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 In the case of using 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. However, in slurry polymerization or solution polymerization, the volume of inert gas existing in the space other than the liquid phase in the polymerization vessel is excluded. On the other hand, when the aluminum dimethyl compound is used as a cocatalyst, 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. When the cation generator is used as a co-catalyst, 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. Further, when the above-mentioned alkylaluminum is used, 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. In the present invention, the polymerization can be carried out by any polymerization method such as slurry polymerization, solution polymerization, and gas phase polymerization.

When slurry polymerization or gas phase polymerization is performed, one or both of the main catalyst component and the cocatalyst component, which are transition metal compounds, can be supported on a carrier. Examples of 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. There is no particular limitation on the method of supporting on a carrier, and a method conventionally known in the art can be used. The olefin may be prepolymerized in advance by a catalyst supported on a carrier, and then the olefin may be polymerized. In the prepolymerization, 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.

When performing solution polymerization / slurry polymerization, an inert hydrocarbon solvent or olefin itself to be used for polymerization can be used as a solvent. Specific examples of 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.

In the present invention, when slurry polymerization is carried out, the polymerization temperature is usually in the range of −20 to 100 ° C., preferably 20 to 90 ° C. . When carrying out the solution polymerization, the polymerization temperature is usually in the range of 0 to 300 ° C, preferably in the range of 100 to 250 ° C. When performing the gas phase polymerization, the polymerization temperature 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.

Examples of the olefin that can be polymerized by the olefin polymerization method according to the present invention include ethylene, and a compound represented by the formula H ₂ C = CHR ⁸ (wherein, R ⁸ represents a C _{1 to} C 18) Alkyl group or carbon number 6 ~ 2 In the aryl group of 0, the poly and alkyl groups are linear, branched, or cyclic. ), A cyclic olefin having 3 to 20 carbon atoms, and a linear, branched or cyclic gen having 4 to 20 carbon atoms. Examples of the compound represented by the above formula H ₂ C = CHR ⁸ include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1eicosene, styrene and the like. Examples of 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. Examples of linear, branched or cyclic gens include vinylcyclohexene 1,5-hexadiene. Also, 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. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the synthesis of the 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.

In the following examples, all solvents used were dried by a standard method. All experiments were performed in a Schlenk method or glove box under a nitrogen atmosphere. The starting compounds and the generated transition metal compounds were identified by elemental analysis, ¹ H-NMR, and mass spectrum.

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.

In addition, Mw means weight average molecular weight, and Mn means number average molecular weight.

Catalyst synthesis

Example 1 Production of bis (1-methylboratabenzene) zirconium dichloride (catalyst 1)

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. After filtering this catalyst solution, the solvent in the filtrate was removed under reduced pressure, and the residue was dissolved in a minimum amount of toluene necessary for dissolution. To this was added 2 ml of n-hexane and filtered. The insoluble matter was removed, and the filtrate was cooled to 178 ° C to obtain a yellow solid. The yield was 25.1%.

The ¹ H-NMR, mass spectrum, and elemental analysis results (% by weight) of the product are shown below.

^{.... 1 H - NMR} : 1 1 5 (6 H), 7 9 8 (4 H), 7 3 0 (4 H), 6 5 1 (2 H)

Mass spectrum: m / e = 3 4 4

Elemental analysis: C (41.9%), H (4.7%), B (6.3%), C1 (20.6%), Zr (26.5%)

Example 2

Screw (1—Feninolebola Tavenzen) Zirconium Dichlora Production of catalyst (catalyst 2)

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. Thereafter, the solvent was distilled off, 5 O ml of toluene was added, and insolubles were removed by filtration. 50 ml of pentane was added to the filtrate, and the orange insoluble material was removed by filtration.Pentane was distilled off from the filtrate, and the residue was dissolved in the minimum amount of toluene necessary for dissolution. And recrystallized to obtain a yellow solid. The yield was 13.9%.

