JPH0912619A - Novel olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel olefin polymerization catalyst containing a transition metal (e.g. Ti) compound having two kinds of ligands i.e., a cyclopetadienyl group and monovalent bidentate chelate ligand having S, Te, etc., or a combination thereof as the coordinated elements. SOLUTION: An olefin polymerization catalyst containing a transition metal compound of formula I or II is provided. In formula I or II, Cp and Cq are each a group having a cyclopentadienyl skeleton, Cq is covalently bonded to A; M is Ti, Zr or Hf; A is a cavalently crosslinkable group such as a hydrocarbon group, a silane group or oxygen; Y is a halogen, a 1-20C hydrocarbon group, an alkoxyl, an amino or the like; (m) is 1-3; (n) is 0-2; L is a bidentate chelate functional group of formula III; R is X<4> R<4> or R<4> ). In formulas III, X<1> to X<4> are each S, Se, Te or X<1> and X<4> are each O; R<2> denotes X<3> R<3> or R<3> ; and R<3> and R<4> are each a 1-20C hydrocarbon group. An olefin (co)polymer obtained by (co)polymerizing an olefin in the presence of this catalyst has excellent imapct strength, stress cracking resistance, transparency and low- temperature sealability and has low stickiness.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel olefin polymerization catalyst and a method for producing an olefin (co) polymer using the same. More specifically, the present invention includes a transition metal compound having at least two kinds of ligands, and the transition metal of the transition metal compound is Ti or Zr.
Or Hf, one ligand is selected from a group having a cyclopentadienyl skeleton, and the other ligand is O,
A catalyst for olefin polymerization, characterized in that it is selected from monovalent bidentate chelate anionic ligands in which an element selected from S, Se or Te and an element selected from S, Se or Te are coordinate atoms. . Further, the present invention relates to a production method for efficiently producing an olefin homopolymer or copolymer using the olefin polymerization catalyst.

The transition metal compound used as the catalyst for olefin polymerization of the present invention is a novel compound. By polymerizing an olefin using the olefin 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, and the resulting polymer has an impact strength. , It is excellent in physical properties such as stress cracking resistance, transparency, low temperature heat sealability, blocking resistance, low stickiness and low extract.

[0003]

2. Description of the Related Art In recent years, as a coordination polymerization catalyst for olefins, a polymerization method using a transition metal complex as a soluble polymerization catalyst component has been proposed. Representative examples of these transition metal complexes are roughly classified into two groups. One group is
It is a group of transition metal of Group 4A of the Periodic Table having two molecules of a ligand having a cyclopentadienyl skeleton, which is a group called a metallocene compound. For the method of using the metallocene compound as the olefin polymerization catalyst component, for example,
JP-A-58-19309, JP-A-60-3500
7, JP-A-61-130314, JP-A-1
It is disclosed in Japanese Patent Laid-Open No. 301706/1990, Japanese Patent Laid-Open No. 41303/1990. The other group is a complex in which a molecule having a cyclopentadienyl skeleton and a donor molecule such as an amide are bridged to form a transition metal-containing condensed ring by coordination with a transition metal of Group 4A of the periodic table. , A group called a geometrically constrained compound. Regarding the method of using the geometrically constrained compound as an olefin polymerization catalyst component, for example, JP-A-3-163088, JP-A-5-1964641, JP-A-5-230123, and JP-A-6-306 are known.
No. 121, etc.

By using these transition metal complexes as an olefin polymerization catalyst component and an aluminoxane or a cation generator as a cocatalyst component, the resulting polymer has a narrow molecular weight distribution, and when a copolymerization reaction is carried out, It is known that a copolymer having a high copolymerizability and a uniform composition distribution can be obtained.

On the other hand, a method of using a transition metal complex of Group 4A of the Periodic Table, which is not included in these two groups, as the olefin polymerization catalyst component has been attempted, but the polymerization activity is lower than that of the above-mentioned two groups of transition metal complexes and practically used. Not reach the active area.
Among them, JP-A-5-170820 discloses a periodic table group 4A having one molecule of a ligand having a cyclopentadienyl skeleton and a chelate group having two oxygen atoms as coordination atoms. Transition metal complex “CpM (R ¹ COCR ² COR
³ ) ₂ X ”(in the formula, M is Zr and Hf, Cp is a group having a cyclopentadienyl skeleton, and R ¹ ,
R ² and R ³ are hydrocarbon groups, and X is a halogen atom or SO ₃ CF ₃ . ) Is disclosed as an olefin polymerization catalyst component. Also, Journal of Chemical Society, Chemical Communications (J. Chem. Soc., Chem. Commun., 18, 1415-1417 (199
3)) has one molecule of a ligand having a cyclopentadienyl skeleton and a chelate group having two nitrogen atoms as coordinating elements, Group 4A transition metal complex “CpM ((NSi
Me ₃ ) ₂ CPh) X ₂ ″ (wherein Me is CH ₃ , Cp is C ₅ H ₅ or C ₅ Me ₅ , and X is Cl.
Or CH ₂ Ph and M is Zr, Ti or Hf. ) Is disclosed as an olefin polymerization catalyst component. However, these complex catalyst components also tend to have low activity. Therefore, there is a demand for the development of a new type of highly active catalyst for olefin polymerization which does not belong to the above two groups.

[0006]

SUMMARY OF THE INVENTION One object of the present invention is to provide a catalyst for olefin polymerization comprising a new type of transition metal complex which has not been known so far. Another object of the present invention is to provide an olefin polymerization catalyst capable of producing a homopolymer having a narrow molecular weight distribution and 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, low extractability and the like. An object of the present invention is to provide a catalyst for olefin polymerization capable of producing a coalescence. Still another object of the present invention is to provide a method for producing an olefin (co) polymer using the above-mentioned polymerization catalyst in order to obtain the above-mentioned various effects. The above objects, features and benefits of the present invention will become apparent from the detailed description below.

[0008]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted extensive studies on transition metal complexes having a high olefin polymerization activity. As a result, a new type of transition metal complex, which has not been known so far, was obtained, and it was found that the complex has a high activity as an olefin polymerization catalyst, and the present invention was completed. That is, the present invention provides a catalyst containing a new type of transition metal compound which has not been known so far and has activity as a catalyst for olefin polymerization.

The transition metal compound of the catalyst of the present invention is O,
Specific monovalent 2 in which an element selected from S, Se and Te and an element selected from S, Se and Te are two coordination atoms.
It is characterized by having a bidentate chelate anionic ligand.
By using the olefin polymerization catalyst of the present invention for the polymerization of olefins, it is possible to produce a polymer having a narrow molecular weight distribution of a homopolymer or a copolymer and a uniform composition distribution of the copolymer. Derived from these catalytic performances, the resulting polymer exhibits excellent physical properties in terms of impact strength, stress cracking resistance, transparency, low temperature heat sealability, blocking resistance, low stickiness, low extract, etc. .

According to one aspect of the present invention, there is provided an olefin polymerization catalyst containing a transition metal compound, wherein the transition metal compound is one transition metal selected from the group consisting of Ti, Zr and Hf. At least two ligands, one of the at least two ligands is a group having a cyclopentadienyl skeleton, and the remaining at least one ligand is O, S, Se or Te. The element selected from the group consisting of S and Se or the element selected from the group consisting of Te is a monovalent bidentate chelate anionic ligand that coordinates with the transition metal, and in some cases, the above An olefin polymerization catalyst is provided in which one of the remaining at least one ligand may be bonded to the above-mentioned group having a cyclopentadienyl skeleton via a bridging group.

There is also provided an olefin polymerization catalyst characterized by using these transition metal compounds and an aluminum oxy compound as a cocatalyst. Furthermore, there is provided an olefin polymerization catalyst characterized by using these transition metal compounds in combination with a cation generator as a cocatalyst. Further, according to another aspect of the present invention, there is provided a method for producing an olefin (co) polymer, which comprises polymerizing an olefin in the presence of the above catalyst.

The olefin polymerization catalyst according to the present invention and the method for producing an olefin (co) polymer using this catalyst will be specifically described below. In the present invention, the term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymer but also copolymer. Used as a meaning. Further, in the present invention, the term “hydrocarbon group” is used to include alkyl, cycloalkyl, alkenyl, alkynyl, arylalkyl, aryl and alkylaryl.