^{..... 1 H -} NMR: 6 7 2 (2 H), 6 8 4 (2 H), 6 9 7 (2 H), 7 2 2 (2 H), 7 4 9 (2 H), 7.58 (2H), 7.70 (2H), 7.80 (2H), 7.95 (2H), 8.05 (2H)

Mass spectrum: m / e = 4 6 8

Elemental analysis: C (56.2%), H (4.4%), B (4.7%), Zr (19.5%) Example 3

Manufacture of bis (1-dimethylaminoboratabenzene) zirconium dichloride (catalyst 3)

Getyl ether 20 m 1 in zirconium tetrachloride 1 mm 0

The solution containing 1 was cooled to 178 ° C, and 10 ml of dimethyl ether was added to 10 ml of getyl ether. eta I., Organome ta I 1cs, 12, 2891-2893 (1993)) Add 2 mm 01, add dropwise the solution cooled to 178 ° C, and add The mixture was returned to room temperature and stirred for 15 hours. After filtering the solution, the solvent in the filtrate is distilled off, and the residue is dissolved in the minimum amount of toluene necessary for dissolution.N-hexane (20 ml) is added to the residue to remove insoluble materials by filtration. After removing the filtrate, the filtrate was cooled to −78 ° C. to obtain a red-brown solid in a yield of 27.2%.

The ¹ H-NMR, mass spectrum, and elemental analysis results (weight ° /.) Of the product are shown below.

^{. 1 H - NMR: 3 1} (1 2 H), 7 8 9 (4 H)

6.44 (4H), 5.76 (2H)

Mass spectrum: m / e = 4 0 2

Elemental analysis: C (41.8%), H (5.5%), B (5

4%), N (7.0%), C1 (17.6), Zr (2 2

7%)

Example 4 Manufacture of bis (1-t-butynolebotarabenzene) zirconium dichloride (catalyst 4)

To a suspension of 10 m 1 of zirconium chloride lmmo1 and 10 ml of getyl ether, cooled to 178 ° C, was added the ligand precursor 1-t-butylbutyltabenzenelithium salt (GE Herberic h , eta I., Organome ta 11 ics, 14, 471-480 (1995).) Add 10 ml of getyl ether to 2 mmo 1 and bring to 1 78 ° C. The cooled solution was added dropwise, and the mixture was returned to room temperature slowly and stirred for 15 hours. The solvent was distilled off, 50 ml of toluene was added, and insolubles were removed by filtration. 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 results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (50.0%), H (6.5%), B (5.0%), Zr (21.4%)

Example 5

Manufacture of (pentamethylcyclyl pentagenenyl) (1-methylboratabenzene) zirconium dichloride (catalyst 5)

A solution obtained by adding (pentamethyltinolechlorene genil) zirconium trichloride lmmo1 to 1 Oml of Jethyl ether is cooled to 178 ° C and coordinated with 1 Oml of Jethyl ether. 1-methylboratabenzene lithium salt (GE salt)

1 mmo 1 was added to Harber ich, eta according to the method described in Organometals, 14, 471-480 (1995)), and the solution cooled to 78 ° C was added dropwise. The mixture was returned to room temperature and stirred for 15 hours. After filtering this catalyst solution, the solvent in the filtrate was removed under reduced pressure, the residue was dissolved in the minimum amount of toluene required for dissolution, and 20 ml of n-hexane was added thereto, followed by filtration. The insoluble matter was removed, and the filtrate was cooled to 178 ° C to obtain a yellow solid. The yield was 25.1%.

The results of elemental analysis of the product are shown below.

Elemental analysis: C (49.5%), H (6.0%), B (2.8%), Zr (23.4%)

Example 6

Production of (pentamethylcyclopentagenenyl) (1—methylboratabenzene) (dimethyl) zirconium (catalyst 6)

Dissolve 0.5 mmo 1 of the compound of catalyst 5 in 10 ml of getyl ether, and add a solution of methyllithium in getyl ether (2 M) 0.6 to a solution cooled to 178 ° C. ml was dissolved in 3 ml of diethyl ether and a solution cooled to 178 ° C was added dropwise. After slowly returning to room temperature and stirring for 6 hours, the solvent was distilled off under reduced pressure, the residue was extracted with pentane, and the solvent was distilled off from the extract under reduced pressure to obtain a yellow solid. The yield was 89.4%.

The results of elemental analysis of the product are shown below. Elemental analysis: C (62.4%) H (8.6%) B (3.4%) Zr (26.0%)

Example 7

(Pentamethylsilicone pentagenil) (1-Methylinoboratabenzene) Production of titanium dichloride (Catalyst 7)

The GETS Chino Les ether 1 0 m 1 a (penta main Chirushiku Ropenta Jeniru) titanium Application Benefits click B Rye de l mm o 1, and the mixture was dissolved solution was cooled to an 7 8 ^Q C, distribution to Jefferies chill ether 1 O ml Lithium salt of 1-methylporatabenzene, a ligand precursor (manufactured by the method described in GE Harberich, eta 1., Organome tallies, 14, 471-480 (1995)) 1 mmo 1 was added, the solution cooled to 178 ° C was added dropwise, and the mixture was slowly returned to room temperature and stirred for 15 hours. After filtering this catalyst solution, the solvent in the filtrate was removed under reduced pressure, the residue was dissolved in the minimum amount of toluene necessary for dissolution, 20 μm of η-xane was added thereto, and the insoluble matter was filtered off. Then, the filtrate was cooled to 178 ° C to obtain a red-brown solid. Yield was 17.2%.

The results of elemental analysis of the product are shown below.

Elemental analysis: C (55. 9%) H (6.6%) B (3.4%) Ti (14.0%)

Example 8

Manufacture of (pentamethylcyclopentagenenyl) (1-methylinoreborata benzene) (dimethyl) titanium (catalyst 8) Dissolve 0.5 mm o 1 of the compound of catalyst 7 in 10 ml of getyl ether and cool it to 178 ° C, and add 0.6 ml of a methyl lithium getyl ether solution (2 M) to 3 ml. A solution dissolved in ml of ethyl ether and cooled to 178 ° C was added dropwise. After slowly returning to room temperature and stirring for 6 hours, the solvent was distilled off under reduced pressure, the residue was extracted with pentane, and the solvent was distilled off from the extract under reduced pressure to obtain a reddish brown solid. The yield was 88.8%.

The results of elemental analysis of the product are shown below.

Elemental analysis: C (71%), H (9.7%), B (3

4%), Ti (15.9%)

Example 9

Production of bis (1-methoxyboratabenzene) zirconium chloride (catalyst 9)

1-Bromo-1,4-dihydroboratabenzene (AJ J. Ashe, eta 1., J. Am. Chem. Soc., 97, 6865-6866 (1975)) 4 mmo 1 was added and the mixture was stirred at room temperature for 6 hours. The solution was filtered, the solvent in the filtrate was distilled off, and the residue was dissolved in 20 ml of tetrahydrofuran. The solution was cooled to 0 ° C and 5 mmo 1 of lithium-2,2,6,6-tetramethylpiperidine was added to the solution and stirred at 0 ° C for 12 hours. The solvent was distilled off, and the residue was dissolved in a small amount of toluene and filtered. Then, the solvent in the filtrate was distilled off under reduced pressure and dried to obtain a solid powder of 1-methoxyboratabenzenelithium salt. Income The rate was 90.6%.

To 1 mmo 1 of zirconium chloride, add 10 ml of ethyl ether cooled to 178 ° C, and add 10 ml of getyl ether to 2 mm o 1 of 1-methoxyboratabenzene lithium salt prepared above. The solution cooled to 178 ° C was added dropwise, and the mixture was returned to room temperature slowly and stirred for 15 hours. After the solution was filtered, the solvent in the filtrate was distilled off, and the residue was dissolved in the minimum amount of toluene required for dissolution. 20 ml of η-hexane was added, and the insoluble material was removed by filtration. The filtrate was cooled to 178 ° C. to give a yellow solid. The yield was 20.5%.