The olefin polymerization catalyst of the present invention comprises one molecule having a cyclopentadienyl skeleton, O,
Having a monovalent bidentate chelate anionic ligand having two coordination atoms of an element selected from S, Se or Te and an element selected from S, Se or Te in the range of 1, 2 or 3 molecules It includes transition metal compounds of Ti, Zr or Hf.

The ligand having a cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or two adjacent carbon atoms of a cyclopentadienyl ring are bonded to another carbon atom. And a condensed ring type cyclopentadienyl group forming a 4-, 5- or 6-membered ring. A substituted cyclopentadienyl group has 1 to 5 substituents. Examples of the substituent include 1 carbon atom
To a hydrocarbon group having 20 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. Examples of the condensed ring type cyclopentadienyl group in which two carbon atoms of the cyclopentadienyl ring are bonded to another carbon atom to form a 4-, 5- or 6-membered ring include indenyl group and tetrahydroindene group. Examples thereof include a nyl group and a fluorenyl group. These fused ring type cyclopentadienyl groups may have a substituent such as a hydrocarbon group having 1 to 20 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the group having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, i
so-propylcyclopentadienyl group, n-butylcyclopentadienyl group, iso-butylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group,
1,3-dimethylcyclopentadienyl group, 1,2,4
-Trimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, trimethylsilyltetramethylcyclopentadiene group Phenyl group, (phenyldimethylsilyl) cyclopentadienyl group, triphenylsilylcyclopentadienyl group, 1,3-di (trimethylsilyl) cyclopentadienyl group, cyclohexylcyclopentadienyl group, allylcyclopentadienyl group , Benzylcyclopentadienyl group, phenylcyclopentadienyl group, tolylcyclopentadienyl group, indenyl group, 1-methylindenyl group, 2-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group Nyl group, 2 4-dimethyl-indenyl group, 4,
7-dimethylindenyl group, 2-methyl-4-ethyl-
Indenyl group, 2-methyl-4,6-diiso-propyl-indenyl group, naphthylindenyl group, 4,5,
6,7-Tetrahydroindenyl group, 2-methyltetrahydroindenyl group, fluorenyl group, 2-methylfluorenyl group, 2,7-ditert-butylfluorenyl group and the like can be mentioned.

Examples of the transition metal compound of the present invention include a transition metal compound having a bidentate chelate ligand L and having a composition represented by the following formula [1] or [2]. _{CpM (L-R) m Y} 3-m ··· [1] (Cq-A-L) M (L-R) n Y 2-n ··· [2] Formula [1] and the formula [2] Among them, Cp is a group having a cyclopentadienyl skeleton, and Cq is a group having a cyclopentadienyl skeleton forming a covalent bond with A. M means a central metal and is a transition metal which is either Ti, Zr or Hf.

L is a bidentate chelate functional group and is represented by the following formula [3].

Embedded image In formula [3], X ¹ and X ² are each a coordination atom, and X is
¹ is O, S, Se or Te and X ² is S, Se or Te. R ² is represented by X ³ R ³ or R ³ ,
X ³ is O, S, Se or Te, and R ³ has 1 carbon atom.
To 20 unsubstituted or substituted hydrocarbon groups.

Specific examples include a methyl group, an ethyl group, and n.
-C1-C20 alkyl groups such as propyl group, iso-propyl group and tert-butyl group; C5-C20 cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl group, tolyl group, naphthyl group, etc. An aryl group having 6 to 20 carbon atoms; an benzyl group, an arylalkyl group having 7 to 20 carbon atoms such as a neophyll group; an allyl group, 2-
Examples include alkenyl groups having 2 to 20 carbon atoms such as butenyl group; alkynyl groups having 2 to 20 carbon atoms such as 2-butynyl group and 2,3-dimethyl-2-butynyl group; and the like.
In these groups, the hydrogen atom is a halogen atom and the carbon number is 1-2.
0 alkoxy group, C 6-20 aryloxy group, C 1-20 alkylsilyl group, or C 6
It may be substituted with an arylsilyl group of -20.

(L-R) in the formula [1] is a bidentate chelate ligand and is represented by the following formula [4].

Embedded image (In the formula [4], X ¹ , X ² , and R ² have the same meanings as in the formula [3].) R is represented by X ⁴ R ⁴ or R ⁴ ,
X ⁴ is O, S, Se or Te, and R ⁴ has 1 carbon atom
To 20 hydrocarbon groups. The hydrogen atom contained in this hydrocarbon group may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

M in the formula [1] is 1, 2 or 3. (Cq-A-L) in the formula [2] is a ligand in which the bidentate chelating functional group L is crosslinked with the group Cq having a cyclopentadienyl skeleton by the crosslinking group A. A is a bridging group _{^{covalent, -CR 5 2 -, - CR}} 5 2 CR 5
^{_{2 -, - CR 5 = CR}} 5 -, - SiR 5 2 -, - SiR
^{_{5 2 SiR 5 2 -, -}} GeR 5 2 -, - BR 5 -, - A
^{lR 5 -, - PR 5 -} , - P (O) R 5 2 -, - NR 5
_{-, - SO 2 -, -} SO -, - O -, - S -, - Ge
-, - Sn -, - it refers to a group or atom selected from CO-, wherein R ⁵ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom contained in this hydrocarbon group may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

N in the formula [2] is 0, 1 or 2. Y in the formulas [1] and [2] is a halogen atom,
Hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, and 6 carbon atoms
To an aryloxy group having 20 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted phosphino group having 1 to 20 carbon atoms.

Specifically, for example, halogen atoms such as fluorine, chlorine, bromine and iodine; methyl group, ethyl group, n-
An alkyl group having 1 to 20 carbon atoms such as propyl group, iso-propyl group, tert-butyl group; cyclopentyl group,
Cycloalkyl group having 5 to 20 carbon atoms such as cyclohexyl group; aryl group having 6 to 20 carbon atoms such as phenyl group, tolyl group and methoxyphenyl group; arylalkyl group having 7 to 20 carbon atoms such as benzyl group and neophyll group Allyl groups,
C2-C20 alkenyl group such as 2-butenyl group; C1-C20 methoxy group, ethoxy group, n-butoxy group and the like
20 alkoxy group; thioisopropoxy group, thiobenzylalkoxy group, etc., thioalkoxy group having 1 to 20 carbon atoms; phenoxy group, p-tolyloxy group, etc., having 6 carbon atoms
20 aryloxy group; C6-20 thioaryloxy group such as thiophenoxy group; C1-C20 hydrocarbon group-substituted amino group such as di-n-propylamino group and dibenzylamino group; diisoamyl And a phosphino group such as a phosphino group and a diphenylphosphino group having a hydrocarbon group having 1 to 20 carbon atoms;

Specific examples of the transition metal compounds represented by the above formulas [1] and [2] include the following compounds. However, the transition metal compound is not limited to these examples. (Cyclopentadienyl) tris (O, O′-dimethyldithiophosphato)
Zirconium, (cyclopentadienyl) tris (O,
O'-diethyldithiophosphato) zirconium, (n
-Butylcyclopentadienyl) tris (O, O'-diethyldithiophosphato) zirconium, (1,3-dimethylcyclopentadienyl) tris (O, O'-diethyldithiophosphato) zirconium, (pentamethylcyclo Pentadienyl) tris (O, O′-diethyldithiophosphato) zirconium, (Indenyl) tris (O, O′-diethyldithiophosphato) zirconium, (Cyclopentadienyl) tris (S, S′-dimethyltetra) Thiophosphato) zirconium, (methylcyclopentadienyl) tris (O, O′-diethyldithiophosphato) zirconium, (ethylcyclopentadienyl) tris (O, O′-diiso-propyldithiophosphato) zirconium , (N-propylcyclopentadienyl) tris (O, O′- Cyclohexyldithiophosphato) zirconium, (n-butylcyclopentadienyl) tris (O, O′-diphenyldithiophosphato) zirconium, (1,3-dimethylcyclopentadienyl) tris (O, O′-dibenzyl) Dithiophosphato) zirconium, (1,3,4-trimethylcyclopentadienyl) tris (O-ethyl-O'-phenyldithiophosphato) zirconium, (tetramethylcyclopentadienyl) tris (S, S'- Dicyclohexyltetrathiophosphato) zirconium, (pentamethylcyclopentadienyl) tris (O, O′-dimethyldiselenophosphato) zirconium, (pentamethylcyclopentadienyl) tris (O, O′-diphenylditellurphos Fat) zirconium, (trimethylsilyl) Ropentajieniru) tris (O, O'-di benzyl mono thio phosphato) zirconium, (trimethylsilyl tetramethylcyclopentadienyl) tris (S,
S'-dibenzyltetrathiophosphato) zirconium, (indenyl) tris (O, O'-diallylmonotelluphosphato) zirconium, (tetrahydroindenyl) tris (O, O'-cyclohexylmonoselenophosphato) zirconium, (Cyclopentadienyl) tris (diethyldithiophosphato) zirconium,
(1,2,4-trimethylcyclopentadienyl) tris (diphenyldithiophosphato) zirconium, (pentamethylcyclopentadienyl) tris (ethylphenyldithiophosphato) zirconium,