The results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (38.0%), H (4.4%), B (5.8%), O (8.6%), Zr (24.0%)

Example 10

(1 — pheninoleboratabenzene) (cyclopentagenyl) zirconium magnesium chloride (catalyst 10)

Ligand precursor, 1-phenylpora-tabenzene sorbent (G. E. Harberich, et al., Chem. Ber. 105, 3413-3423)

(1972), manufactured by GE Harberich, eta 1., Chem. Ber., 109, 23 82-2388 (1976). Cool to 78 ° C

(Cyclopentagenyl) dinoreconitrim chlorily Add 10 ml of getyl ether to Kimmo 1 and cool to 78 ° C. The solution was added dropwise. After stirring for 2 hours while cooling, the mixture was returned to room temperature and stirred for 18 hours. The solvent is distilled off and toluene

50 ml was added and insolubles were removed by filtration. The filtrate is concentrated to 10 ml, 50 ml of pentane is added, insoluble matter is removed by filtration, pentane is distilled from the filtrate, and the residue is dissolved using the minimum amount of toluene to dissolve. The solution was cooled to 178 ° C and recrystallized, and a yellow solid was obtained by filtration. The yield was 23.9%.

The results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (50.7%), H (4.0%), B (2.

6%), Zr (23.7%)

Example 1 1

(11-t-butylboratabenzene) (1,3-Dimethyl-cyclopentagenil) zirconium umdichloride (catalyst 11)

Bis (1,3-dimethylcyclopentagenenyl) zirconium dimethyl chloride 1 mm 0 1 and cooled to 178 ° C with dimethyl ether 10 m 1 Lithium salt of 1 t-butylbutylbenzene which is a precursor (manufactured by the method described in GE Herbrich, eta 1., 0 rganome ta 11ics, 14, 471-480 (1995)) 1 To the mmo 1 was added 10 m 1 of Jetlje Tenoré, a solution cooled to 178 ° C. was added dropwise, and the mixture was slowly returned to room temperature and stirred for 12 hours. 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 results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (49.4%), H (5.7%), B (2.

9%), Zr (23.6%)

Example 1 2

Manufacture of (indenyl) (1—methylportabenzene) benzophenone chloride (catalyst 12)

Screw {one black mouth (dichro mouth) (indeninole) hafnium;

To a suspension obtained by adding 10 ml of getyl ether cooled to 0.5 mm 01 to -78 ° C, 1-methylboratabenzene lithium salt (a ligand precursor) was added. GE Harberich, eta 1., Org anometallies, 14, 471-480 (1995).) Add 1 Om1 of getyl ether to lmmo1 and add 1 78 ° C. The cooled solution was added dropwise to the mixture, and the mixture was returned to room temperature slowly and stirred for 12 hours. The solvent was distilled off, 50 ml of toluene was added, and insolubles were removed by filtration. 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%.

The results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (39.3%), H (3.3%), B (2.

6%), Hf (39.4%)

Example 13

Manufacture of (n-butynolecyclopentagenenyl) (1-dimethinorea mino-boratabenzene) zirconium dichloride (catalyst 13)

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 results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (47.6%), H (6.0%), B (2. 7%), Zr (22.6%), N (3.5%)

Example 14

Production of (n-butylcyclopentagenyl) (1-dimethylamino-boratabenzene) (dimethyl) zirconium (catalyst 14)

0.5 mmol of the compound of catalyst 13 was dissolved in 10 ml of jetiethyl ether and cooled to a temperature of 78 ° C, and a solution of methyllithium in getyl ether (2 M) 0.6 was added. ml was dissolved in 3 ml of ethyl ether, and a solution cooled to 178 ° C was added dropwise. After slowly returning to room temperature and stirring for 6 hours, the solvent was distilled off under reduced pressure, the residue was extracted with pentane, and the solvent was distilled off from the extract under reduced pressure to obtain a yellow solid. The yield was 79.4%.

The results of elemental analysis (% by weight) of the product are shown below.

Elemental analysis: C (59.4%), H (8.3%), B (3.0%), Zr (25.4%), N (3.9%)

Polymerization reaction

Example 15

A 1.5-liter reactor with a vacuum degassed and purged with nitrogen was charged with 400 ml of dehydrated and deoxygenated toluene and lmmo1 of aluminum alumoxane methylalumoxane (Japan, MMA O manufactured by Tohoku Sozo Co., Ltd.) Toluene solution (0 ^: .1 m 0 1 Z liter in terms of aluminum atom) 10 m 1 and 1 μm 01 of catalyst 1 Add 5 ml of toluene solution and heat to 80 ° C. Was. Maintaining the internal temperature of the O-Tok slave to 8 0 ° C, was added ethylene Len at 8 kg / cm ² G. Polymerization was performed while maintaining the total pressure while replenishing ethylene. One hour after the start of the polymerization, the reaction system was poured into methanol-hydrochloric acid solution to terminate the reaction, the polymer was precipitated, and the obtained polymer was filtered through a filter and washed with hexane. Then, it was dried overnight under reduced pressure. The resulting polymer weight is 5

2.0 g. The polymer Mw is 480, 00 Mw

/ Mn was 3.2.2.

Example 16

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 17

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 18

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

100 ml of glass reactor with internal volume of 100 m1 fully purged with nitrogen, containing 10 ml of Tonolene solution containing catalyst 6 at Ιμπιοοΐ, and lmmo1 of triisobutylaluminum Toluene solution (10 ml) containing 10 ml of toluene solution and 2 μmo 1 of tris (pentaphnoleolopheninole) borate was added, and the mixture was stirred and mixed at 30 ° C. for 10 minutes to obtain a toluene solution. .

1.5 ml of the toluene preparation solution obtained above and 50 ml of dehydrated and deoxygenated toluene were added to a 1.6 liter autoclave which had been degassed under vacuum and purged with nitrogen. The inside of the autoclave was kept at 80 ° C., and polymerization was carried out while flowing ethylene gas at 10 kg / cm SG. One hour after the start of the polymerization, the reaction system was put into a methanol-hydrochloric acid solution to terminate the reaction. The obtained polymer was filtered through a filter, washed with hexane, and dried under reduced pressure for 24 hours. The resulting polymer weight was 22.5 g. The Mw of the polymer was 38.5,000, and the MwZMn was 4.30.

Example 20

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 μππο1 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. Ethylene One hour after the start of the polymerization, the reaction system was put into a methanolic hydrochloric acid solution to terminate the reaction, and the obtained polymer was filtered. After washing with hexane, the polymer was dried under reduced pressure for 24 hours, and the obtained polymer weighed 17.2 g. It was. Mw of the poly-mer 2 5

2, 000, 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.

Example 22

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 4

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

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-butene. The obtained polymer direct amount was 26.4 g. Polymer Mw

344, OOO MwZM n was 2.79 and the density was 0.914 g Z cm ³ .

Example 26

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. M w of port re-mer 2 9 8, 0 0 0, MwZM n is 3.3 1, and the density was 0. 9 1 0 g Z cm 3.

Example 2 7

In a glass reactor with an internal volume of 10 Om1 with sufficient nitrogen exchange In addition, 10 ml of toluene solution containing lmo 1 containing catalyst 14, 10 ml of tonolen solution containing triisobutylaluminum lmmo 1, and triphenylcanolebonium tetrakis (pentafluorophenyl) 10 ml of a toluene solution containing 2 μππιοι of borate was added, and the mixture was heated and stirred at 30 ° C for 10 minutes to obtain a toluene preparation.

To a 1.6 liter autoclave whose inside was degassed under vacuum and purged with nitrogen, 15 ml of the toluene preparation solution obtained above and 500 ml of toluene dehydrated and deoxygenated were added. Then 100 ml of 1-hexene was added. The inside of the autoclave was kept at 120 ° C, ethylene gas was supplied with 20 kgcm ² G, ethylene was supplied, and polymerization was carried out while maintaining the total pressure. One hour after the start of the polymerization, the reaction system was put into a methanol-hydrochloric acid solution to terminate the reaction. The obtained polymer was filtered through a filter, washed with hexane, and then dried under reduced pressure for 24 hours. The resulting polymer weight was 27.2. Polymer! ^ Is 2 8 4, 0 0 0, w / M n 3. 9 density was 0. 9 1 0 g Z cm 3

Industrial applicability

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 π electrons. It shows superior catalytic activity compared to catalysts for use. When an orifice is polymerized using the orefin polymerization catalyst 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 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.

Claims

The scope of the claims

-A transition metal compound represented by the following formula (1).