(Cyclopentadienyl) bis (O, O '
-Diethyldithiophosphato) chlorozirconium,
(Methylcyclopentadienyl) bis (O, O′-di-n-propyldithiophosphato) bromozirconium,
(2,7-ditert-butylfluorenyl) bis (O, O′-diethyldithiophosphato) chlorozirconium, (cyclopentadienyl) bis (O, O′-diethyldithiophosphato) benzylzirconium, ( Pentamethylcyclopentadienyl) bis (S, S′-dicyclohexyltetrathiophosphato) iso-butylzirconium, (pentamethylcyclopentadienyl)
Bis (O, O'-diiso-amylmonothiophosphato) phenoxyzirconium, (1,2,4-trimethylcyclopentadienyl) (O, O'-di-n-butyldithiophosphato) dibromozirconium, ( 1,3-Dimethylmethylcyclopentadienyl) (O, O′-dicyclohexylmonothiophosphato) dibenzylzirconium, (n-butylcyclopentadienyl) (O, O ′
-Diiso-butyldiselenophosphato) diphenylzirconium, (indenyl) (O, O'-diphenylditellurphosphato) dichlorozirconium, [(cyclopentadienyl) dimethylsilylene (O-phenyldithiophosphato)] dichloro Zirconium, [(tetramethylcyclopentadienyl) dimethylsilylene (O-
2,4,6-Trimethylphenylphosphato)] dichlorozirconium, [(3,4-dimethylcyclopentadienyl) dimethylsilylene (O-ethyldithiophosphato)] dichlorozirconium, [(3-methylcyclopentadienyl) ) Tetraethyldisilylene (O-3,5-
Xylyldithiophosphato)] dichlorozirconium,
[(Cyclopentadienyl) isopropylene (Op-
Trilyldithiophosphato)] dichlorozirconium,
[(Tetramethylcyclopentadienyl) ethylene (phenyldithiophosphato)] dimethoxyzirconium,
[(Indenyl) dimethylsilylene (O-phenyldithiophosphato)] bis (O, O′-diphenyldithiophosphato) zirconium, [(tetrahydroindenyl) isopropylene (O-n-butyldithiophosphato)] dichlorozirconium , [(Fluorenyl) dimethylborene (O-ethylphosphato)] dichlorozirconium, [(tetramethylcyclopentadienyl) dimethylsilylene (O- (2,4,6-trimethylphenyl) phosphato)] dichlorozirconium and the like. .

Further, in the zirconium compounds shown in the above examples, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be mentioned as a specific example. Transition metal compound "CpM (L-
R) _m Y _3-m "can be produced by several methods.
For example, the transition metal compound represented by the formula [5] and the formula [6]
It is a method for producing from the compound represented by the following reaction formula [7]. CpMY ₃ ... [5] (In the formula [5], M, Cp, and Y have the same meanings as in the formula [1].) Z (LR) ... [6] (Formula [6] Z is an alkali metal such as Li, Na or K,
NH ₄ or Ag. L has the same meaning as in formula [1] and is represented by formula [3]. ) CpMY ₃ + m Z (LR) → CpM (LR) _m Y _3-m + m ZY ・ ・ ・ [7] In this reaction, compound [6] is different from compound [5] when m = 1. It is efficient to use an equimolar amount, a double molar amount when m = 2, and a triple molar amount when m = 3.

Further, the transition metal compound "Cp" in which m = 3
"M (LR) ₃ " can be efficiently produced according to the following reaction formula [9] from the metallocene compound represented by the formula [8] and the compound represented by the formula [6]. Cp ₂ MY ₂ + [8] (M, Cp, and Y in formula [8] have the same meanings as in formula [1].) Cp ₂ MY ₂ + 3 Z (LR) → CpM (LR ) ₃ + CpZ + 2 ZY ... [9] In any of the reaction formulas [7] and [9], the reaction temperature is −
It is in the range of 20 ° C to 100 ° C, preferably 0 ° C to 80 ° C, and the reaction time is 0.1 to 70 hours, preferably 0.5 to
It is in the range of 50 hours. Solvents used in the reaction include aliphatic hydrocarbons such as hexane and decane; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; halogens such as carbon tetrachloride, chloroform and methylene chloride. Chemical hydrocarbons and the like can be mentioned. Of these, halogenated carbon is preferable. Such a reaction solvent is generally used in an amount within the range of 10 to 500 times the amount of the compound [5] or the compound [8].

On the other hand, a transition metal compound having a bridging ligand (Cq-A-L) "(Cq-A-L) M (L-R) n Y
_2-n "is manufactured, for example, as follows. That is, a compound having a group having a cyclopentadienyl skeleton and a bridging group of the formula [10], an organophosphorus compound represented by the formula [11],
From the compound represented by the formula [12], the organic alkali metal compound represented by the formula [13], and the transition metal compound represented by the formula [14], the following reaction formulas [15] [16] [17] [1
8] according to the above method. Cq-AW ... [10] (In the formula [10], Cq and A have the same meanings as in the formula [2]. W is a reactive group such as a halogen atom, a hydrogen atom or an alkoxy group. Z (PR ² H) ... [11] (In the formula [11], Z is an alkali metal such as Li, Na, and K, P is a phosphorus atom, and H is a hydrogen atom. R ²
Has the same meaning as in formula [3]. ) X ¹ X ² ... [12] (In the formula [12], X ¹ and X ² have the same meanings as in the formula [3] and represent a single substance or a mixture.) R ⁶ -Z ... [13] (In the formula [13], R ⁶ is a hydrocarbon group, Z is Li,
Alkali metals such as Na and K. ) MY ₄ ... [14] (In the formula [14], M and Y have the same meanings as in the formula [2].) Cq-AW + Z (PR ² H) → Cq-A-PR ² H + ZW ・ ・ ・ [15] Cq-A-PR ² H + X ¹ X ² → Cq-A-PR ² X ¹ X ² H ・ ・ ・ [16] Cq-A-PR ² X ¹ X ² H + 2 R ⁶ -Z → [Cq-AL] Z ₂ + 2 R ⁶ -H ・ ・ ・ [17] [Cq-AL] Z ₂ + MY ₄ → (Cq-AL) MY ₂ + 2 ZY ・ ・ ・[18]

When n is 1 or 2 in the formula [2], for example, (Cq-AL) MY ₂ obtained by the reaction formula [18] is prepared according to the reaction formula [19]. Z
A method of producing each by reacting (LR) in an equimolar amount or a double molar amount can be mentioned. Formula Z (L-
R) has the same meaning as in the above formula [6]. _{(Cq-AL) MY 2 +} n Z (LR) → (Cq-AL) M (LR) n Y 2-n + ZY ··· [19] Reaction Scheme [15], [16], [17], Regarding the reaction conditions of [18] and [19], in each case, the reaction temperature is −20 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C., and the reaction time is 0.1 to 70 hours. It is preferably in the range of 0.5 to 50 hours. Solvents used in the reaction include aliphatic hydrocarbons such as hexane and decane; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; halogens such as carbon tetrachloride, chloroform and methylene chloride. Chemical hydrocarbons; alcohols such as methanol and ethanol; water and the like. Among these, reaction formulas [15] and [1
In [7] and [18], ethers are preferable, and the reaction formula [1
In [6], aromatic hydrocarbons are preferable, and the reaction formula [19]
For, halogenated hydrocarbons are preferred. Such a reaction solvent is usually used in the range of 10 to 500 times by weight of the compound.