[In equation (1):

M ¹ is a transition metal of Group 4A in the periodic table

The following equation (2)

(2)

Four The cyclic structural unit (H) represented by is a ligand,

In equation (2),

Next formula

Is the formula B i C i Nk (where B is a boron atom, C is a carbon atom, N is a nitrogen atom, i is an integer from 1 to 3, j is an integer from 1 to 5, k Is an integer from 0 to 2, where i + j + k = 6 and i 1 k = l). This is a 6-membered ring having 6 π electrons.

1 ~! ^ ⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, C i C zo alkyl group, C ₅ ~ C _2. Sik b Al Kill group, C _₂ ~ C _2. Alkenyl, unsubstituted or C i to C _2. Hydrocarbon-substituted silyl group, C ₆ -C ₂ Q aryl group, C ₇ -C ₂ . Arylalkyl group, unsubstituted or substituted hydrocarbon group; ! ~. ^ Acyl group or C i

~ C _2. In an alkoxy group, two adjacent groups in R ¹ ! ^ ⁶ may be bonded to each other to form a six-membered ring.

L ⁷ is a ligand, and the cyclic structural unit (β) represented by the above formula (2) (where the structural unit (α) and the structural unit are the same) A halogen atom, a ligand having an unsubstituted or substituted cyclopentagenenyl skeleton, C ₁ -C ₂ . Alkoxy group! ~. Chioaruko alkoxy group, C ₆ ~ C _2. Aryloxy group, C ₆ -C ₂ . Thioaryloxy group, or unsubstituted or CiCs. It is a hydrocarbon-substituted amino group.

The structural units _(alpha) and ^seven (except halogen atoms), but one CR ⁷ ₂ - one CR ⁷ ₂ CR ⁷ ₂ - one CR ⁷ = CR ⁷ -, one S i R ⁷ ₂ - , One S i R ⁷ ₂ S i R ⁷ ₂ —, one Ge R — ' ₂ —, — BR ⁷ —, one A 1 R ⁷ —, — PR ⁷ —,-P (O) R ⁷ —, one NR ⁷ —, one S 0 ₂ —, one SO—, one O—, one S—, —G e one, —S n—, one C〇—bonded via a bridging group or a bridging atom when rather good [that even if, for each of the cyclic structure unit β of the cyclic structure unit (α) and L ^7, ¹ ~! ^ ⁶ is substituted with one substituent selected from the group consisting of a bridging group and one end of a bridging atom bonded thereto], wherein R ⁷ is a hydrogen atom, a halogen atom or a C i C ^ hydrocarbon group. The hydrogen atom included in the hydrocarbon group may be substituted with a halogen atom, a C i C alkoxy group or a C ₆ to C _2Q aryloxy group.

Y ¹ and Y ² are each independently a hydrogen atom, a halogen atom,,. ^ Alkyl group, C ₆ ~ C _2. § Li Lumpur groups, C ₇ - C ₂₀ § Li Ruarukiru group, Ji ~. ;! Alkoxy group, C ₁ -C ₂ . Chio alkoxy group, c ₆ ~c _2. Aryloxy group, C ₆ -C ₂ . Chio Aryloxy group, unsubstituted or,. ^ A hydrocarbon-substituted amino group or an unsubstituted or CiC hydrocarbon-substituted phosphoamino group. ]

[In equation (1):

M ¹ is a transition metal of Group 4A in the periodic table

The following equation (2)

The cyclic structural unit ( _α ) represented by is a ligand,

In equation (2),

Next formula

Is the formula B i C j Nk (where 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, k Is an integer from 0 to 2, where i + j + k = 6 and i — k = l). This is a six-membered ring with six π electrons.

! ^ ¹ ~! ^ ⁶ is each independently a hydrogen atom, a halogen atom, a hydroxyl group, C! Cs. Alkyl group, C ₅ ~ C _2. Sik b Al Kill group, C _₂ ~ C _2. An alkenyl group, unsubstituted or C 1, to C ₂ . Hydrocarbon-substituted silyl groups, C ₆ -C ₂ . § Li Lumpur group, C ₇ ~ C _2. § Li Ruarukiru group, an unsubstituted or C! C ao hydrocarbon substituent A Mi amino group, C i C zo Ashiru group or C i ~ C _2,. Adjacent in R i R ^{6 with} an alkoxy group The two groups may form a 6-membered ring by bonding to each other.

L ⁷ is a ligand, and a cyclic structural unit (β) represented by the above formula (2) (provided that the structural unit (α) and the structural unit (β) may be the same or different), A halogen atom, a ligand having an unsubstituted or substituted cycle-open pentagenenyl skeleton, C i to C ₂ . Alkoxy group, J! ~. ^ Chioarukokishi group, C ₆ ~ C _2. Aryloxy group, c _{6 to} c ₂ . It is a thioaryloxy group or an unsubstituted or CiCao hydrocarbon-substituted amino group.

Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a CiCso alkyl group, a C ₆ -C _{2 Q} aryl group, a C ₇ -C ₂₀ aryl alkyl group; ! - Ji ^ alkoxy group, C ₁ ~ C _2. Chio alkoxy group, c ₆ ~c _2. Aryloxy group, C ₆ -C ₂ . A thiolyloxy group, an unsubstituted or CiCao hydrocarbon-substituted amino group, or an unsubstituted or CiC ^ hydrocarbon-substituted phosphino group. ]

M ¹ X ¹ ₄ (3)

Wherein M ¹ is as defined in formula (1), and X ¹ is a halogen atom, and a compound represented by formula (5)

Wherein, M ² is alkali metal, ¹ to 1 ^ ⁶ and 1 ¹ ~ 1¾ ⁶ are passing Li defined in formula (2)], or Ca is reacted with a compound represented by the formula (1) In the case of producing a compound in which L ⁷ is other than the cyclic structural unit represented by the formula (2),

Equation (4)

M ¹ XL ⁷ (4)

[Wherein M ¹ and X ¹ are the same as defined above, and L ⁷ is the same as defined in the formula (1), but the cyclic structural unit (^) represented by the formula (2) Is excluded. And a compound represented by the formula

Reacting with the compound represented by (5), and in formula (1), each of Y ¹ and Y ² is a halogen atom, and L ⁷ is a cyclic structural unit (β) or a cyclic structural unit (β). A transition metal compound that is other than; and

(b) In the case where at least one of the transition metal compounds selected from Y ¹ and Y ² in the formula (1) other than a halogen atom is desired, the transition metal compound obtained in the step (a) is converted to a compound of the formula Y ³ M ²

[Where Y ³ has the same meaning as defined above for Y ¹ and Y ² , except for halogen atoms]. M ² is calculated by the above formula ( 5) to replace at least one halogen atom of Y ¹ and Y ² with Y ³ .

A manufacturing method characterized by including the above.

3. A manufacturing method of the formula (1 ') in the represented and the formula (1') below the annular structural units (alpha) and the following L ⁷ 'and the transition metal compound are crosslinked in,

(1,)

[In equation (1 '):

M ¹ is a transition metal of Group 4A in the periodic table

The following equation (2)

The cyclic structural unit (α) represented by is a ligand,

In equation (2),

Next formula

Is the formula B i C j Nk (where 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, k Is an integer from 0 to 2, where i + j + k = 6 and i — k = l). This is a 6-membered ring with 6 π electrons.

R i to R ⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, C _l to C ₂ . Alkyl group, C ₅ ~ C _2. Sik b Al Kill group, C _₂ ~ C _2. Alkenyl, unsubstituted or C i to C _2. Hydrocarbon-substituted silyl groups, C ₆ -C ₂ . Aryl group, C ₇ ~ C _2. Arylalkyl group, unsubstituted or. ^ Hydrocarbon substituent amino group, ~ ^ Ashiru group, or d-C _2. An alkoxy group, two adjacent groups in R ¹ to R ⁶ may be bonded to each other to form a 6-membered ring;

L ⁷ ′ is a ligand, and the cyclic structural unit (β) represented by the above formula (2) [however, the structural unit ( _α ) and the structural unit (J3) may be the same or different] A ligand having an unsubstituted or substituted cyclopentagenyl skeleton, a C i C ^ alkoxy group, d to C ₂ . Chioarukokishi group, C ₆ ~ C _2. § Riruokishi group, C ₆ ~ C _2. A thioaryloxy group or an unsubstituted or C i Cs hydrocarbon-substituted amino group.