Further, the bridging group A is a substituted methylene group CR ⁷ ₂
A transition metal compound having a bridging ligand of "(Cq-A
-L) M (L-R) n Y 2-n "can be prepared in the following way. That is, to produce a ^{"(Cq-A-PR 2 H} ) " in accordance with the following reaction formula from a compound represented by the formula [20] with the compound [11] [21]. Next, the obtained ^{"(Cq-A-PR 2 H} ) " Reaction Scheme using [1
6], [17], [18] and further [19].

[0030]

Embedded image (In the formula [20], R ⁷ is a hydrogen atom; a methyl group, tert.
-Represents a hydrocarbon group having 1 to 20 carbon atoms such as a butyl group, a cyclohexyl group and a phenyl group, and two R ^{7 s} may be the same or different. R ⁸ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, or two adjacent carbon atoms bonded to another carbon atom to form 4, 5 or It is a group forming a 6-membered ring. The four R ⁸ may be the same or different. )

[0031]

Embedded image

Regarding the reaction conditions of the reaction formula [21], the reaction temperature is -20 ° C to 100 ° C, preferably 0 ° C to 80 ° C.
And the reaction time is 0.1 to 20 hours, preferably 0.5 to 10 hours. Solvents used in the reaction include aliphatic hydrocarbons such as hexane and decane; ethers such as diethyl ether and tetrahydrofuran;
Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride are used. Among these, ethers are preferable, and usually 10 to 5 by weight relative to the compound [20].
It is used in the range of 00 times.

The desired transition metal compound can be produced by the above-mentioned production method and the like. The transition metal compound produced by these production methods can be purified by isolating the filtrate obtained by filtering the reaction solution under reduced pressure, recrystallizing and drying under reduced pressure. The olefin polymerization catalyst according to the present invention advantageously contains, in addition to the above-mentioned specific transition metal compound, at least one co-catalyst selected from the group consisting of an aluminum oxy compound and a cation generator. As the catalyst, a compound known in the art can be used.

That is, the aluminum oxy compound is an aluminoxane represented by any one of the general formula [22] and the general formula [23].

[Chemical 6]

[0035]

Embedded image (In the formulas [22] and [23], R ⁹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms,
p is an integer of 1-40. )

Examples of R ⁹ are hydrogen atom; halogen atom such as chlorine and bromine; methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl. Examples thereof include groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, and other alkyl groups; or mixtures thereof, with a methyl group or a mixture of methyl groups and other groups being particularly preferred. The repeating number p is preferably selected from the range of 2 to 40, and more preferably 5 or more.

A known method for synthesizing this aluminoxane is, for example, a method in which a trialkylaluminum is dissolved in a hydrocarbon solvent, and water is gradually added to the trialkylaluminum in this solution to hydrolyze it. A method in which copper sulfate hydrate or aluminum sulfate hydrate is suspended, and trialkylaluminum is brought into contact with the hydrate crystal water in the suspension to slowly hydrolyze the trialkylaluminum, or carbonization It can be produced by a method of bringing trialkylaluminum into contact with adsorbed water of undehydrated silica gel suspended in a hydrogen solvent, and slowly hydrolyzing the trialkylaluminum.

On the other hand, examples of the cation generator include neutral type and ion pair type, and examples of the neutral type include organic boron compounds represented by the following formula [24]. BR ¹⁰ ₃ ... [24] (In the formula [24], R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms.) That is, if it is a boron compound in which a hydrocarbon group is bonded to boron as a substituent. There is no particular limitation, and any one can be used. In these groups, a hydrogen atom may be replaced with a halogen atom. Examples of R ¹⁰ include methyl group, ethyl group, n-propyl group, amyl group,
and alkyl groups such as iso-amyl group, iso-butyl group and n-octyl group; or aryl groups such as phenyl group, fluorophenyl group, tolyl group and xylyl group. The three R ^{3 s} may be the same as or different from each other.

Specific examples of the organic boron compound represented by the formula [24] include triphenylboron, tri (pentafluorophenyl) boron and tri (2,3,4,5-).
Tetrafluorophenyl) boron, tri (2,4,6-)
Trifluorophenyl) boron, tri (2,3-difluorophenyl) boron, tri (2-fluorophenyl)
Boron, tri [(3,5-di (trifluoromethyl) phenyl] boron, tri [(4- (trifluoromethyl))
Phenyl] boron, trimethylboron, triethylboron, tri (trifluoromethyl) boron, diphenylfluoroboron, di (pentafluorophenyl) chloroboron and the like. Of these, tri (pentafluorophenyl) boron is particularly desirable.

The ion pair type cation generator is a cation generator represented by the following formula [25]. _{^{[On] + [BR 11 4}} ] - in ... [25] (Equation [25], [On] ⁺ is, 1B Group, 2B Group or Group 8 metal ions such as metal cations; or a carbonium, Shironiumu , Oxonium, sulfonium, ammonium, and phosphonium, and [B
R ¹¹ _4] ^- are poor anion non-coordinating or coordinating. R ¹¹ is the same as R ¹⁰ in formula [24]. )

Examples of preferred compounds represented by the general formula [25] include ferrocenium tetra (pentafluorophenyl) borate, silver (I) tetra (pentafluorophenyl) borate and copper (I) tetra (pentafluoro). Phenyl) borate, mercury (II) bis (tetra (pentafluorophenyl) borate, palladium (II)
Bis (tetra (pentafluorophenyl) borate, platinum (II) bis (tetra (pentafluorophenyl) borate, diphenylhydrocarbonium tetra (pentafluorophenyl) borate, triphenylcarbonium tetra (pentafluorophenyl) borate, triphenyl Silonium tetra (pentafluorophenyl) borate, tricyclohexylcarbonium tetra (pentafluorophenyl) borate, triethyloxonium tetra (pentafluorophenyl) borate, triethylsulfonium tetra (pentafluorophenyl)
Borate, diethylanilinium tetra (pentafluorophenyl) borate, trimethylammonium tetra (pentafluorophenyl) borate, triethylammonium tetra (pentafluorophenyl) borate,
Tetra (pentafluorophenyl) borate salts such as tetra-n-butylammonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate and the like can be mentioned.

In the practice of the present invention, for the purpose of stabilizing the catalyst, stabilizing the aluminum oxy compound or the cation generator as a co-catalyst, and reducing the amount used, a formula [as a further co-catalyst] 26] can be allowed to coexist. R ¹² ₃ Al _q ... [26] (In the formula [26], R ¹² represents a hydrogen atom, a halogen group or an alkyl group having 1 to 10 carbon atoms.) As an example of R ¹² , a hydrogen atom; Halogen atom such as chlorine and bromine; methyl group, ethyl group, n-propyl group, iso-
Propyl group, n-butyl group, iso-butyl group, sec
-Butyl group, pentyl group, hexyl group, octyl group, alkyl group such as decyl group; or a mixture thereof.

In carrying out the polymerization of olefins in the present invention, the olefin polymerization catalyst is at least selected from the group consisting of the main catalyst component which is the above specific transition metal compound, an aluminum oxy compound and a cation generator. It can be prepared by adding one type of co-catalyst component and further a co-catalyst component which is an alkylaluminum to an inert hydrocarbon solvent or an olefin medium to be polymerized and dissolving it. The order of addition at this time is arbitrarily selected, and the main catalyst component and the co-catalyst component may be premixed and used before the polymerization, or they may be independently added and used in the polymerization reaction system. The catalyst of the present invention is
Other than the above components, other components effective for olefin polymerization may be contained. Furthermore, when multimodal polymerization or the like is performed to improve polymer properties, a combination of two or more transition metal compounds, which are the main components of the catalyst of the present invention, and other main catalyst components known in the art are used. Can be used in combination with.