The above structural unit (H) and L ⁷ 'are one CR ⁷ ₂

One CR ^⁷ _₂ CR ⁷ ₂ -, one CR ^⁷ = CR ⁷ -, one S i R ⁷ ₂ -, one ^{_{S i R 7 2 S i R}} 7 2 -, one G e R ⁷ ₂ -, one BR ⁷ - ,

— A 1 R ⁷ —, — PR ⁷ —, — P (0) R ⁷ —, — NR ⁷ —, one S 0 ₂ —, one SO—, one O—, one S—, one Ge—,

One S n-, when coupled [thereof via a bridging group or a bridging atom selected from a CO-, for each of the cyclic structural units (alpha) and L ⁷ of the ring structure units (beta) is! ^ ¹ ~! One substituent selected from ^ ⁶ is substituted, and one bonding end of a bridging group or a bridging atom is bonded thereto]. Here, R ⁷ is a hydrogen atom, a halogen atom, or a CiCao hydrocarbon group, which is included in the hydrocarbon group. Examples of the hydrogen atom include a halogen atom, a C i C ^ alkoxy group or C ₆ to C ₂ . It may be substituted with an aryloxy group.

Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, C! C alkyl group, C ₆ ~ C _2. § Li Lumpur groups, C ₇ - C ₂₀ § reel alkyl group, C i C alkoxy group, Ji ~ ^ Chio alkoxy group, C ₆ ~ C _2. Aryloxy group, C ₆ -C ₂ . It is a thioaryloxy group, an unsubstituted or CiC ^ hydrocarbon-substituted amino group, or an unsubstituted or CiC ^ hydrocarbon-substituted phosphino group. ]

(i) Equation (5)

[Wherein, M ² is an alkali metal, ¹ to! ^ ⁶ and R i R ⁶ are the same as defined in the formula (2)] and a compound represented by the formula XAX wherein A is a bridge linking the above-mentioned cyclic structural unit ( _α ) and L ⁷ ′ X is a halogen atom), and X is a halogen atom.

⁷ 'M ² [L ^7, the Ri Tsuri der defined in formula (1,), M Is the same as defined in formula (5)], and the reaction is further carried out. Further, formula RM ² [where R is an alkyl group having 1 to 10 carbon atoms, and M ² is defined in formula (5)] a is] a compound is reacted by adding represented Tsuri, [cyclic structural unit (α) - Α- L ⁷ '] M ² ₂ becomes formula wherein one coupling end of the a cyclic structural unit

(a) is substituted with one substituent of R i to R ⁶ and bonded, and the other bonding end of A is substituted and bonded with one substituent of L ⁷ ′

M ¹ X (3)

Wherein M ¹ is as defined in formula (1 ′), X ¹ is a halogen atom, and is reacted with a compound represented by formula (1 ′) Obtaining a transition metal compound in which the cyclic structural unit ( _α ) in (1 ′) and L ⁷ ′ are cross-linked; and

(iii) In the case where at least one transition metal compound selected from Y ¹ and Y ² in the formula (1 ′) other than a halogen atom is desired, the transition metal compound obtained in the step (ii) is converted to a compound of the formula Y ³ M ² [where Y ³ has the same meaning as defined above for Y ¹ and Y ² , except halogen atoms. M ² is the same as defined in the above formula (5)]. ^1. A production method comprising substituting at least one halogen atom of Y ² with Y ³ .

4. A catalyst for polymerization of olefins comprising the transition metal compound according to claim 1.

5. The catalyst for olefin polymerization according to claim 4, further comprising at least one cocatalyst selected from the group consisting of an organoaluminumoxy compound and a cation generator.

6. The catalyst of claim 5, further comprising an alkylaluminum.

7. A method for homopolymerizing an olefin or copolymerizing an olefin with a comonomer other than the olefin using the catalyst according to any one of claims 4 to 6.

8. The ethylene is ethylene and the comonomer is represented by the formula HaC = CHR ⁸ (wherein R ⁸ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms) And the alkyl group is linear, branched, or cyclic.), A cyclic olefin having 3 to 20 carbon atoms, and a linear chain having 4 to 20 carbon atoms. 8. The method according to claim 7, wherein at least one member selected from the group consisting of a branched or cyclic gen is used.