The transition metal compound used for the olefin polymerization is usually in the range of 10 ^-8 to 10 ^-1 mol / olefin monomer volume (liter), preferably 10 ^-7 to 10 ^-3 mol / olefin monomer volume (liter). Used in catalyst concentration. The olefin monomer capacity generally means the capacity of the raw material olefin monomer, but when a solvent is used in slurry polymerization or solution polymerization, it means the total capacity of the capacity of the olefin monomer and the capacity of the solvent, and the gas phase When a diluent gas that is an inert gas such as nitrogen or argon is used in addition to the gaseous olefin monomer in the polymerization, it means the total capacity of the capacity of the olefin monomer and the capacity of the diluent gas. However, the volume of the inert gas existing in the space other than the liquid phase portion in the polymerization vessel in slurry polymerization or solution polymerization is excluded.

On the other hand, when the aluminum oxy compound is used as the cocatalyst, the transition metal compound is
Aluminum atom / transition metal atom ratio is usually 10 to 10
⁵ , preferably in the range of 50 to ⁵ × 10 ³ .
When the cation generator is used as a cocatalyst, the cation generator / transition metal compound molar ratio is usually 0.5 to 10, preferably 1 with respect to the transition metal compound.
Used in the range of ~ 3. Further, when the alkylaluminum is used, the aluminum atom / transition metal atom ratio is usually 1 to 10 ⁵ , preferably 10 to 10 ³ with respect to the transition metal compound.

Among the transition metal compounds according to the present invention, when a transition metal compound having two or three molecules of bidentate chelate ligands is used as a catalyst, it is necessary to carry out a pretreatment before the polymerization. It may be desirable to improve. It is particularly effective when the polymerization temperature is about 90 ° C. or lower. As the method of pretreatment, a method of mixing the transition metal compound, the cocatalyst, and the olefin in an inert hydrocarbon solvent and heating and holding the resulting mixed solution can be adopted. Specific examples of the inert hydrocarbon solvent include butane, iso-butane, pentane, hexane, octane,
Aliphatic hydrocarbons such as decane, dodecane, hexadecane, octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene; naphtha, Examples include petroleum fractions such as kerosene and light oil.

The amount ratio of the transition metal compound to the cocatalyst may be within the range of the amount ratio relationship used in the polymerization reaction. As the olefin, the olefin itself used in the polymerization reaction or an olefin having another carbon number of 2 to 20 can be adopted, and the amount of the olefin is within the range of about 5 to 10 ³ in terms of olefin / transition metal compound molar ratio. Can be used in. The conditions for heating and holding the mixed solution are approximately 80 ° C.
A temperature of ~ 120 ° C and a time of about 5-60 minutes can be selected. In the present invention, the polymerization is slurry polymerization,
It can be carried out in any polymerization method such as solution polymerization and gas phase polymerization.

When carrying out slurry polymerization or gas phase polymerization, either or both of the main catalyst component and the cocatalyst component, which are the transition metal compounds, can be used by supporting them 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; organic carrier such as polystyrene, polyethylene, polypropylene and carbon. The method of loading on a carrier is not particularly limited, and a method known in the art can be used. The catalyst supported on the carrier may be preliminarily prepolymerized with the olefin during the polymerization of the olefin. The prepolymerization is preferably carried out such that the amount of the obtained olefin prepolymer is 0.1 to 500 g, preferably 1 to 100 g per 1 g of the supported catalyst. The method of carrying the main catalyst component and the co-catalyst component on the carrier and using them for polymerization is an effective method for improving the particle shape and bulk density of the polymer produced in the case of slurry polymerization or gas phase polymerization.

When carrying out solution polymerization or slurry polymerization, an inert hydrocarbon solvent or the olefin itself to be subjected to polymerization can be used as a solvent. Specific examples of the inert hydrocarbon solvent include butane, iso-butane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane, cyclohexane, cyclooctane. Alicyclic hydrocarbons such as benzene, toluene,
Aromatic hydrocarbons such as xylene; petroleum fractions such as naphtha, kerosene, and light oil; and the like.

In the present invention, when carrying out slurry polymerization, 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 0 to 300 ° C, preferably 100 to 250 ° C. When carrying out gas phase polymerization, the polymerization temperature is usually 0 to 1.
The temperature is preferably 20 ° C, preferably 20 to 100 ° C.

The polymerization pressure is not particularly limited, but is usually atmospheric pressure to 300 kg / cm ² , preferably atmospheric pressure to 100 kg / cm ² .
The condition of cm ² can be adopted. The polymerization can be carried out in any of batch system, anti-continuous system and continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization reaction system or by changing the polymerization temperature.

The olefins which can be polymerized by the olefin polymerization method of the present invention include ethylene; propylene, 1-butene, 1-pentene, 1-hexene,
C3-C20 α-olefins such as 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclopentene, cycloheptene, norbornene, 5 -Methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,
Cyclic olefins having 3 to 20 carbon atoms such as 2,3,4,4a, 5,8,8a-octahydronaphthalene can be mentioned. In addition, a compound partially having an olefin bond, for example, styrene, vinylcyclohexene, 1,5
-Hexadiene and the like can also be used. Also, ethylene / propylene, ethylene / 1-butene, ethylene / 1
-Hexene, ethylene / 1-octene, ethylene / cyclopentene, ethylene / styrene, ethylene / propylene / ethylidene norbornene, etc. are copolymerized by combining two or more olefins and copolymerized with a uniform composition distribution and a low-density copolymer. Coalescence can be produced.

[0053]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described below based on Examples, but the present invention is not limited to these Examples. In synthesizing the transition metal compound of the present invention, the raw material dithiophosphate is a commercially available product or literature (Inorga
nic Chemistry, 29, 4974 (1990)) or a method similar thereto. As the metallocene compound and the transition metal compound as the raw materials, commercially available products or those synthesized by a method known in the art were used.

All the synthesis and isolation of the catalyst were performed in the Schlenk method or a glove box under a nitrogen atmosphere. The raw material compound and the produced transition metal compound were identified by elemental analysis and ¹ H-NMR. The molecular weight and the molecular weight distribution of the homopolymer or copolymer obtained by the polymerization reaction were measured by the differential refractive index method using 150CV gel permeation chromatography (GPC) manufactured by Waters. The comonomer distribution of the copolymer obtained by the copolymerization reaction is M
It was measured by a 550 Fourier transform infrared spectrophotometer (FT-IR). In addition, Mw means a weight average molecular weight and Mn means a number average molecular weight.

Catalyst Synthesis (Example 1) (Pentamethylcyclopentadienyl) tris (O,
O'-diethyldithiophosphato) zirconium {Cp
^* Synthesis of Zr (S ₂ P (OEt) ₂ ) ₃ } (Catalyst 1) In a glass reactor having an inner volume of 100 ml which was sufficiently replaced with nitrogen, 2.0 g of (pentamethylcyclopentadienyl) zirconium trichloride was added. 50 ml of methylene chloride was added to a mixture of 3.7 g of O, O'-diethyldithiophosphate ammonium salt, and the mixture was stirred at room temperature for 12 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oily matter was washed with hexane and dried under reduced pressure to obtain 3.2 g of a yellow oily matter (yield 68%). ¹ H-NM of product
R (δ: ppm, solvent: deuterated chloroform) and elemental analysis results (% by weight) are shown below. δ1.3 (m, 18H), 2.0 (s, 15H), 4.
1 (m, 12H) C: 33.4, H: 5.7, P: 12.3, S: 24.
8, Zr: 11.5

Example 2 (n-Butylcyclopentadienyl) tris (O, O ')
- dicyclohexyl dithio phosphato) zirconium ^{{(n BuCp) Zr (S} 2 P (OC 6 H 11) 2) 3}
Synthesis of (Catalyst 2) 2.0 g of bis (n-butylcyclopentadienyl) zirconium dichloride and O, O'-disycyclohexyldithiophosphate ammonium were prepared in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen. 50 ml of methylene chloride was added to 6 g of the mixture, and the mixture was stirred at room temperature for 18 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oil was washed with hexane and dried under reduced pressure to obtain 3.8 g of a yellow oil (yield 70%). The results of elemental analysis (% by weight) are shown below. C: 49.5, H: 7.4, P: 8.3, S: 17.
6, Zr: 8.4

Example 3 (Pentamethylcyclopentadienyl) (O, O'-diethyldithiophosphato) dichlorozirconium {Cp
^* Synthesis of Zr (S ₂ P (OEt) ₂ ) Cl ₂ } (Catalyst 3) 2.0 g of (pentamethylcyclopentadienyl) zirconium trichloride was prepared in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen. 50 ml of methylene chloride was added to a mixture of 1.2 g of and ammonium O, O′-diethyldithiophosphate, and the mixture was stirred at room temperature for 12 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oil was washed with hexane and dried under reduced pressure to obtain 2.1 g of a yellow oil (yield 72%). The results of elemental analysis (% by weight) are shown below. C: 34.9, H: 5.4, P: 6.6, S: 13.
1, Zr: 18.7

Example 4 (1,2,4-Trimethylcyclopentadienyl) tris (O, O'-diphenyldithiophosphato) zirconium {(1,2,4-Me ₃ Cp) Zr (S ₂ P (OP
h) ₂ ) ₃ } (Catalyst 4) Synthesis In a glass reactor having an internal volume of 100 ml which was sufficiently replaced with nitrogen, 2.0 g of bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride and O, O'-
50 ml of methylene chloride was added to a mixture of 4.8 g of ammonium diphenyldithiophosphate, and the mixture was stirred at room temperature for 18 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oil was washed with hexane and dried under reduced pressure to give 3.6 g of a yellow oil (yield 65%). The results of elemental analysis (% by weight) are shown below. C: 50.9, H: 4.2, P: 8.6, S: 17.
9, Zr: 8.6

Example 5 (Cyclopentadienyl) tris (O, O'-diethyldithiophosphato) hafnium {CpHf (S ₂ P (O
Synthesis of Et) ₂ ) ₃ } (Catalyst 5) 2.0 g of bis (cyclopentadienyl) hafnium dichloride and ammonium O, O′-diethyldithiophosphate were prepared in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen. 50 ml of methylene chloride was added to 3.2 g of the mixture, and the mixture was stirred at room temperature for 18 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. This oil was washed with hexane and dried under reduced pressure to give 1.8 g of a yellow oil.
Obtained (yield 42%). The results of elemental analysis (% by weight) are shown below. C: 50.9, H: 4.2, P: 8.6, S: 17.
9, Zr: 8.6

Example 6 (Pentamethylcyclopentadienyl) tris (O,
O'-diethyldiselenophosphato) zirconium {C
Synthesis of p ^* Zr (Se ₂ P (OEt) ₂ ) ₃ } (Catalyst 6) 2.0 g of (pentamethylcyclopentadienyl) zirconium trichloride was prepared in a glass reactor having an inner volume of 100 ml which was sufficiently replaced with nitrogen. 50 ml of methylene chloride was added to a mixture of 5.4 g of O, O′-ammonium diethyldiselenophosphate and stirred at room temperature for 12 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oil was washed with hexane and dried under reduced pressure to obtain 3.4 g of a yellow oil (yield 53%). The results of elemental analysis (% by weight) are shown below. C: 24.9, H: 4.4, P: 8.5, Zr: 8.4

Example 7 [(Tetramethylcyclopentadienyl) dimethylsilylene (0-ethyldithiophosphato)] dichloride zirconium {[Cp ^* SiMe ₂ PS ₂ (OEt)] Z
Synthesis of rCl ₂ } (Catalyst 7) 4.3 g of (tetramethylcyclopentadienyl) dimethylsilyl chloride was added to 50 m of tetrahydrofuran in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen.
l was dissolved, 1.7 g of lithium ethoxyphosphine was added, and the mixture was stirred at room temperature for 3 hours. The obtained reaction liquid was filtered, and then the filtrate was distilled off to obtain 2.3 g of an oily substance. To this, 30 ml of tetrahydrofuran and 0.9 g of sulfur were added, and the mixture was stirred at room temperature for 12 hours. After filtering the reaction solution, the filtrate was evaporated to obtain 2.2 g of an oily substance. To this oily product were added 50 ml of tetrahydrofuran and 13.8 ml of a hexane solution of n-butyllithium (1 mol / l), and the mixture was stirred at room temperature for 6 hours. Thereafter, 1.6 g of zirconium tetrachloride was added to this reaction solution, and the mixture was stirred at room temperature for 12 hours. After filtering the obtained reaction solution, the filtrate was evaporated. More toluene 3
0 ml was added and filtered, the filtrate was distilled off, and the solid was obtained.
After recrystallizing with methylene chloride, it was dried under reduced pressure to obtain 1.4 g of a yellow solid (yield 15%). Elemental analysis results (wt%)
Is shown below. C: 32.8, H: 4.6, P: 6.4, S: 14.
0, Zr: 18.4

Example 8 (Trimethylsilyltetramethylcyclopentadienyl) tris (O, O'-di-n-butyldithiophosphato) zirconium {(Me ₃ SiCp ^* ) Zr (S ₂ P
Synthesis of (O ⁿ Bu) ₂ ) ₃ } (Catalyst 8) In a glass reactor having an internal volume of 100 ml, which was sufficiently replaced with nitrogen, 2.0 g of (trimethylcysyltetramethylcyclopentadienyl) zirconium trichloride and O,
O'-Di-n-butyldithiophosphate ammonium 4.0 g
50 ml of methylene chloride was added to the mixture of 1 and mixed at room temperature for 1
Stir for 2 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. This oil was washed with hexane and dried under reduced pressure to obtain 3.3 g of a yellow oil (yield 63.
%). The results of elemental analysis (% by weight) are shown below. C: 42.6, H: 6.4, P: 8.8, S: 18.
5, Zr: 8.9

Example 9 (Pentamethylcyclopentadienyl) tris (ethylphenyldithiophosphato) zirconium {Cp ^* Zr
Synthesis of (S ₂ PEtPh) ₃ } (Catalyst 9) 2.0 g of (pentamethylcyclopentadienyl) zirconium trichloride and ammonium ethylphenyldithiophosphate 4 were placed in a glass reactor having an internal volume of 100 ml which had been sufficiently replaced with nitrogen. 50 g of methylene chloride in 0.0 g of the mixture
ml was added, and the mixture was stirred at room temperature for 12 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oil was washed with hexane and dried under reduced pressure to obtain 3.4 g of a yellow oil (yield 68%). Elemental analysis results (wt%)
Is shown below. C: 49.5, H: 5.0, P: 11.3, S: 23.
6, Zr: 10.6

Example 10 (Pentamethylcyclopentadienyl) (O, O'-diphenyldithiocarbonato) dimethoxytitanium {C
Synthesis of p ^* Ti (S ₂ P (OPh) ₂ ) (OMe) ₂ } (Catalyst 10) (pentamethylcyclopentadienyl) titanium trichloride was prepared in a 100-ml glass reactor fully substituted with nitrogen. 2.0 g of diethyl ether 30 ml
21.0 ml of a diethyl ether solution of methoxylithium (1 mol / l) was added. After stirring at room temperature for 6 hours, the solvent was distilled off to obtain a solid. Toluene was added to this solid and filtered, and the solvent was distilled off from the filtrate to obtain a solid. 50 ml of methylene chloride was added to a mixture of this solid and 2.1 g of ammonium O, O′-diphenyldithiophosphate, and the mixture was stirred at room temperature for 12 hours. After filtering the obtained reaction liquid, the filtrate was distilled off to obtain a solid. This solid was recrystallized from methylene chloride and dried under reduced pressure to obtain 1.2 g of a yellow solid.
Obtained (yield 32%). The results of elemental analysis (% by weight) are shown below. C: 54.6, H: 6.1, P: 5.5, S: 12.
4, Ti: 8.7

Example 11 (Cyclopentadienyl) tris (O, O′-dimethylditelluphosphato) zirconium {CpZr (Te ₂
Synthesis of P (OMe) ₂ ) ₃ } (Catalyst 11) 2.0 g of bis (cyclopentadienyl) zirconium dichloride and O, O'-dimethyldichloride were placed in a glass reactor having an internal volume of 100 ml that had been sufficiently replaced with nitrogen. 50 ml of methylene chloride to a mixture of 7.5 g of ammonium tellurium phosphate
Was added and stirred at room temperature for 18 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. This oil was washed with hexane and dried under reduced pressure to give a yellow oil (3.
5 g was obtained (yield 43%). The results of elemental analysis (% by weight) are shown below. C: 10.3, H: 2.2, P: 7.9, Zr: 7.5

Example 12 [(Tetramethylcyclopentadienyl) dimethylsilylene (phenyldithiophosphato)] dichloride zirconium {[Cp ^* SiMe ₂ PPhS ₂ ] ZrC
1 ₂ } (Catalyst 12) Synthesis of (tetramethylcyclopentadienyl) dimethylsilyl chloride 4.3 g in tetrahydrofuran 50 m
2.3 g of phenylphosphine lithium was added, and the mixture was stirred at room temperature for 3 hours. The obtained reaction liquid was filtered and then the filtrate was distilled off to obtain 4.0 g of an oily substance. To this, 30 ml of tetrahydrofuran and 0.9 g of sulfur were added, and the mixture was stirred at room temperature for 12 hours. After the reaction solution was filtered, the filtrate was distilled off to obtain 2.3 g of an oily substance. To this oily substance, 30 ml of tetrahydrofuran, a hexane solution of n-butyllithium (1 m
ol / l) 12.9 ml was added, and the mixture was stirred at room temperature for 6 hours. Thereafter, 1.5 parts of zirconium tetrachloride was added to this reaction solution.
g was added, and the mixture was stirred at room temperature for 12 hours. After filtering the obtained reaction solution, the filtrate was evaporated. 30 ml of toluene
Was added and filtered, and the filtrate was evaporated to obtain a solid. Recrystallize with methylene chloride and dry under reduced pressure to give a yellow solid of 1.5.
g was obtained (15% yield). The results of elemental analysis (% by weight) are shown below. C: 40.4, H: 4.7, P: 6.6, S: 13.
0, Zr: 18.1

Example 13 [(Cyclopentadienyl) methylene (O-methyldithiophosphato)] dichloride zirconium {[CpC
Synthesis of H ₂ PS ₂ (OMe)] ZrCl ₂ } (Catalyst 13) 1.3 g of methoxyphosphine was dissolved in 30 ml of tetrahydrofuran in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen to dissolve butyl lithium. 20.0 ml of a hexane solution (1 mol / l) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1.6 g of fulvene was added, and the mixture was stirred at room temperature for 12 hours. To the resulting reaction solution was added 40 ml of water, extracted with ether and the solvent was distilled off to give 1.8 g of an oily substance.
Obtained. To this oily substance, 30 ml of tetrahydrofuran and 0.8 g of sulfur were added, and the mixture was stirred at room temperature for 12 hours. After filtering the reaction solution, the filtrate was distilled off to obtain 1.3 g of an oily substance. To this oily substance, 50 ml of tetrahydrofuran and 10.7 ml of a hexane solution of n-butyllithium (1 mol / l) were added, and the mixture was stirred at room temperature for 6 hours. Thereafter, 1.2 g of zirconium tetrachloride was added to this reaction solution, and the mixture was stirred at room temperature for 12 hours. After filtering the obtained reaction solution, the filtrate was evaporated.
Further, 30 ml of toluene was added and filtered, and the filtrate was distilled off to obtain a solid. After recrystallizing with methylene chloride, it was dried under reduced pressure to obtain 1.1 g of a yellow solid (yield 14%). The results of elemental analysis (% by weight) are shown below. C: 21.8, H: 2.6, P: 7.5, S: 16.
6, Zr: 22.6

Example 14 (1,3-Dimethylcyclopentadienyl) tris (O, O'-diiso-propyldithiophosphato) zirconium {(1,3-Me ₂ Cp) Zr (S ₂ P (O
ⁱ Pr) _{2) 3}} (a synthetic fully purged with nitrogen content volume glass reactor of 100ml of catalyst 14), bis (1,3-dimethyl cyclopentadienyl)
Zirconium dichloride 2.0 g and O, O'-diis
50 ml of methylene chloride was added to a mixture of 4.0 g of ammonium o-propyldithiophosphate, and the mixture was stirred at room temperature for 18 hours. The obtained reaction liquid was filtered and the filtrate was evaporated to give an oily substance. The oil was washed with hexane and dried under reduced pressure to obtain 2.6 g of a yellow oil (yield 56%). The results of elemental analysis (% by weight) are shown below. C: 36.3, H: 6.2, P: 11.6, S: 22.
8, Zr: 11.0

Polymerization reaction (Example 15) 1.6 l of which the inside was deaerated in vacuum and replaced with nitrogen
5m containing 0.5μmol of catalyst 1 in the autoclave
1 toluene solution and a toluene solution of methylaluminoxane MMAO manufactured by Tosoh Akzo Co., Ltd.
1 mol / l) 5 ml (aluminum amount 0.5 mmo
1) was added together with 0.6 l of dehydrated and deoxygenated toluene. The internal temperature of the autoclave was maintained at 80 ° C., and ethylene gas was added at 10 kg / cm ² G. Polymerization was carried out for 1 hour while supplementing ethylene and maintaining the total pressure. 61.0 g of polymer was obtained. The obtained polymer has a molecular weight Mw of 52300.
0, the molecular weight distribution Mw / Mn was 2.66.

(Example 16) Example 1 using catalyst 2
Polymerization was carried out in the same manner as in 5 to obtain 49.1 g of a polymer. The obtained polymer has a molecular weight Mw of 559.
000, and the molecular weight distribution Mw / Mn was 2.94. (Example 17) Polymerization was carried out in the same manner as in Example 15 using Catalyst 3, to obtain 57.2 g of a polymer.
The obtained polymer had a molecular weight Mw of 476000 and a molecular weight distribution Mw / Mn of 3.02.

Example 18 1 μmol of catalyst 4 was placed in a glass reactor having an internal volume of 100 ml which had been sufficiently replaced with nitrogen.
Toluene solution containing 10 ml, and toluene solution of methylaluminoxane MMAO manufactured by Tosoh Akzo Co., Ltd. (0.1 mol / l in terms of aluminum) 10 ml (aluminum amount 1
mmol) and 1 ml of octene, and then 10
The mixture was heated and stirred at 0 ° C. for 30 minutes to obtain a toluene preparation liquid.
Into a 1.6 l autoclave whose interior was degassed in vacuum and purged with nitrogen, 10.5 ml of the toluene preparation liquid was placed together with 0.6 l of dehydrated and deoxygenated toluene. The internal temperature of the autoclave was maintained at 80 ° C., and ethylene gas was added at 10 kg / cm ² G. Polymerization was carried out for 1 hour while supplementing ethylene and maintaining the total pressure. 53.4 g of polymer was obtained. The obtained polymer has a molecular weight Mw of 521,000 and a molecular weight distribution Mw / M.
n was 2.35.

(Example 19) Example 1 using the catalyst 5
Polymerization was carried out in the same manner as in 8 to obtain 31.6 g of a polymer. The obtained polymer has a molecular weight Mw of 652.
000, and the molecular weight distribution Mw / Mn was 4.22. (Example 20) Polymerization was performed in the same manner as in Example 18 using Catalyst 6, to obtain 38.7 g of a polymer.
The obtained polymer had a molecular weight Mw of 498,000 and a molecular weight distribution Mw / Mn of 3.65.

(Example 21) 1 μmol of catalyst 7 was placed in a glass reactor having an internal volume of 100 ml which had been sufficiently replaced with nitrogen.
10 ml of a toluene solution containing 1 mmol of triisobutylaluminum, 10 ml of a toluene solution containing 1 mmol of triisobutylaluminum, and 10 ml of a toluene solution containing 2 μmol of tris (pentafluorophenyl) borate were mixed, and then at 10 ° C. at 10 ° C.
After stirring for a minute, a toluene preparation liquid was obtained. Into a 1.6 l autoclave whose interior was degassed in vacuum and purged with nitrogen, 15 ml of a toluene preparation liquid was placed together with 0.6 l of dehydrated and deoxygenated toluene. The internal temperature of the autoclave was 80 ° C., ethylene gas was added at 10 kg / cm ² G, ethylene was supplied, and polymerization was carried out for 1 hour while maintaining the total pressure. 58.5 g of polymer was obtained. The obtained polymer has a molecular weight Mw of 3850.
00, the molecular weight distribution Mw / Mn was 4.50.

Example 22 0.5 μm of catalyst 8 was placed in a 1.6 l autoclave whose inside was degassed in vacuum and purged with nitrogen.
of toluene solution containing 5 ml of toluene solution of methylaluminoxane MMAO (0.1 mol / l in terms of aluminum) manufactured by Tosoh Akzo Co., Ltd.
I put it in with. Further, 100 ml of 1-hexene was added, the internal temperature of the autoclave was maintained at 120 ° C., and ethylene gas was added at 20 kg / cm ² G. Polymerization was carried out for 1 hour while supplementing ethylene and maintaining the total pressure. 63.4 g of polymer was obtained. The obtained polymer has a molecular weight Mw of 2320.
00, the molecular weight distribution Mw / Mn was 2.12. Moreover, the density is 0.923 g / cm ³ , and GPC-FTIR
From the measurement, it was confirmed that 1-hexene was distributed almost uniformly from the low molecular weight region to the high molecular weight region.

(Example 23) Example 2 using the catalyst 9
Polymerization was carried out in the same manner as in 2 to obtain 55.8 g of a polymer. The obtained polymer has a molecular weight Mw of 284.
000, the molecular weight distribution Mw / Mn is 2.68, and the density is 0.
It was 921 g / cm ³ . (Example 24) Polymerization was performed in the same manner as in Example 22 by using the catalyst 10, to obtain 39.9 g of a polymer. The obtained polymer has a molecular weight Mw of 256000,
Molecular weight distribution Mw / Mn is 3.65, density is 0.920 g.
/ Cm ³ .

Example 25 Polymerization was carried out in the same manner as in Example 22 by using the catalyst 11 to obtain 48.7 g of a polymer. The obtained polymer has a molecular weight Mw of 31.
The molecular weight distribution was 9000, the Mw / Mn was 3.28, and the density was 0.916 g / cm ³ . (Example 26) Polymerization was performed in the same manner as in Example 22 by using the catalyst 12, and 76.2 g of a polymer was obtained. The obtained polymer has a molecular weight Mw of 275,000,
Molecular weight distribution Mw / Mn is 3.35 and density is 0.908 g.
/ Cm ³ . (Example 27) Polymerization was carried out in the same manner as in Example 22 by using the catalyst 13, and 64.1 g of a polymer was obtained. The obtained polymer has a molecular weight Mw of 260000,
Molecular weight distribution Mw / Mn is 3.85, density is 0.905 g.
/ Cm ³ .

(Example 28) In a glass reactor having an internal volume of 100 ml which had been sufficiently replaced with nitrogen, 1 μmo of the catalyst 14 was added.
1 ml of 10 ml toluene solution, 10 ml of toluene solution containing 1 mmol of triisobutylaluminum, and 10 ml toluene solution containing 2 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate were mixed, and then heated and stirred at 30 ° C. for 10 minutes. A toluene preparation liquid was obtained. The inside was vacuum degassed and replaced with nitrogen.
To a 6-liter autoclave, add 15 ml of the toluene preparation liquid,
It was added together with 0.5 liter of dehydrated and deoxygenated toluene. Further, 100 ml of 1-hexene was added, the internal temperature of the autoclave was 80 ° C., 10 kg / cm ² G of ethylene gas was added, and ethylene was supplied to carry out polymerization for 1 hour while maintaining the total pressure.
46.8 g of polymer was obtained. The obtained polymer has a molecular weight Mw of 274,000 and a molecular weight distribution Mw / Mn.
Was 2.84 and the density was 0.918 g / cm ³ .

[0078] (Comparative Example 1) was synthesized according to JP-A 5-170820 discloses "CpZr (CH ₃ COCH ₂ CO
CH ₃ ) ₂ Cl ”was used to carry out the polymerization reaction in the same manner as in Example 16. The amount of polymer obtained was 5.5 g,
The molecular weight Mw was 344000, the molecular weight distribution Mw / Mn was 2.35, and the density was 0.925 g / cm ³ . Comparative Example 2 Literature Journal of Chemical Society,
Chemical Communications (J.Chem. Soc., Chem. C
ommun., 18, 1415-1417 (1993)).
_{^{p * r ((NSiMe 3)}} 2 CPh) (CH 2 Ph) 2
Was used to carry out a polymerization reaction in the same manner as in Example 16. The amount of polymer obtained was 3.4 g, and the molecular weight Mw was 67.
000, the molecular weight distribution Mw / Mn is 4.35, and the density is 0.
It was 931 g / cm ³ . From a comparison between each Example and Comparative Examples 1 and 2, it is understood that an olefin polymer can be efficiently obtained by polymerizing an olefin using the olefin polymerization catalyst of the present invention.

[0079]

The olefin polymerization catalyst comprising the novel transition metal compound of the present invention exhibits excellent catalytic activity as compared with the conventional olefin polymerization catalyst comprising a transition metal compound having a chelate ligand. By polymerizing an olefin using the catalyst for olefin polymerization 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 exhibits excellent physical properties in terms of impact strength, stress cracking resistance, transparency, low temperature heat sealability, blocking resistance, low stickiness, low extract and the like.

[Brief description of the drawings]

FIG. 1 is a flow chart showing a preparation process in olefin polymerization of a catalyst according to the present invention.

Claims (3)

[Claims] 1. An olefin polymerization catalyst comprising a transition metal compound represented by the following general formula [1] or [2]. _{CpM (L-R) m Y} 3-m ··· [1] (Cq-A-L) M (L-R) n Y 2-n ··· [2] ( Formula [1] and [2] In the above, Cp is a group having a cyclopentadienyl skeleton, Cq is a group having a cyclopentadienyl skeleton forming a covalent bond with A. M is T
i, Zr or Hf. L is a bidentate chelate functional group and is represented by the following formula [3]. Embedded image In formula [3], X ¹ and X ² are each a coordination atom, and X is
¹ is O, S, Se or Te and X ² is S, Se or Te. R ² is represented by X ³ R ³ or R ³ ,
X ³ is O, S, Se or Te, and R ³ has 1 carbon atom.
To 20 unsubstituted or substituted hydrocarbon groups. R is X ⁴
Represented by R ⁴ or R ⁴ , X ⁴ is O, S, Se or T
e and R ⁴ is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms. A is a bridging group by a covalent bond,
CR ⁵ ₂₋ , −CR ⁵ ₂ CR ⁵ ₂₋ , −CR ⁵ = CR ^{5
_{-, - SiR 5 2 -,}} - SiR 5 2 SiR 5 2 -, - G
^{_{eR 5 2 -, - BR 5}} -, - AlR 5 -, - PR 5 -,
_{^{-P (O) R 5 2 -}} , - NR 5 -, - SO 2 -, - SO
Is a group or atom selected from-, -O-, -S-, -Ge-, -Sn-, and -CO-, wherein R ⁵ is a hydrogen atom, a halogen atom, or a C 1-20 unsubstituted or It is a substituted hydrocarbon group. Y is a halogen atom and has 1 carbon atom
To 20 hydrocarbon groups, an alkoxy group having 1 to 20 carbon atoms,
C1-C20 thioalkoxy group, C6-C20 aryloxy group, C6-C20 thioaryloxy group, C1-C20 hydrocarbon group-substituted amino group or C1-C20 It is a phosphino group substituted with a hydrocarbon group.
m is 1, 2 or 3. n is 0, 1 or 2. ) 2. The catalyst for olefin polymerization according to claim 1, further comprising at least one promoter selected from the group consisting of an aluminum oxy compound and a cation generator. 3. A method for producing an olefin homopolymer or copolymer using the catalyst according to claim 1.